Sample records for condensed phase reactions

  1. Ultrafast Dynamics of Chemical Reactions in Condensed Phase ...

    Indian Academy of Sciences (India)

    Ultrafast Dynamics of Chemical Reactions in Condensed Phase: Intramolecular Energy Transfer, Charge Transfer & Hydrogen Bond. Dipak K. Palit Radaition & Photochemistry Division Bhabha Atomic Research Centre Mumbai 400 085, India.

  2. Initial Reaction Steps in the Condensed-Phase Decomposition of Propellants

    Energy Technology Data Exchange (ETDEWEB)

    Melius, C F; Piqueras, M C


    Understanding the reaction mechanisms for the decomposition of energetic materials in the condensed phase is critical to our development of detailed kinetic models of propellant combustion. To date, the reaction mechanisms in the condensed phase have been represented by global, reactions. The detailed elementary reactions subsequent to the initial NO{sub 2} bond scissioning are not known. Using quantum chemical calculations, we have investigated the possible early steps in the decomposition of energetic materials that can occur in the condensed phase. We have used methylnitrate, methylnitramine, and nitroethane as prototypes for O-NO{sub 2}, N-NO{sub 2} and C-NO{sub 2} nitro compounds. We find the energetic radicals formed from the initial NO{sub 2} bond scissioning can be converted to unsaturated non-radical intermediates as an alternative to the unzipping of the energetic radical. We propose a new, prompt oxidation mechanism in which the trapped HONO can add back onto the energetic molecule. This produces oxidation products in the condensed phase that normally would not be produced until much later in the flame. We have shown that this prompt oxidation mechanism is a general feature of both nitramines and nitrate esters. The resulting HONO formed by the H-atom abstraction will be strongly influenced by the cage effect of the condensed phase. The applicability of this mechanism is demonstrated for decomposition of ethylnitrate, illustrating the importance of the cage effect in enabling this mechanism to occur at low temperatures.

  3. Theory of reversible electron transfer reactions in a condensed phase. (United States)

    Dhole, Kajal; Modak, Brindaban; Samanta, Alok; Ghosh, Swapan K


    We have derived an exact analytical expression for the average forward rate of a reversible electron transfer reaction, modeled through a reaction coordinate undergoing diffusive motion in arbitrary potential wells of the reactant and the product in presence of a localized sink of arbitrary location and strength. The dynamics of diffusive motion is described by employing two coupled generalized diffusion reaction (Smoluchowski) equations with coordinate dependent diffusivity and delta sink. The average forward electron transfer rate constant obtained here for the system, with equilibrium or nonequilibrium distributions as initial condition, is determined by the forward and backward rate constants calculated based on the transition state theory and the weighted average rate for the well dynamics. We also discuss various limiting cases for the rate of electron transfer reactions corresponding to the different experimental situations. As an illustrative example, we have considered back electron transfer (ET) reaction and shown that the present theory can explain the non-Marcus free energy gap dependence of the rate of ET reactions. More importantly, the approach presented here can easily be extended to systems describing the dynamics of diffusive motion in coupled multipotential surfaces associated with electron transfer reactions.

  4. Electron transfer reactions in condensed phase: effect of reversibility. (United States)

    Dhole, Kajal; Jena, Naresh K; Samanta, Alok; Ghosh, Swapan K


    We propose a generalized one-dimensional kinetic equation for multidimensional reversible electron transfer (ET) reaction with a nonequilibrium situation as the initial condition. The rate constant for the forward reversible ET reaction obtained here consists of the rate for the corresponding irreversible ET reaction, and an extra term due to reversibility of the ET process which includes the rates of diffusion dynamics in the reactant and product wells. In order to understand the effect of reversibility, we consider back ET reaction in a system consisting of an electron donor-acceptor pair in a solvent modeled through low frequency solvent collective coordinates (multidimensional) characterized by the orientational polarization and slowly relaxing one-dimensional vibrational mode. We propose here a new generalized polarization energy functional corresponding to the extension of the continuum version for the same, which has opened up the possibility of inclusion of molecular nature of the solvent into the solvent reorganization energy. We then derive an exact expression for the ET rate for this model system. The numerical results calculated by using the proposed one-dimensional approach are shown to be in good agreement with the available experimental results. Non-Marcus free energy gap dependence of the rates observed here for the reversible and irreversible ET reactions are very close to each other in the barrierless region, while for other situations, the rate for the former process is found to be less than the latter. The extra term, which makes the difference between the rate constants for irreversible and reversible ET reactions, is found to be contributed by the diffusion dynamics from both reactant and product wells but the dominating contribution is provided mainly by the product well.

  5. Spectroscopy and kinetics of germylene and digermene reactions photogenerated in the condensed phase

    Energy Technology Data Exchange (ETDEWEB)

    Plyusnin, V F; Kaletina, M V; Leshina, T V [Institute of Chemical Kinetics and Combustion, Siberian Branch of the Russian Academy of Sciences, Novosibirsk (Russian Federation)


    The state of the art in the spectroscopic identification and kinetic analysis of condensed-phase reactions of bivalent germanium derivatives and their dimers is considered. Considerable attention is drawn to the comparison of results obtained by laser flash photolysis and spin chemistry methods.

  6. One-dimensional description of multidimensional electron transfer reactions in condensed phase. (United States)

    Dhole, Kajal; Samanta, Alok; Ghosh, Swapan K


    We derive a one-dimensional energy diffusion equation for describing the dynamics of multidimensional electron transfer reactions in condensed phase, which is conceptually simpler and computationally more economic than the conventional approaches. We also obtain an analytical expression for the rate of electron transfer reactions for a general one-dimensional effective potential as well as an energy dependent diffusitivity. As an illustrative example, we consider application to electron transfer in a contact ion pair system modeled through harmonic potentials consisting of two slow classical modes and a high frequency vibrational mode for which the numerical results calculated using the proposed one-dimensional approach are shown to be in good agreement with experimental results. The energy diffusion equation and the rate expression for electron transfer obtained from the present theory, therefore, open up the possibility of describing the dynamics of electron transfer in complex systems, through a simpler approach.

  7. Charge constrained density functional molecular dynamics for simulation of condensed phase electron transfer reactions. (United States)

    Oberhofer, Harald; Blumberger, Jochen


    We present a plane-wave basis set implementation of charge constrained density functional molecular dynamics (CDFT-MD) for simulation of electron transfer reactions in condensed phase systems. Following the earlier work of Wu and Van Voorhis [Phys. Rev. A 72, 024502 (2005)], the density functional is minimized under the constraint that the charge difference between donor and acceptor is equal to a given value. The classical ion dynamics is propagated on the Born-Oppenheimer surface of the charge constrained state. We investigate the dependence of the constrained energy and of the energy gap on the definition of the charge and present expressions for the constraint forces. The method is applied to the Ru2+-Ru3+ electron self-exchange reaction in aqueous solution. Sampling the vertical energy gap along CDFT-MD trajectories and correcting for finite size effects, a reorganization free energy of 1.6 eV is obtained. This is 0.1-0.2 eV lower than a previous estimate based on a continuum model for solvation. The smaller value for the reorganization free energy can be explained by the fact that the Ru-O distances of the divalent and trivalent Ru hexahydrates are predicted to be more similar in the electron transfer complex than for the separated aqua ions.

  8. Path-integral calculations of heavy atom kinetic isotope effects in condensed phase reactions using higher-order Trotter factorizations. (United States)

    Vardi-Kilshtain, Alexandra; Azuri, Asaf; Major, Dan Thomas


    A convenient approach to compute kinetic isotope effects (KIEs) in condensed phase chemical reactions is via path integrals (PIs). Usually, the primitive approximation is used in PI simulations, although such quantum simulations are computationally demanding. The efficiency of PI simulations may be greatly improved, if higher-order Trotter factorizations of the density matrix operator are used. In this study, we use a higher-order PI method, in conjunction with mass-perturbation, to compute heavy-atom KIE in the decarboxylation of orotic acid in explicit sulfolane solvent. The results are in good agreement with experiment and show that the mass-perturbation higher-order Trotter factorization provides a practical approach for computing condensed phase heavy-atom KIE. Copyright © 2011 Wiley Periodicals, Inc.

  9. Golden rule kinetics of transfer reactions in condensed phase: the microscopic model of electron transfer reactions in disordered solid matrices. (United States)

    Basilevsky, M V; Odinokov, A V; Titov, S V; Mitina, E A


    local modes immersed in the continuum harmonic medium is formulated for both classical and quantum regimes, and accounts explicitly for the mode∕medium interaction. The kinetics of the energy exchange between the local ET subsystem and the surrounding environment essentially determine the total ET rate. The efficient computer code for rate computations is elaborated on. The computations are available for a wide range of system parameters, such as the temperature, external field, local mode frequency, and characteristics of mode/medium interaction. The relation of the present approach to the Marcus ET theory and to the quantum-statistical reaction rate theory [V. G. Levich and R. R. Dogonadze, Dokl. Akad. Nauk SSSR, Ser. Fiz. Khim. 124, 213 (1959); J. Ulstrup, Charge Transfer in Condensed Media (Springer, Berlin, 1979); M. Bixon and J. Jortner, Adv. Chem. Phys. 106, 35 (1999)] underlying it is discussed and illustrated by the results of computations for practically important target systems.

  10. Textbook Forum: Equilibrium Constants of Chemical Reactions Involving Condensed Phases: Pressure Dependence and Choice of Standard State. (United States)

    Perlmutter-Hayman, Berta


    Problems of equilibria in condensed phases (particularly those involving solutes in dilute solutions) are encountered by students in their laboratory work; the thermodynamics of these equilibria is neglected in many textbooks. Therefore, several aspects of this topic are explored, focusing on pressure dependence and choice of standard state. (JN)

  11. Reaction Mechanisms of Energetic Materials in the Condensed Phase: Long-term Aging, Munition Safety and Condensed-Phase Processes in Propellants and Explosives (United States)


    HMX crystal polymorphs using a flexible molecule force field, Journal Of Computer Aided Materials Design 8, 2-3 (2002). 67. T. R. Botcher, and C. A...Park, NC 27709-2211 15. SUBJECT TERMS propellants, explosives, reaction mechanisms, kinetics, safety, aging, IM, complex reaction processes, HMX , RDX...summarizes work on the decomposition of BDNPA/F and several HMX -based explosive formulations: PBX9501, LX-04, LX-10, LX-14 and EDC-37. The results on the

  12. Scrutinizing the pion condensed phase

    Energy Technology Data Exchange (ETDEWEB)

    Carignano, Stefano; Mammarella, Andrea; Mannarelli, Massimo [INFN, Laboratori Nazionali del Gran Sasso, Assergi (Italy); Lepori, Luca [Universita di Padova, Dipartimento di Fisica e Astronomia, Padova (Italy); Universita dell' Aquila, Dipartimento di Scienze Fisiche e Chimiche, Coppito-L' Aquila (Italy); Pagliaroli, Giulia [INFN, Laboratori Nazionali del Gran Sasso, Assergi (Italy); Gran Sasso Science Institute, L' Aquila (Italy)


    When the isospin chemical potential exceeds the pion mass, charged pions condense in the zero-momentum state forming a superfluid. Chiral perturbation theory provides a very powerful tool for studying this phase. However, the formalism that is usually employed in this context does not clarify various aspects of the condensation mechanism and makes the identification of the soft modes problematic. We re-examine the pion condensed phase using different approaches within the chiral perturbation theory framework. As a first step, we perform a low-density expansion of the chiral Lagrangian valid close to the onset of the Bose-Einstein condensation. We obtain an effective theory that can be mapped to a Gross-Pitaevskii Lagrangian in which, remarkably, all the coefficients depend on the isospin chemical potential. The low-density expansion becomes unreliable deep in the pion condensed phase. For this reason, we develop an alternative field expansion deriving a low-energy Lagrangian analog to that of quantum magnets. By integrating out the ''radial'' fluctuations we obtain a soft Lagrangian in terms of the Nambu-Goldstone bosons arising from the breaking of the pion number symmetry. Finally, we test the robustness of the second-order transition between the normal and the pion condensed phase when next-to-leading-order chiral corrections are included. We determine the range of parameters for turning the second-order phase transition into a first-order one, finding that the currently accepted values of these corrections are unlikely to change the order of the phase transition. (orig.)

  13. Heterogeneous catalysis in complex, condensed reaction media

    Energy Technology Data Exchange (ETDEWEB)

    Cantu, David C.; Wang, Yang-Gang; Yoon, Yeohoon; Glezakou, Vassiliki-Alexandra; Rousseau, Roger; Weber, Robert S.


    Many reactions required for the upgrading of biomass into fuels and chemicals—hydrogenation, hydrodeoxygenation, hydrocracking—are ostensibly similar to those practiced in the upgrading of petroleum into fuels. But, repurposing hydroprocessing catalysts from refinery operations to treat bio-oil has proved to be unsatisfactory. New catalysts are needed because the composition of the biogenic reactants differs from that of petroleum-derived feedstocks (e.g. the low concentration of sulfur in cellulose-derived biomass precludes use of metal sulfide catalysts unless sulfur is added to the reaction stream). New processes are needed because bio-oils oligomerize rapidly, forming intractable coke and “gunk”, at temperatures so low that the desired upgrading reactions are impractically slow, and so low that the bio-oil upgrading must be handled as a condensed fluid. Ideally, the new catalysts and processes would exploit the properties of the multiple phases present in condensed bio-oil, notably the polarizability and structure of the fluid near a catalyst’s surface in the cybotactic region. The results of preliminary modeling of the cybotactic region of different catalyst surfaces in the hydrogenation of phenol suggest that Pd catalysts supported on hydrophilic surfaces are more active than catalysts based on lipophilic supports because the former serve to enhance the concentration of the phenol in the vicinity of the Pd. The effect stems from thermodynamics, not the rate of mass transport. This work was supported by the US Department of Energy, Office of Energy Efficiency and Renewable Energy, Bioenergy Technologies Office. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle.

  14. Charge-dependent non-bonded interaction methods for use in quantum mechanical modeling of condensed phase reactions (United States)

    Kuechler, Erich R.

    Molecular modeling and computer simulation techniques can provide detailed insight into biochemical phenomena. This dissertation describes the development, implementation and parameterization of two methods for the accurate modeling of chemical reactions in aqueous environments, with a concerted scientific effort towards the inclusion of charge-dependent non-bonded non-electrostatic interactions into currently used computational frameworks. The first of these models, QXD, modifies interactions in a hybrid quantum mechanical/molecular (QM/MM) mechanical framework to overcome the current limitations of 'atom typing' QM atoms; an inaccurate and non-intuitive practice for chemically active species as these static atom types are dictated by the local bonding and electrostatic environment of the atoms they represent, which will change over the course of the simulation. The efficacy QXD model is demonstrated using a specific reaction parameterization (SRP) of the Austin Model 1 (AM1) Hamiltonian by simultaneously capturing the reaction barrier for chloride ion attack on methylchloride in solution and the solvation free energies of a series of compounds including the reagents of the reaction. The second, VRSCOSMO, is an implicit solvation model for use with the DFTB3/3OB Hamiltonian for biochemical reactions; allowing for accurate modeling of ionic compound solvation properties while overcoming the discontinuous nature of conventional PCM models when chemical reaction coordinates. The VRSCOSMO model is shown to accurately model the solvation properties of over 200 chemical compounds while also providing smooth, continuous reaction surfaces for a series of biologically motivated phosphoryl transesterification reactions. Both of these methods incorporate charge-dependent behavior into the non-bonded interactions variationally, allowing the 'size' of atoms to change in meaningful ways with respect to changes in local charge state, as to provide an accurate, predictive and

  15. Atmospheric gas phase reactions (United States)

    Platt, Ulrich

    This chapter introduces the underlying physicochemical principles and the relevance of atmospheric gas phase reactions. In particular, reaction orders, the concept of elementary reactions, definition of and factors determining reaction rates (kinetic theory of chemical reactions), and photochemical reactions are discussed. Sample applications of the pertinent reaction pathways in tropospheric chemistry are presented, particularly reactions involving free radicals (OH, NO3, halogen oxides) and their roles in the self-cleaning of the troposphere. The cycles of nitrogen and sulfur species as well as the principles of tropospheric ozone formation are introduced. Finally, the processes governing the stratospheric ozone layer (Chapman Cycle and extensions) are discussed.

  16. Analytical solution for transient partitioning and reaction of a condensing vapor species in a droplet (United States)

    Liu, Albert Tianxiang; Zaveri, Rahul A.; Seinfeld, John H.


    We present the exact analytical solution of the transient equation of gas-phase diffusion of a condensing vapor to, and diffusion and reaction in, an aqueous droplet. Droplet-phase reaction is represented by first-order chemistry. The solution facilitates study of the dynamic nature of the vapor uptake process as a function of droplet size, Henry's law coefficient, and first-order reaction rate constant for conversion in the droplet phase.

  17. Solution-phase reaction dynamics: Gaining control (United States)

    Case, Amanda S.


    Using infrared light to control the outcome of a chemical reaction is problematic in solution because of numerous interactions and non-specific sample heating. Now, condensed-phase results showing the vibrational enhancement of an otherwise thermally driven reaction may reinvigorate discussion of the practical applications of vibrational control.

  18. Intermolecular interactions in the condensed phase

    DEFF Research Database (Denmark)

    Christensen, Anders S.; Kromann, Jimmy Charnley; Jensen, Jan Halborg


    the performance of a set of semi-empirical quantum mechanical (SQM) methods that include DFTB3-D3, DFTB3/CPE-D3, OM2-D3, PM6-D3, PM6-D3H+, and PM7 as well as the HF-3c method. We find that while all tested SQM methods tend to underestimate binding energies in the gas phase with a root-mean-squared error (RMSE...... in solution is computed via a thermodynamic cycle that integrates dimer binding energy in the gas phase at the coupled cluster level and solute-solvent interaction with density functional theory; the estimated uncertainty of such calculated interaction energy is ±1.5 kcal/mol. The dataset is used to benchmark...... and solution phases. As most approximate QM methods are parametrized and evaluated using data measured or calculated in the gas phase, the dataset represents an important first step toward calibrating QM based methods for application in the condensed phase where polarization and exchange repulsion need...

  19. Intramolecular charge transfer reaction in 3-amino-4-methyl benzoic acid: a study from condensed phase to jet-cooled molecular beam (United States)

    Ghosh, S.; Paul, B. K.; Chakraborty, A.; Nath, D. N.; Guchhait, N.


    The present work reports the spectral signatures of intramolecular charge transfer (ICT) reaction in 3-amino-4-methyl benzoic acid (AMBA). AMBA exhibits large red-shifted emission in various solvents with the emission maxima being highly sensitive to the solvent polarity. Solvatochromic measurements of AMBA on the basis of its steady state absorption and emission properties appears to confirm the operation of photoinduced ICT reaction in it with the ICT state being characterized by a higher excited state dipole moment than that of the ground state. Laser induced fluorescence excitation spectra and dispersed fluorescence spectra of AMBA and its solvated clusters with polar solvent methanol in the cooled jet yield quite distinct evidence for the occurrence of ICT reaction in polar solvent.

  20. Clusters: Elucidating the dynamics of ionization events and ensuing reactions in the condensed phase. Final technical report, March 1, 1991--February 28, 1994

    Energy Technology Data Exchange (ETDEWEB)

    Castleman, A.W. Jr.


    Chemical reactions that proceed following either a photophysical or ionizing event, are directly influenced by the mechanisms of energy transfer and dissipation away from the site of absorption. Neighboring solvent or solute molecules can affect this by collisional deactivation (removal of energy), through effects in which dissociating molecules are kept in relatively close proximity for comparatively long periods of time due to the presence of the solvent, and in other ways where the solvent influences the energetics of the reaction coordinate. Research on clusters offers promise of elucidating the molecular details of these processes. The studies have focused on providing critical information on problems in radiation biology through investigations of reactions of molecules which simulate functional groups in biological systems, as they proceed following the absorption of ionizing radiation. The overall objective of the program has been to undertake basic underpinning research that contributes to a quantification of the behavior of radionuclides and pollutants associated with advanced energy activities after these materials emanate from their source and are transferred through the environment to the biota and human receptor. Some of the studies have dealt with the interaction of electromagnetic radiation with matter yielding new data that finds value in assessing photoinduced transformation of pollutants including reactions which take place on aerosol particles, as well as those of species which become transformed into aerosols as a result of their chemical and physical interactions.

  1. Condensed species in products of the reaction of SF6 with Cu up to 4000 K (United States)

    Coufal, O.; Toman, P.


    This paper is concerned with condensed species in the equilibrium composition of a system of products of the reaction of sulphur hexafluoride with copper. It is assumed that SF6 is an insulation medium in the circuit breaker and reacts with the Cu contained in the circuit breaker contacts or in other parts of the circuit breaker. The system of products of the reaction of SF6 with Cu is assumed to be in local thermodynamic equilibrium for temperatures ranging from ambient temperature to 4000 K, with the pressure in the system being within an interval from 0.1 MPa to 2 MPa. The occurrence of condensed species and their phase transformations significantly affect the composition and thus also the system properties in a range of temperatures at which arc ignition or arc extinction take place. Data on the condensed species considered are analysed and the effects of the phase rule and the selected theoretical model on the occurrence of condensed species in the equilibrium composition are examined.

  2. Summer Research Institute Interfacial and Condensed Phase Chemical Physics

    Energy Technology Data Exchange (ETDEWEB)

    Barlow, Stephan E.


    Pacific Northwest National Laboratory (PNNL) hosted its first annual Summer Research Institute in Interfacial and Condensed Phase Chemical Physics from May through September 2004. During this period, fourteen PNNL scientists hosted sixteen young scientists from eleven different universities. Of the sixteen participants, fourteen were graduate students; one was transitioning to graduate school; and one was a university faculty member.

  3. A Facile, Choline Chloride/Urea Catalyzed Solid Phase Synthesis of Coumarins via Knoevenagel Condensation

    Directory of Open Access Journals (Sweden)

    Hosanagara N. Harishkumar


    Full Text Available The influence of choline chloride/urea ionic liquid in solid phase on the Knoevenagel condensation is demonstrated. The active methylene compounds such as meldrum’s acid, diethylmalonate, ethyl cyanoacetate, dimethylmalonate, were efficiently condensed with various salicylaldehydes in presence of choline chloride/urea ionic liquid without using any solvents or additional catalyst. The reaction is remarkably facile because of the air and water stability of the catalyst, and needs no special precautions. The reactions were completed within 1hr with excellent yields (95%. The products formed were sufficiently pure, and can be easily recovered. The use of ionic liquid choline chloride/urea in solid phase offered several significant advantages such as low cost, greater selectivity and easy isolation of products.

  4. Quantum mechanical force fields for condensed phase molecular simulations (United States)

    Giese, Timothy J.; York, Darrin M.


    Molecular simulations are powerful tools for providing atomic-level details into complex chemical and physical processes that occur in the condensed phase. For strongly interacting systems where quantum many-body effects are known to play an important role, density-functional methods are often used to provide the model with the potential energy used to drive dynamics. These methods, however, suffer from two major drawbacks. First, they are often too computationally intensive to practically apply to large systems over long time scales, limiting their scope of application. Second, there remain challenges for these models to obtain the necessary level of accuracy for weak non-bonded interactions to obtain quantitative accuracy for a wide range of condensed phase properties. Quantum mechanical force fields (QMFFs) provide a potential solution to both of these limitations. In this review, we address recent advances in the development of QMFFs for condensed phase simulations. In particular, we examine the development of QMFF models using both approximate and ab initio density-functional models, the treatment of short-ranged non-bonded and long-ranged electrostatic interactions, and stability issues in molecular dynamics calculations. Example calculations are provided for crystalline systems, liquid water, and ionic liquids. We conclude with a perspective for emerging challenges and future research directions.

  5. Synthesis of condensed phases containing polycyclic aromatic hydrocarbons fullerenes and nanotubes (United States)

    Reilly, Peter T. A.


    The invention relates to methods for producing polycyclic aromatic hydrocarbons, fullerenes, and nanotubes, comprising: a. heating at least one carbon-containing material to form a condensed phase comprising at least one polycyclic aromatic hydrocarbon; b. collecting at least some of the condensed phase; c. reacting the condensed phase to form fullerenes and/or nanotubes.

  6. Geometric phase gate for entangling two Bose-Einstein condensates


    Hussain, Mahmood Irtiza; Ilo-Okeke, Ebubechukwu O.; Byrnes, Tim


    We propose a method of entangling two spinor Bose-Einstein condensates using a geometric phase gate. The scheme relies upon only the ac Stark shift and a common controllable optical mode coupled to the spins. Our scheme allows for the creation of an SzSz type interaction where Sz is the total spin. The geometric phase gate can be executed in times of the order of 2{\\pi} /G, where G is the magnitude of the Stark shift. In contrast to related schemes which relied on a fourth order interaction t...

  7. Synthesis of diverse dihydropyrimidine-related scaffolds by fluorous benzaldehyde-based Biginelli reaction and post-condensation modifications

    Directory of Open Access Journals (Sweden)

    Bruno Piqani


    Full Text Available Dihydropyrimidinones and dihydropyrimidinethiones generated from the Biginelli reactions of perfluorooctanesulfonyl-attached benzaldehydes are used as common intermediates for post-condensation modifications such as cycloaddition, Liebeskind–Srogl reaction and Suzuki coupling to form biaryl-substituted dihydropyrimidinone, dihydropyrimidine, and thiazolopyrimidine compounds. The high efficiency of the diversity-oriented synthesis is achieved by conducting a multicomponent reaction for improved atom economy, under microwave heating for fast reaction, and with fluorous solid-phase extractions (F-SPE for ease of purification.

  8. Classical Keggin Intercalated into Layered Double Hydroxides: Facile Preparation and Catalytic Efficiency in Knoevenagel Condensation Reactions. (United States)

    Jia, Yueqing; Fang, Yanjun; Zhang, Yingkui; Miras, Haralampos N; Song, Yu-Fei


    The family of polyoxometalate (POM) intercalated layered double hydroxide (LDH) composite materials has shown great promise for the design of functional materials with numerous applications. It is known that intercalation of the classical Keggin polyoxometalate (POM) of [PW12 O40 ](3-) (PW12 ) into layered double hydroxides (LDHs) is very unlikely to take place by conventional ion exchange methods due to spatial and geometrical restrictions. In this paper, such an intercalated compound of Mg0.73 Al0.22 (OH)2 [PW12 O40 ]0.04 ⋅0.98 H2 O (Mg3 Al-PW12 ) has been successfully obtained by applying a spontaneous flocculation method. The Mg3 Al-PW12 has been fully characterized by using a wide range of methods (XRD, SEM, TEM, XPS, EDX, XPS, FT-IR, NMR, BET). XRD patterns of Mg3 Al-PW12 exhibit no impurity phase usually observed next to the (003) diffraction peak. Subsequent application of the Mg3 Al-PW12 as catalyst in Knoevenagel condensation reactions of various aldehydes and ketones with Z-CH2 -Z' type substrates (ethyl cyanoacetate and malononitrile) at 60 °C in mixed solvents (V2-propanol :Vwater =2:1) demonstrated highly efficient catalytic activity. The synergistic effect between the acidic and basic sites of the Mg3 Al-PW12 composite proved to be crucial for the efficiency of the condensation reactions. Additionally, the Mg3 Al-PW12 -catalyzed Knoevenagel condensation of benzaldehyde with ethyl cyanoacetate demonstrated the highest turnover number (TON) of 47 980 reported so far for this reaction. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Flows of a Vapor due to Phase Change Processes at the Condensed Phases with Temperature Fields as their Internal Structures

    National Research Council Canada - National Science Library

    Onishi, Yoshimoto; Ooshida, Takeshi


    Transient to steady motions of a vapor caused by the evaporation and condensation processes occurring at the condensed phases placed in parallel have been studied based on the Boltzmann equation of BGK type...

  10. Theory of molecular nonadiabatic electron dynamics in condensed phases (United States)

    Takatsuka, Kazuo


    In light of the rapid progress of ultrafast chemical dynamics driven by the pulse lasers having width as short as several tens of attoseconds, we herein develop a theory of nonadiabatic electron wavepacket dynamics in condensed phases, with which to directly track the dynamics of electronic-state mixing such as electron transfer in liquid solvents. Toward this goal, we combine a theory of path-branching representation for nonadiabatic electron wavepacket dynamics in vacuum {a mixed quantum-classical representation, Yonehara and Takatsuka [J. Chem. Phys. 129, 134109 (2008)]} and a theory of entropy functional to treat chemical dynamics in condensed phases {a mixed dynamical-statistical representation, Takatsuka and Matsumoto [Phys. Chem. Chem. Phys. 18, 1771 (2016)]}. Difficulty and complexity in the present theoretical procedure arise in embedding the Schrödinger equation into classically treated statistical environment. Nevertheless, the resultant equations of motion for electronic-state mixing due to the intrinsic nonadiabatic interactions and solute-solvent interactions, along with the force matrix that drives nuclear branching paths, both turn out to be clear enough to make it possible to comprehend the physical meanings behind. We also discuss briefly the nonvalidness of naive application of the notion of nonadiabatic transition dynamics among free energy surfaces.

  11. Theory of molecular nonadiabatic electron dynamics in condensed phases. (United States)

    Takatsuka, Kazuo


    In light of the rapid progress of ultrafast chemical dynamics driven by the pulse lasers having width as short as several tens of attoseconds, we herein develop a theory of nonadiabatic electron wavepacket dynamics in condensed phases, with which to directly track the dynamics of electronic-state mixing such as electron transfer in liquid solvents. Toward this goal, we combine a theory of path-branching representation for nonadiabatic electron wavepacket dynamics in vacuum {a mixed quantum-classical representation, Yonehara and Takatsuka [J. Chem. Phys. 129, 134109 (2008)]} and a theory of entropy functional to treat chemical dynamics in condensed phases {a mixed dynamical-statistical representation, Takatsuka and Matsumoto [Phys. Chem. Chem. Phys. 18, 1771 (2016)]}. Difficulty and complexity in the present theoretical procedure arise in embedding the Schrödinger equation into classically treated statistical environment. Nevertheless, the resultant equations of motion for electronic-state mixing due to the intrinsic nonadiabatic interactions and solute-solvent interactions, along with the force matrix that drives nuclear branching paths, both turn out to be clear enough to make it possible to comprehend the physical meanings behind. We also discuss briefly the nonvalidness of naive application of the notion of nonadiabatic transition dynamics among free energy surfaces.

  12. Quantum phase slips: from condensed matter to ultracold quantum gases (United States)

    D'Errico, C.; Abbate, S. Scaffidi; Modugno, G.


    Quantum phase slips (QPS) are the primary excitations in one-dimensional superfluids and superconductors at low temperatures. They have been well characterized in most condensed-matter systems, and signatures of their existence have been recently observed in superfluids based on quantum gases too. In this review, we briefly summarize the main results obtained on the investigation of phase slips from superconductors to quantum gases. In particular, we focus our attention on recent experimental results of the dissipation in one-dimensional Bose superfluids flowing along a shallow periodic potential, which show signatures of QPS. This article is part of the themed issue 'Breakdown of ergodicity in quantum systems: from solids to synthetic matter'.

  13. Quantum chemical approach for condensed-phase thermochemistry: Proposal of a harmonic solvation model (United States)

    Nakai, Hiromi; Ishikawa, Atsushi


    We propose a novel quantum chemical method, called the harmonic solvation model (HSM), for calculating thermochemical parameters in the condensed phase, particularly in the liquid phase. The HSM represents translational and rotational motions of a solute as vibrations interacting with a cavity wall of solvent molecules. As examples, the HSM and the ideal-gas model (IGM) were used for the standard formation reaction of liquid water, combustion reactions of liquid formic acid, methanol, and ethanol, vapor-liquid equilibration of water and ethanol, and dissolution of gaseous CO2 in water. The numerical results confirmed the reliability and applicability of the HSM. In particular, the temperature dependence of the Gibbs energy of liquid molecules was accurately reproduced by the HSM; for example, the boiling point of water was reasonably determined using the HSM, whereas the conventional IGM treatment failed to obtain a crossing of the two Gibbs energy curves for gaseous and liquid water.

  14. Quantum chemical approach for condensed-phase thermochemistry: proposal of a harmonic solvation model. (United States)

    Nakai, Hiromi; Ishikawa, Atsushi


    We propose a novel quantum chemical method, called the harmonic solvation model (HSM), for calculating thermochemical parameters in the condensed phase, particularly in the liquid phase. The HSM represents translational and rotational motions of a solute as vibrations interacting with a cavity wall of solvent molecules. As examples, the HSM and the ideal-gas model (IGM) were used for the standard formation reaction of liquid water, combustion reactions of liquid formic acid, methanol, and ethanol, vapor-liquid equilibration of water and ethanol, and dissolution of gaseous CO2 in water. The numerical results confirmed the reliability and applicability of the HSM. In particular, the temperature dependence of the Gibbs energy of liquid molecules was accurately reproduced by the HSM; for example, the boiling point of water was reasonably determined using the HSM, whereas the conventional IGM treatment failed to obtain a crossing of the two Gibbs energy curves for gaseous and liquid water.

  15. Angular distribution and atomic effects in condensed phase photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Davis, R.F.


    A general concept of condensed phase photoelectron spectroscopy is that angular distribution and atomic effects in the photoemission intensity are determined by different mechanisms, the former being determined largely by ordering phenomena such as crystal momentum conservation and photoelectron diffraction while the latter are manifested in the total (angle-integrated) cross section. In this work, the physics of the photoemission process is investigated in several very different experiments to elucidate the mechanisms of, and correlation between, atomic and angular distribution effects. Theoretical models are discussed and the connection betweeen the two effects is clearly established. The remainder of this thesis, which describes experiments utilizing both angle-resolved and angle-integrated photoemission in conjunction with synchrotron radiation in the energy range 6 eV less than or equal to h less than or equal to 360 eV and laboratory sources, is divided into three parts.

  16. Stability of Chapman Jouguet detonations for a stiffened-gas model of condensed-phase explosives (United States)

    Short, Mark; Bdzil, John B.; Anguelova, Iana I.


    The analysis of the linear stability of a planar Chapman Jouguet detonation wave is reformulated for an arbitrary caloric (incomplete) equation of state in an attempt to better represent the stability properties of detonations in condensed-phase explosives. Calculations are performed on a ‘stiffened-gas’ equation of state which allows us to prescribe a finite detonation Mach number while simultaneously allowing for a detonation shock pressure that is substantially larger than the ambient pressure. We show that the effect of increasing the ambient sound speed in the material, for a given detonation speed, has a stabilizing effect on the detonation. We also show that the presence of the slow reaction stage, a feature of detonations in certain types of energetic materials, where the detonation structure is characterized by a fast reaction stage behind the detonation shock followed by a slow reaction stage, tends to have a destabilizing effect.

  17. Simulation of inviscid compressible multi-phase flow with condensation

    NARCIS (Netherlands)

    Kelleners, P.H.


    Condensation of vapours in rapid expansions of compressible gases is investigated. In the case of high temperature gradients the condensation will start at conditions well away from thermodynamic equilibrium of the fluid. In those cases homogeneous condensation is dominant over heterogeneous

  18. Topological phases in condensed matter systems: A study of symmetries, quasiparticles and phase transitions

    NARCIS (Netherlands)

    Haaker, S.M.


    The research described in this thesis focuses on topological phases in condensed matter systems. It can be roughly divided into two parts. In the first part noninteracting systems are studied. The symmetry algebra of a charged spin-1/2 particle coupled to a non-Abelian magnetic field is determined,

  19. Simulation of Inviscid Compressible Multi-Phase Flow with Condensation (United States)

    Kelleners, Philip


    Condensation of vapours in rapid expansions of compressible gases is investigated. In the case of high temperature gradients the condensation will start at conditions well away from thermodynamic equilibrium of the fluid. In those cases homogeneous condensation is dominant over heterogeneous condensation. The present work is concerned with development of a simulation tool for computation of high speed compressible flows with homogeneous condensation. The resulting ow solver should preferably be accurate and robust to be used for simulation of industrial flows in general geometries.

  20. Molecular Photofragmentation Dynamics in the Gas and Condensed Phases (United States)

    Ashfold, Michael N. R.; Murdock, Daniel; Oliver, Thomas A. A.


    Exciting a molecule with an ultraviolet photon often leads to bond fission, but the final outcome of the bond cleavage is typically both molecule and phase dependent. The photodissociation of an isolated gas-phase molecule can be viewed as a closed system: Energy and momentum are conserved, and the fragmentation is irreversible. The same is not true in a solution-phase photodissociation process. Solvent interactions may dissipate some of the photoexcitation energy prior to bond fission and will dissipate any excess energy partitioned into the dissociation products. Products that have no analog in the corresponding gas-phase study may arise by, for example, geminate recombination. Here, we illustrate the extent to which dynamical insights from gas-phase studies can inform our understanding of the corresponding solution-phase photochemistry and how, in the specific case of photoinduced ring-opening reactions, solution-phase studies can in some cases reveal dynamical insights more clearly than the corresponding gas-phase study.

  1. Electron emission from condensed phase material induced by fast protons† (United States)

    Shinpaugh, J. L.; McLawhorn, R. A.; McLawhorn, S. L.; Carnes, K. D.; Dingfelder, M.; Travia, A.; Toburen, L. H.


    Monte Carlo track simulation has become an important tool in radiobiology. Monte Carlo transport codes commonly rely on elastic and inelastic electron scattering cross sections determined using theoretical methods supplemented with gas-phase data; experimental condensed phase data are often unavailable or infeasible. The largest uncertainties in the theoretical methods exist for low-energy electrons, which are important for simulating electron track ends. To test the reliability of these codes to deal with low-energy electron transport, yields of low-energy secondary electrons ejected from thin foils have been measured following passage of fast protons. Fast ions, where interaction cross sections are well known, provide the initial spectrum of low-energy electrons that subsequently undergo elastic and inelastic scattering in the material before exiting the foil surface and being detected. These data, measured as a function of the energy and angle of the emerging electrons, can provide tests of the physics of electron transport. Initial measurements from amorphous solid water frozen to a copper substrate indicated substantial disagreement with MC simulation, although questions remained because of target charging. More recent studies, using different freezing techniques, do not exhibit charging, but confirm the disagreement seen earlier between theory and experiment. One now has additional data on the absolute differential electron yields from copper, aluminum and gold, as well as for thin films of frozen hydrocarbons. Representative data are presented. PMID:21183539

  2. Coherent Control of Multiphoton Transitions in the Gas and Condensed Phases with Shaped Ultrashort Pulses

    Energy Technology Data Exchange (ETDEWEB)

    Marcos Dantus


    Controlling laser-molecule interactions has become an integral part of developing devices and applications in spectroscopy, microscopy, optical switching, micromachining and photochemistry. Coherent control of multiphoton transitions could bring a significant improvement of these methods. In microscopy, multi-photon transitions are used to activate different contrast agents and suppress background fluorescence; coherent control could generate selective probe excitation. In photochemistry, different dissociative states are accessed through two, three, or more photon transitions; coherent control could be used to select the reaction pathway and therefore the yield-specific products. For micromachining and processing a wide variety of materials, femtosecond lasers are now used routinely. Understanding the interactions between the intense femtosecond pulse and the material could lead to technologically important advances. Pulse shaping could then be used to optimize the desired outcome. The scope of our research program is to develop robust and efficient strategies to control nonlinear laser-matter interactions using ultrashort shaped pulses in gas and condensed phases. Our systematic research has led to significant developments in a number of areas relevant to the AMO Physics group at DOE, among them: generation of ultrashort phase shaped pulses, coherent control and manipulation of quantum mechanical states in gas and condensed phases, behavior of isolated molecules under intense laser fields, behavior of condensed phase matter under intense laser field and implications on micromachining with ultrashort pulses, coherent control of nanoparticles their surface plasmon waves and their nonlinear optical behavior, and observation of coherent Coulomb explosion processes at 10^16 W/cm^2. In all, the research has resulted in 36 publications (five journal covers) and nine invention disclosures, five of which have continued on to patenting

  3. Condensed Matter Deuterium Cluster Target for Study of Pycnonuclear Reactions (United States)

    Yang, Xiaoling; George, Miley


    Fusion reactions have two main classes: thermonuclear and the pycnonuclear. Thermonuclear fusion occurs in low density high temperature plasmas, and is very sensitive to the ion temperature due to Columbic repulsion effects. As the density increases, the Columbic potential barrier is depressed by increased electron screening, allowing fusion at lower temperatures. This type of nuclear reaction is termed a pycnonuclear fusion and is the basis for astrophysical fusion. Ichimarua [1] proposed a laboratory study of this process using explosive mechanical compression of H/D to metallic densities, which would be extremely difficult to implement. Instead, our recent research suggests that metallic-like H/D ``clusters'' can be formed in dislocation loops of thin Palladium foils through electrochemical processes. [2] If this technique is used as a laser compression target, the compressed cluster density would allow study of pycnonuclear reactions. This provides a means of studying astrophysical fusion process, and could also lead to an important non-cryogenic ICF target. [2] [4pt] [1] S. Ichimaru, H. Kitamura. Phys. Plasmas, 6, 2649 (1999) [0pt] [2] G. Miley and X. Yang, Deuterium Cluster Target for Ultra-High Density, 18TH TOFE, San Francisco, CA Sep. 28 -- Oct. 2, 2008

  4. Photoinduced Processes in Cobalt-Complexes: Condensed Phase and Gas Phase

    Directory of Open Access Journals (Sweden)

    Niedner-Schatteburg Y.


    Full Text Available Femtosecond time-resolved, steady-state spectroscopic methods and quantum chemical calculations are employed to study ultrafast photoinduced processes in [Co(III-(L-N4Me2(dbc](BPh4 and [Co(II-(L-N4tBu2(dbsq](B(p-C6H4Cl4 and to characterise the transient redox- and spin-states in condensed and gas phase.

  5. Detonation propagation in annular arcs of condensed phase explosives (United States)

    Ioannou, Eleftherios; Schoch, Stefan; Nikiforakis, Nikolaos; Michael, Louisa


    We present a numerical study of detonation propagation in unconfined explosive charges shaped as an annular arc (rib). Steady detonation in a straight charge propagates at constant speed, but when it enters an annular section, it goes through a transition phase and eventually reaches a new steady state of constant angular velocity. This study examines the speed of the detonation wave along the annular charge during the transition phase and at steady state, as well as its dependence on the dimensions of the annulus. The system is modeled using a recently proposed diffuse-interface formulation which allows for the representation of a two-phase explosive and of an additional inert material. The explosive considered is the polymer-bonded TATB-based LX-17 and is modeled using two Jones-Wilkins-Lee (JWL) equations of state and the ignition and growth reaction rate law. Results show that steady state speeds are in good agreement with experiment. In the transition phase, the evolution of outer detonation speed deviates from the exponential bounded growth function suggested by previous studies. We propose a new description of the transition phase which consists of two regimes. The first regime is caused by local effects at the outer edge of the annulus and leads to a dependence of the outer detonation speed on the angular position along the arc. The second regime is induced by effects originating from the inner edge of the annular charge and leads to the deceleration of the outer detonation until steady state is reached. The study concludes with a parametric study where the dependence of the steady state and the transition phase on the dimensions of the annulus is investigated.

  6. Boehmite-An Efficient and Recyclable Acid-Base Bifunctional Catalyst for Aldol Condensation Reaction. (United States)

    Reshma, P C Rajan; Vikneshvaran, Sekar; Velmathi, Sivan


    In this work boehmite was used as an acid-base bifunctional catalyst for aldol condensation reactions of aromatic aldehydes and ketones. The catalyst was prepared by simple sol-gel method using Al(NO3)3·9H2O and NH4OH as precursors. The catalyst has been characterized by X-ray diffraction (XRD), Fourier Transform Infrared (FTIR), Scanning Electron Microscopy (SEM), UV-visible spectroscopy (DRS), BET surface area analyses. Boehmite is successfully applied as catalyst for the condensation reaction between 4-nitrobenzaldehyde and acetone as a model substrate giving α, β-unsaturated ketones without any side product. The scope of the reaction is extended for various substituted aldehydes. A probable mechanism has been suggested to explain the cooperative behavior of the acidic and basic sites. The catalyst is environmentally friendly and easily recovered from the reaction mixture. Also the catalyst is reusable up to 3 catalytic cycles.

  7. An atomic perspective of the photodissociation and geminate recombination of triiodide in condensed phases

    Energy Technology Data Exchange (ETDEWEB)

    Xian, Rui


    The thesis presents progress made towards a thorough understanding of the photodissociation and geminate recombination of triiodide anion (I{sub 3}{sup -}) in solution and solid state using novel time-resolved spectroscopic and structural methods that have matured in the past decade. An isolated I{sub 3}{sup -} has only three degrees of freedom, but in the condensed phase, the case of an open quantum system, its chemistry is transformed because other degrees of freedom from the surroundings (the bath) need to be fully taken into account. This system is a textbook example for understanding dissociation and recombination processes in condensed phases, but unresolved issues about the reaction pathways remain. To probe the issues, firstly, mid-UV pulse shaper-based closed-loop adaptive control as well as open-loop power and chirp control schemes were used in conjunction with single-color pump-probe detection of the yield of the photoproduct diiodide (I{sub 2}{sup -.}) to study the above reaction in ethanol solution. The experiments revealed a strong pump-chirp dependence of the I{sub 2}{sup -.}-yield (as much as 40% change). Subsequently, two possible mechanisms involving additional reaction channels were postulated in order to explain such effect. Secondly, pump-supercontinuum-probe spectroscopy and ultrafast electron diffraction were performed separately on solid state triiodide compound n-(C{sub 4}H{sub 9}){sub 4}NI{sub 3} (TBAT). This system was chosen to provide a well-defined lattice for the bath and to avail atomic resolution of the condensed phase reaction dynamics. In the optical experiment, coherent oscillations were observed within a probe delay of 1 ps that bear strong resemblance to the stretching modes of ground-state I{sub 3}{sup -} and I{sub 2}{sup -.} fragment, which makes it the first to reliably distinguish the two species in a single measurement. In addition, the spectroscopic signature of a novel intermediate, the tetraiodide anion (I{sub 4}{sup

  8. Is the Chiral Phase Transition in Non-Compact Lattice QED Driven by Monopole Condensation?


    Goeckeler, M.; Horsley, R.; Rakow, P. E. L.; Schierholz, G.


    We investigate the recent conjecture that the chiral phase transition in non-compact lattice QED is driven by monopole condensation. The comparison of analytic and numerical results shows that we have a quantitative understanding of monopoles in both the quenched and dynamical cases. We can rule out monopole condensation.

  9. Heterogeneous oxidation of pesticides on aerosol condensed phase (United States)

    Socorro, Joanna; Durand, Amandine; Temime-Roussel, Brice; Ravier, Sylvain; Gligorovski, Sasho; Wortham, Henri; Quivet, Etienne


    Pesticides are widely used all over the world. It is known that they exhibit adverse health effects and environmental risks due to their physico-chemical properties and their extensive use which is growing every year. They are distributed in the atmosphere, an important vector of dissemination, over long distances away from the target area. The partitioning of pesticides between the gas and particulate phases influences their atmospheric fate. Most of the pesticides are semi-volatile compounds, emphasizing the importance of assessing their heterogeneous reactivity towards atmospheric oxidants. These reactions are important because they are involved in, among others, direct and indirect climate changes, adverse health effects from inhaled particles, effects on cloud chemistry and ozone production. In this work, the importance of atmospheric degradation of pesticides is evaluated on the surface of aerosol deliquescent particles. The photolysis processing and heterogeneous reactivity towards O3 and OH, was evaluated of eight commonly used pesticides (cyprodinil, deltamethrin, difenoconazole, fipronil, oxadiazon, pendimethalin, permethrin, tetraconazole) adsorbed on silica particles. Silicate particles are present in air-borne mineral dust in atmospheric aerosols, and heterogeneous reactions can be different in the presence of these mineral particles. Depending on their origin and conditioning, aerosol particles containing pesticides can have complex and highly porous microstructures, which are influenced by electric charge effects and interaction with water vapour. Therefore, the kinetic experiments and consecutive product studies were performed at atmospherically relevant relative humidity (RH) of 55 %. The identification of surface bound products was performed using GC-(QqQ)-MS/MS and LC-(Q-ToF)-MS/MS and the gas-phase products were on-line monitored by PTR-ToF-MS. Based on the detected and identified reaction products, it was observed that water plays a crucial

  10. Recommendations for the presentation of infrared absorption spectra in data collections condensed phases

    CERN Document Server

    Becker, E D


    Recommendations for the Presentation of Infrared Absorption Spectra in Data Collections-A. Condensed Phases presents the recommendations related to the infrared spectra of condensed phase materials that are proposed for permanent retention in data collections. These recommendations are based on two reports published by the Coblentz Society. This book emphasizes the three levels of quality evaluation for infrared spectra as designated by the Coblentz Society, including critically defined physical data, research quality analytical spectra, and approved analytical spectra. This text discusses the

  11. Microwave Assisted Condensation Reactions of 2-Aryl Hydrazonopropanals with Nucleophilic Reagents and Dimethyl Acetylenedicarboxylate

    Directory of Open Access Journals (Sweden)

    Rita M. Borik


    Full Text Available The reaction of methyl ketones 1a-g with dimethylformamide dimethylacetal (DMFDMA afforded the enaminones 2a-g, which were coupled with diazotized aromatic amines 3a,b to give the corresponding aryl hydrazones 6a-h. Condensation of compounds 6a-h with some aromatic heterocyclic amines afforded iminoarylhydrazones 9a-m. Enaminoazo compounds 12a,b could be obtained from condensation of 6c with secondary amines. The reaction of 6e,h with benzotriazolylacetone yielded 14a,b. Also, the reaction of 6a,b,d-f,h with glycine and hippuric acid in acetic anhydride afforded pyridazinone derivatives 17a-f. Synthesis of pyridazine carboxylic acid derivatives 22a,b from the reaction of 6b,e with dimethyl acetylenedicarboxylate (DMAD in the presence of triphenylphosphine at room temperature is also reported. Most of these reactions were conducted under irradiation in a microwave oven in the absence of solvent in an attempt to improve the product yields and to reduce the reaction times.

  12. Metal Organic Frameworks as Solid Catalysts in Condensation Reactions of Carbonyl Groups

    Czech Academy of Sciences Publication Activity Database

    Dhakshinamoorthy, A.; Opanasenko, Maksym; Čejka, Jiří; Garcia, H.


    Roč. 355, 2-3 (2013), s. 247-268 ISSN 1615-4150 R&D Projects: GA ČR GBP106/12/G015 Grant - others:European Commission(XE) FP7/2007-2013, contract 228862 Institutional support: RVO:61388955 Keywords : alcohol condensation * green chemistry * Henry reaction Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.542, year: 2013

  13. Refrigerant pressurization system with a two-phase condensing ejector (United States)

    Bergander, Mark [Madison, CT


    A refrigerant pressurization system including an ejector having a first conduit for flowing a liquid refrigerant therethrough and a nozzle for accelerating a vapor refrigerant therethrough. The first conduit is positioned such that the liquid refrigerant is discharged from the first conduit into the nozzle. The ejector includes a mixing chamber for condensing the vapor refrigerant. The mixing chamber comprises at least a portion of the nozzle and transitions into a second conduit having a substantially constant cross sectional area. The condensation of the vapor refrigerant in the mixing chamber causes the refrigerant mixture in at least a portion of the mixing chamber to be at a pressure greater than that of the refrigerant entering the nozzle and greater than that entering the first conduit.

  14. Carbonitriding reactions of diatomaceous earth: phase evolution and reaction mechanisms

    Directory of Open Access Journals (Sweden)



    Full Text Available The possibility of using diatomaceous earth as Si precursor for low temperature synthesis of non-oxide powders by carbothermal reduction-nitridation was studied. It was found that carbonitriding reactions produce phases of the Si–Al–O–N system. Already at 1300 °C, nanosized, non-oxide powders were obtained. The comparatively low reaction temperatures is attributred to the nano-porous nature of the raw material. The evolution of crystalline phases proceeded via many intermediate stages. The powders were characterized by X-ray and SEM investigations. The results showed that diatomaceous earth can be a very effective source for obtaining non-oxide powders.

  15. Trace Anomaly and Dimension Two Gluon Condensate Above the Phase Transition

    Energy Technology Data Exchange (ETDEWEB)

    Megias,E.; Ruiz Arriola, E.; Salcedo, L.L.


    The dimension two gluon condensate has been used previously within a simple phenomenological model to describe power corrections from available lattice data for the renormalized Polyakov loop and the heavy quark-antiquark free energy in the deconfined phase of QCD. The QCD trace anomaly of gluodynamics also shows unequivocal inverse temperature power corrections which may be encoded as dimension two gluon condensate. We analyze lattice data of the trace anomaly and compare with other determinations of the condensate from previous references, yielding roughly similar numerical values.

  16. Catalytic performance of Metal-Organic-Frameworks vs. extra-large pore zeolite UTL in condensation reactions (United States)

    Shamzhy, Mariya; Opanasenko, Maksym; Shvets, Oleksiy; Čejka, Jiří


    Catalytic behavior of isomorphously substituted B-, Al-, Ga-, and Fe-containing extra-large pore UTL zeolites was investigated in Knoevenagel condensation involving aldehydes, Pechmann condensation of 1-naphthol with ethylacetoacetate, and Prins reaction of β-pinene with formaldehyde and compared with large-pore aluminosilicate zeolite beta and representative Metal-Organic-Frameworks Cu3(BTC)2 and Fe(BTC). The yield of the target product over the investigated catalysts in Knoevenagel condensation increases in the following sequence: (Al)beta condensation of 1-naphthol with ethylacetoacetate. PMID:24790940

  17. Wetting phase transition of two segregated Bose–Einstein condensates restricted by a hard wall

    Energy Technology Data Exchange (ETDEWEB)

    Thu, Nguyen Van [Department of Physics, Hanoi Pedagogical University No. 2, Hanoi (Viet Nam); Phat, Tran Huu [Vietnam Atomic Energy Commission, 59 Ly Thuong Kiet, Hanoi (Viet Nam); Song, Pham The, E-mail: [Tay Bac University, Son La (Viet Nam)


    Highlights: • System of two segregated Bose–Einstein condensates limited by a wall is studied. • Double-parabola approximation is applied to Gross–Pitaevskii theory. • Interface tension and wetting phase diagram are established. - Abstract: The wetting phase transition in the system of two segregated Bose–Einstein condensates (BECs) restricted by a hard wall is studied by means of the double-parabola approximation (DPA) applied to the Gross–Pitaevskii (GP) theory. We found the interfacial tension and the wetting phase diagram which depend weakly on the spatial restriction.

  18. Carbon in condensed hydrocarbon phases, steels and cast irons

    Directory of Open Access Journals (Sweden)

    GAFAROVA Victoria Alexandrovna


    Full Text Available The article presents a review of studies carried out mainly by the researchers of the Ufa State Petroleum Technological University, which are aimed at detection of new properties of carbon in such condensed media as petroleum and coal pitches, steels and cast irons. Carbon plays an important role in the industry of construction materials being a component of road and roof bitumen and setting the main mechanical properties of steels. It was determined that crystal-like structures appear in classical glass-like substances – pitches which contain several thousands of individual hydrocarbons of various compositions. That significantly extends the concept of crystallinity. In structures of pitches, the control parameter of the staged structuring process is paramagnetism of condensed aromatic hydrocarbons. Fullerenes were detected in steels and cast irons and identified by various methods of spectrometry and microscopy. Fullerene С60, which contains 60 carbon atoms, has diameter of 0,7 nm and is referred to the nanoscale objects, which have a significant influence on the formation of steel and cast iron properties. It was shown that fullerenes appear at all stages of manufacture of cast irons; they are formed during introduction of carbon from the outside, during crystallization of metal in welded joints. Creation of modified fullerene layers in steels makes it possible to improve anticorrosion and tribological properties of structural materials. At the same time, outside diffusion of carbon from the carbon deposits on the metal surface also leads to formation of additional amount of fullerenes. This creates conditions for occurrence of local microdistortions of the structure, which lead to occurrence of cracks. Distribution of fullerenes in iron matrix is difficult to study as the method is labor-intensive, it requires dissolution of the matrix in the hydrofluoric acid and stage fullerene separation with further identification by spectral methods.

  19. A new correlation of two-phase frictional pressure drop for condensing flow in pipes

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Yu; Fang, Xiande, E-mail:


    Highlights: • Survey of two-phase frictional pressure drop (THFPD) experimental data of condensing flow is conducted. • Applicability of the existing THFPD correlations to condensing flow is assessed. • A new THFPD correlation for condensing flow in pipes is proposed. -- Abstract: The calculation of two-phase frictional pressure drop for condensing flow in pipes is essential in many areas. Although numerous studies concerning this issue have been conducted, an accurate correlation is still required. In this paper, an overall survey of correlations and experimental investigations of two-phase frictional pressure drop is carried out. There 525 experimental data points of 9 refrigerants are gathered from literature, with hydraulic diameter from 0.1 to 10.07 mm, mass flux from 20 to 800 kg/m{sup 2} s, and heat flux from 2 to 55.3 kW/m{sup 2}. The 29 existing correlations are evaluated against the experimental database, among which the best one has a mean absolute relative deviation (MARD) of 25.2%. Based on all the experimental data, a new correlation which has an MARD of 19.4% is proposed, improving significantly the prediction of two-phase frictional pressure drop for pipe condensing flow.

  20. Flows with fractional quantum circulation in Bose-Einstein condensates induced by nontopological phase defects (United States)

    Kanai, Toshiaki; Guo, Wei; Tsubota, Makoto


    It is a common view that rotational motion in a superfluid can exist only in the presence of topological defects, i.e., quantized vortices. However, in our numerical studies on the merging of two concentric Bose-Einstein condensates with axial symmetry in two-dimensional space, we observe the emergence of a spiral dark soliton when one condensate has a nonzero initial angular momentum. This spiral dark soliton enables the transfer of angular momentum between the condensates and allows the merged condensate to rotate even in the absence of quantized vortices. Our examination of the flow field around the soliton strikingly reveals that its sharp endpoint can induce flow like a vortex point but with a fraction of a quantized circulation. This interesting nontopological "phase defect" may generate broad interest since rotational motion is essential in many quantum transport processes.

  1. Phases and phase transition in insoluble and adsorbed monolayers of amide amphiphiles: Specific characteristics of the condensed phases. (United States)

    Vollhardt, D


    For understanding the role of amide containing amphiphiles in inherently complex biological processes, monolayers at the air-water interface are used as simple biomimetic model systems. The specific characteristics of the condensed phases and phase transition in insoluble and adsorbed monolayers of amide amphiphiles are surveyed to highlight the effect of the chemical structure of the amide amphiphiles on the interfacial interactions in model monolayers. The mesoscopic topography and/or two-dimensional lattice structures of selected amino acid amphiphiles, amphiphilic N-alkylaldonamide, amide amphiphiles with specific tailored headgroups, such as amide amphiphiles based on derivatized ethanolamine, e.g. acylethanolamines (NAEs) and N-,O-diacylethanolamines (DAEs) are presented. Special attention is devoted the dominance of N,O-diacylated ethanolamine in mixed amphiphilic acid amide monolayers. The evidence that a first order phase transition can occur in adsorption layers and that condensed phase domains of mesoscopic scale can be formed in adsorption layers was first obtained on the basis of the experimental characteristics of a tailored amide amphiphile. New thermodynamic and kinetic concepts for the theoretical description of the characteristics of amide amphiphile's monolayers were developed. In particular, the equation of state for Langmuir monolayers generalized for the case that one, two or more phase transitions occur, and the new theory for phase transition in adsorbed monolayers are experimentally confirmed at first by amide amphiphile monolayers. Despite the significant progress made towards the understanding the model systems, these model studies are still limited to transfer the gained knowledge to biological systems where the fundamental physical principles are operative in the same way. The study of biomimetic systems, as described in this review, is only a first step in this direction. Copyright © 2014 Elsevier B.V. All rights reserved.

  2. Phase transitions in a holographic s + p model with back-reaction

    Energy Technology Data Exchange (ETDEWEB)

    Nie, Zhang-Yu [Kunming University of Science and Technology, Kunming (China); Chinese Academy of Sciences, State Key Laboratory of Theoretical Physics, Institute of Theoretical Physics, Beijing (China); Shanghai Jiao Tong University, INPAC, Department of Physics, and Shanghai Key Laboratory of Particle Physics and Cosmology, Shanghai (China); Cai, Rong-Gen [Chinese Academy of Sciences, State Key Laboratory of Theoretical Physics, Institute of Theoretical Physics, Beijing (China); Gao, Xin [Virginia Tech, Department of Physics, Blacksburg, VA (United States); Li, Li [University of Crete, Department of Physics, Crete Center for Theoretical Physics, Heraklion (Greece); Zeng, Hui [Kunming University of Science and Technology, Kunming (China); Chinese Academy of Sciences, State Key Laboratory of Theoretical Physics, Institute of Theoretical Physics, Beijing (China)


    In a previous paper (Nie et al. in JHEP 1311:087, arXiv:1309.2204 [hep-th], 2013), we presented a holographic s + p superconductor model with a scalar triplet charged under an SU(2) gauge field in the bulk. We also study the competition and coexistence of the s-wave and p-wave orders in the probe limit. In this work we continue to study the model by considering the full back-reaction. The model shows a rich phase structure and various condensate behaviors such as the ''n-type'' and ''u-type'' ones, which are also known as reentrant phase transitions in condensed matter physics. The phase transitions to the p-wave phase or s + p coexisting phase become first order in strong back-reaction cases. In these first order phase transitions, the free energy curve always forms a swallow tail shape, in which the unstable s + p solution can also play an important role. The phase diagrams of this model are given in terms of the dimension of the scalar order and the temperature in the cases of eight different values of the back-reaction parameter, which show that the region for the s + p coexisting phase is enlarged with a small or medium back-reaction parameter but is reduced in the strong back-reaction cases. (orig.)

  3. Phase-ordering percolation and an infinite domain wall in segregating binary Bose-Einstein condensates (United States)

    Takeuchi, Hiromitsu; Mizuno, Yumiko; Dehara, Kentaro


    Percolation theory is applied to the phase-transition dynamics of domain pattern formation in segregating binary Bose-Einstein condensates in quasi-two-dimensional systems. Our finite-size-scaling analysis shows that the percolation threshold of the initial domain pattern emerging from the dynamic instability is close to 0.5 for strongly repulsive condensates. The percolation probability is universally described with a scaling function when the probability is rescaled by the characteristic domain size in the dynamic scaling regime of the phase-ordering kinetics, independent of the intercomponent interaction. It is revealed that an infinite domain wall sandwiched between percolating domains in the two condensates has a noninteger fractal dimension and keeps the scaling behavior during the dynamic scaling regime. This result seems to be in contrast to the argument that the dynamic scale invariance is violated in the presence of an infinite topological defect in numerical cosmology.

  4. Enabling Computational Technologies for the Accurate Prediction/Description of Molecular Interactions in Condensed Phases (United States)


    aspect of this collection of information, including suggesstions for reducing this burden, to Washington Headquarters Services, Directorate for...Chemistry Conference, Modeling Condensed Phase Effects on Structure and Spectroscopy, Urbana, IL, May 31, 2013. Challenges in Computational Homogeneous ... Catalysis - 2013, Modeling Catalysis Relevant to Energy Sustainability, Cramer, C. J., Stockholm, Sweden, June 13, 2013. (c) Presentations 15.00

  5. 2005 Annual Report Summer Research Institute Interfacial and Condensed Phase Chemical Physics

    Energy Technology Data Exchange (ETDEWEB)

    Barlow, Stephan E.


    The Pacific Northwest National Laboratory (PNNL) hosted its second annual Summer Research Institute in Interfacial and Condensed Phase Chemical Physics from May through September 2005. During this period, sixteen PNNL scientists hosted fourteen young scientists from eleven different universities. Of the fourteen participants, twelve were graduate students; one was a postdoctoral fellow; and one was a university faculty member.

  6. A Study of the Reaction Between Quinone and 2R4F Cigarette Smoke Condensate

    Directory of Open Access Journals (Sweden)

    Coleman WM


    Full Text Available A study using atomic emission detection (AED as an approach to explore the fate of quinone added into 2R4F cigarette smoke condensate (CSC have been performed. Both natural isotope quinone and 13C labeled quinone were used in the study. When coupled with a gas chromatographic separation (GC/AED, the AED provided informative new data on 13C isotope enriched products generated following reactions between 2R4F CSC and the quinone. Two 13C containing species were detected by GC/AED. Matching chromatographic separation using gas chromatography/mass selective detection (GC/MSD allowed for a structural assignment of a relatively minor CSC 13C 6quinone reaction product as nitrohydroquinone (13C6NO2HQ. The chemical mechanism accounting for the formation of 13C6NO2HQ in the CSC was envisioned to be a reaction product between HONO and 13C 6Quinone (13C6Q to form 13C6NO2Q, followed by reduction of 13C6NO2Q to 13C6NO2HQ. The amount of 13C6NO2HQ accounted for ~6% of the added 13C6Q. Identical trends in reaction chemistries were found for experiments with 12C6Q. The major reaction product detected upon addition of 13C6Q to the 2R4F CSC sample was 13C6HQ. 13C6HQ accounted for, on average, ~47% of the initial 13C6Q concentration. Identical trends in reaction chemistries were found for experiments with 12C6Q. No additional 13C containing species were detected. A 13C AED compound independent calibration (CIC approach under the operating conditions was not possible. This work further expands the knowledge regarding possible reactions of quinone and hydroquinone in CSC.

  7. Phase separation and dynamics of two-component Bose-Einstein condensates

    DEFF Research Database (Denmark)

    Lee, Kean Loon; Jørgensen, Nils Byg; Liu, I-Kang


    The miscibility of two interacting quantum systems is an important testing ground for the understanding of complex quantum systems. Two-component Bose-Einstein condensates enable the investigation of this scenario in a particularly well controlled setting. In a homogeneous system, the transition...... critically on atom numbers. We demonstrate how monitoring of damping rates and frequencies of dipole oscillations enables the experimental mapping of the phase diagram by numerical implementation of a fully self-consistent finite-temperature kinetic theory for binary condensates. The change in damping rate...

  8. The role of boronic acids in accelerating condensation reactions of [small alpha]-effect amines with carbonyls


    Gillingham, Dennis


    A broad palette of bioconjugation reactions are available for chemical biologists, but an area that still requires investigation is high-rate constant reactions. These are indispensable in certain applications, particularly for in vivo labelling. Appropriately positioned boronic acids accelerate normally sluggish Schiff base condensations of α-effect nucleophiles by five orders of magnitude – providing a new entry to the rare set of reactions that have a rate constant above 100 M−1 s−1 under ...

  9. Planar blast scaling with condensed-phase explosives in a shock tube

    Energy Technology Data Exchange (ETDEWEB)

    Jackson, Scott L [Los Alamos National Laboratory


    walls. Such a technique has previously been used to obtain blast scaling measurements in the planar geometry with gaseous explosives and the condensed-phase explosive nitroguanidine. Recently, there has been much interest in the blast characterization of various non-ideal high explosive (NIHE) materials. With non-ideals, the detonation reaction zone is significantly larger (up to several cm for ANFO) than more ideal explosives. Wave curvature, induced by charge-geometry, can significantly affect the energy release associated with NIHEs. To measure maximum NIHE energy release accurately, it is desirable to minimize any such curvature and, if possible, to overdrive the detonation shock to ensure completion of chemical reactions ahead of the sonic locus associated with the reaction zone. This is achieved in the current study through use of a powerful booster HE and a charge geometry consisting of short cylindrical lengths of NIHE initiated along the charge centerline.

  10. Theoretical and computational studies of non-equilibrium and non-statistical dynamics in the gas phase, in the condensed phase and at interfaces. (United States)

    Spezia, Riccardo; Martínez-Nuñez, Emilio; Vazquez, Saulo; Hase, William L


    In this Introduction, we show the basic problems of non-statistical and non-equilibrium phenomena related to the papers collected in this themed issue. Over the past few years, significant advances in both computing power and development of theories have allowed the study of larger systems, increasing the time length of simulations and improving the quality of potential energy surfaces. In particular, the possibility of using quantum chemistry to calculate energies and forces 'on the fly' has paved the way to directly study chemical reactions. This has provided a valuable tool to explore molecular mechanisms at given temperatures and energies and to see whether these reactive trajectories follow statistical laws and/or minimum energy pathways. This themed issue collects different aspects of the problem and gives an overview of recent works and developments in different contexts, from the gas phase to the condensed phase to excited states.This article is part of the themed issue 'Theoretical and computational studies of non-equilibrium and non-statistical dynamics in the gas phase, in the condensed phase and at interfaces'. © 2017 The Author(s).

  11. Confined Phase Envelope of Gas-Condensate Systems in Shale Rocks (United States)

    Nagy, Stanislaw; Siemek, Jakub


    Natural gas from shales (NGS) and from tight rocks are one of the most important fossil energy resource in this and next decade. Significant increase in gas consumption, in all world regions, will be marked in the energy sector. The exploration of unconventional natural gas & oil reservoirs has been discussed recently in many conferences. This paper describes the complex phenomena related to the impact of adsorption and capillary condensation of gas-condensate systems in nanopores. New two phase saturation model and new algorithm for search capillary condensation area is discussed. The algorithm is based on the Modified Tangent Plane Criterion for Capillary Condensation (MTPCCC) is presented. The examples of shift of phase envelopes are presented for selected composition of gas-condensate systems. Gaz ziemny z łupków (NGS) oraz z ze złóż niskoprzepuszczalnych (typu `tight') staje się jednym z najważniejszych zasobów paliw kopalnych, w tym i następnym dziesięcioleciu. Znaczący wzrost zużycia gazu we wszystkich regionach świata zaznacza się głównie w sektorze energetycznym. Rozpoznawanie niekonwencjonalnych złóż gazu ziemnego i ropy naftowej w ostatnim czasie jest omawiane w wielu konferencjach. Niniejszy artykuł opisuje złożone zjawiska związane z wpływem adsorpcji i kapilarnej kondensacji w nanoporach w złożach gazowo-kondensatowych. Pokazano nowy dwufazowy model równowagowy dwufazowy i nowy algorytm wyznaczania krzywej nasycenia w obszarze kondensacji kapilarnej. Algorytm bazuje na kryterium zmodyfikowanym płaszczyzny stycznej dla kapilarnej kondensacji (MTPCCC). Przykłady zmiany krzywych nasycenia są przedstawiane w wybranym składzie systemów gazowo- kondensatowych

  12. 2006 Annual Report Summer Research Institute Interfacial and Condensed Phase Chemical Physics

    Energy Technology Data Exchange (ETDEWEB)

    Avery, Nikki B.; Barlow, Stephan E.


    The Pacific Northwest National Laboratory (PNNL) hosted its third annual Summer Research Institute in Interfacial and Condensed Phase Chemical Physics from May through September 2006. During this period, twenty PNNL scientists hosted twenty-seven scientists from twenty-five different universities. Of the twenty-seven participants, one was a graduating senior; twenty-one were graduate students; one was a postdoctoral fellow; and four were university faculty members.

  13. 2007 Annual Report Summer Research Institute Interfacial and Condensed Phase Chemical Physics

    Energy Technology Data Exchange (ETDEWEB)

    Beck, Kenneth M.


    The Pacific Northwest National Laboratory (PNNL) hosted its fourth annual Summer Research Institute in Interfacial and Condensed Phase Chemical Physics from April through September 2007. During this time, 21 PNNL scientists hosted 23 participants from 20 different universities. Of the 23 participants, 20 were graduate students, 1 was a postdoctoral fellow, and 2 were university faculty members. This report covers the essense of the program and the research the participants performed.

  14. Phase operators and blurring time of a pair-condensed Fermi gas (United States)

    Kurkjian, H.; Castin, Y.; Sinatra, A.


    Due to atomic interactions and dispersion in the total atom number, the order parameter of a pair-condensed Fermi gas experiences a collapse in a time that we derive microscopically. As in the bosonic case, this blurring time depends on the derivative of the gas chemical potential with respect to the atom number and on the variance of that atom number. The result is obtained first using linearized time-dependent Bogoliubov-de Gennes equations, then in the random-phase approximation, and then it is generalized to beyond the mean field. In this framework, we construct and compare two phase operators for the paired fermionic field: The first one, issuing from our study of the dynamics, is the infinitesimal generator of adiabatic translations in the total number of pairs. The second one is the phase operator of the amplitude of the field of pairs on the condensate mode. We explain that these two operators differ due to the dependence of the condensate wave function on the atom number.

  15. Explorations of Magnetic Phases in F = 1 Rubidium-87 Spinor Condensates (United States)

    Guzman, Jennie Sara

    Spinor Bose Einstein condensates have widely been sought after as perfect emulators of condensed matter phenomena, providing widely tunable and highly controlled systems. Utilizing a novel spin sensitive phase contrast imaging technique, the vector magnetization is measured in-situ with high spatial and temporal resolution and applied to a number of experiments. Using optically trapped F = 1 87Rb spinor condensates, the equilibrium phase diagram of a spin-1 Bose gas is quantitatively explored by observing the evolution of unmagnetized spin textures and their thermal equilibrium properties. Spin domain coarsening and a strong dependence of the spin configuration on the quadratic Zeeman shift is observed, supporting the predicted mean-field equilibrium phase diagram for small values of the quadratic shift. Additionally, spinor Bose gases are demonstrated to be an effective tool in calibrating and characterizing experimental imaging systems. Sinusoidal test patterns of varying pitch are created and used to extract the modulation transfer function and quantify optical aberrations which are of immense importance in systems which claim to have high spatial resolution. Lastly we realize an optical kagome geometry in a two-dimensional optical superlattice with a scalar Bose gases. The optical superlattice can be tuned between various geometries, including kagome, one-dimensional stripe, and decorated triangular lattice. Using atom optics we characterize the various geometries and demonstrate the versatility of this optical superlattice. The kagome geometry presents a new experimental arena for studies of geometrically frustrated systems.

  16. Phase space structures governing reaction dynamics in rotating molecules

    NARCIS (Netherlands)

    Ciftci, Unver; Waalkens, Holger

    Recently, the phase space structures governing reaction dynamics in Hamiltonian systems have been identified and algorithms for their explicit construction have been developed. These phase space structures are induced by saddle type equilibrium points which are characteristic for reaction type

  17. Phase Diagram of the Bose Condensation of Interwell Excitons in GaAs/AlGaAs Double Quantum Wells

    DEFF Research Database (Denmark)

    Dremin, A. A.; Timofeev, V. B.; Larionov, A. V.


    observed in the experiment was attributed to Bose–Einstein condensation in a quasi-two-dimensional system of interwell excitons. In the temperature interval studied (0.5–3.6) K, the critical exciton density and temperature were determined and a phase diagram outlining the exciton condensate region...

  18. Ab initio calculations concerning the reaction mechanism of the copper(II) catalyzed glycine condensation in aqueous sodium chloride solution (United States)

    Liedl, Klaus R.; Rode, Bernd M.


    Starting from results of detailed experimental work concerning the copper(II) catalyzed glycine condensation, quantum-mechanical studies of species which should be relevant for the reaction mechanism are presented. This reaction is of special interest because it could be important in explaining the formation of the first peptides on prebiotic earth. SCF geometry optimizations of aquo-chloro-glycinato—copper(II) complexes at Hartree—Fock level were performed especially to study the necessity of chlorine for the reaction. In that way a hypothetical reaction mechanism could be confirmed. Structural distortions as expected from the Jahn—Teller effect resulted from optimizations of copper complexes in C1 geometry.

  19. Intermolecular interactions in the condensed phase: Evaluation of semi-empirical quantum mechanical methods (United States)

    Christensen, Anders S.; Kromann, Jimmy C.; Jensen, Jan H.; Cui, Qiang


    To facilitate further development of approximate quantum mechanical methods for condensed phase applications, we present a new benchmark dataset of intermolecular interaction energies in the solution phase for a set of 15 dimers, each containing one charged monomer. The reference interaction energy in solution is computed via a thermodynamic cycle that integrates dimer binding energy in the gas phase at the coupled cluster level and solute-solvent interaction with density functional theory; the estimated uncertainty of such calculated interaction energy is ±1.5 kcal/mol. The dataset is used to benchmark the performance of a set of semi-empirical quantum mechanical (SQM) methods that include DFTB3-D3, DFTB3/CPE-D3, OM2-D3, PM6-D3, PM6-D3H+, and PM7 as well as the HF-3c method. We find that while all tested SQM methods tend to underestimate binding energies in the gas phase with a root-mean-squared error (RMSE) of 2-5 kcal/mol, they overestimate binding energies in the solution phase with an RMSE of 3-4 kcal/mol, with the exception of DFTB3/CPE-D3 and OM2-D3, for which the systematic deviation is less pronounced. In addition, we find that HF-3c systematically overestimates binding energies in both gas and solution phases. As most approximate QM methods are parametrized and evaluated using data measured or calculated in the gas phase, the dataset represents an important first step toward calibrating QM based methods for application in the condensed phase where polarization and exchange repulsion need to be treated in a balanced fashion.

  20. Quantitative investigation of free radicals in bio-oil and their potential role in condensed-phase polymerization. (United States)

    Kim, Kwang Ho; Bai, Xianglan; Cady, Sarah; Gable, Preston; Brown, Robert C


    We report on the quantitative analysis of free radicals in bio-oils produced from pyrolysis of cellulose, organosolv lignin, and corn stover by EPR spectroscopy. Also, we investigated their potential role in condensed-phase polymerization. Bio-oils produced from lignin and cellulose show clear evidence of homolytic cleavage reactions during pyrolysis that produce free radicals. The concentration of free radicals in lignin bio-oil was 7.5×10(20)  spin g(-1), which was 375 and 138 times higher than free-radical concentrations in bio-oil from cellulose and corn stover. Pyrolytic lignin had the highest concentration in free radicals, which could be a combination of carbon-centered (benzyl radicals) and oxygen-centered (phenoxy radicals) organic species because they are delocalized in a π system. Free-radical concentrations did not change during accelerated aging tests despite increases in molecular weight of bio-oils, suggesting that free radicals in condensed bio-oils are stable. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Probing the exciton condensate phase in 1T-TiSe{sub 2} with photoemission

    Energy Technology Data Exchange (ETDEWEB)

    Monney, C; Schwier, E F; Garnier, M G; Mariotti, N; Didiot, C; Beck, H; Aebi, P [Departement de Physique and Fribourg Center for Nanomaterials, Universite de Fribourg, CH-1700 Fribourg (Switzerland); Cercellier, H; Marcus, J [Institut Neel, CNRS-UJF, BP 166, 38042 Grenoble (France); Berger, H [EPFL, Institut de Physique de la Matiere Condensee, CH-1015 Lausanne (Switzerland); Titov, A N, E-mail: [Institute of Metal Physics UrD RAS, Ekaterinburg 620219 (Russian Federation)


    We present recent results obtained using angle-resolved photoemission spectroscopy performed on 1T-TiSe{sub 2}. Emphasis is put on the peculiarity of the bandstructure of TiSe{sub 2} compared to other transition metal dichalcogenides, which suggests that this system is an excellent candidate for the realization of the excitonic insulator phase. This exotic phase is discussed in relation to the BCS theory, and its spectroscopic signature is computed via a model adapted to the particular bandstructure of 1T-TiSe{sub 2}. A comparison between photoemission intensity maps calculated with the spectral function derived for this model and experimental results is shown, giving strong support for the exciton condensate phase as the origin of the charge density wave transition observed in 1T-TiSe{sub 2}. The temperature-dependent order parameter characterizing the exciton condensate phase is discussed, both on a theoretical and an experimental basis, as well as the chemical potential shift occurring in this system. Finally, the transport properties of 1T-TiSe{sub 2} are analyzed in the light of the photoemission results.

  2. Condensation Polymerization

    Indian Academy of Sciences (India)

    Condensation polymerizations, as thename suggests, utilizes bond-forming reactions that generatea small molecule condensate, which often needs to be continuouslyremoved to facilitate the formation of the polymer. Inthis article, I shall describe some of the essential principles ofcondensation polymerizations or more ...

  3. Theoretical insights into the sites and mechanisms for base catalyzed esterification and aldol condensation reactions over Cu. (United States)

    Neurock, Matthew; Tao, Zhiyuan; Chemburkar, Ashwin; Hibbitts, David D; Iglesia, Enrique


    Condensation and esterification are important catalytic routes in the conversion of polyols and oxygenates derived from biomass to fuels and chemical intermediates. Previous experimental studies show that alkanal, alkanol and hydrogen mixtures equilibrate over Cu/SiO 2 and form surface alkoxides and alkanals that subsequently promote condensation and esterification reactions. First-principle density functional theory (DFT) calculations were carried out herein to elucidate the elementary paths and the corresponding energetics for the interconversion of propanal + H 2 to propanol and the subsequent C-C and C-O bond formation paths involved in aldol condensation and esterification of these mixtures over model Cu surfaces. Propanal and hydrogen readily equilibrate with propanol via C-H and O-H addition steps to form surface propoxide intermediates and equilibrated propanal/propanol mixtures. Surface propoxides readily form via low energy paths involving a hydrogen addition to the electrophilic carbon center of the carbonyl of propanal or via a proton transfer from an adsorbed propanol to a vicinal propanal. The resulting propoxide withdraws electron density from the surface and behaves as a base catalyzing the activation of propanal and subsequent esterification and condensation reactions. These basic propoxides can readily abstract the acidic C α -H of propanal to produce the CH 3 CH (-) CH 2 O* enolate, thus initiating aldol condensation. The enolate can subsequently react with a second adsorbed propanal to form a C-C bond and a β-alkoxide alkanal intermediate. The β-alkoxide alkanal can subsequently undergo facile hydride transfer to form the 2-formyl-3-pentanone intermediate that decarbonylates to give the 3-pentanone product. Cu is unique in that it rapidly catalyzes the decarbonylation of the C 2n intermediates to form C 2n-1 3-pentanone as the major product with very small yields of C 2n products. This is likely due to the absence of Brønsted acid sites

  4. Emergence of a low spin phase in group field theory condensates (United States)

    Gielen, Steffen


    Recent results have shown how quantum cosmology models can be derived from the effective dynamics of condensate states in group field theory (GFT), where ‘cosmology is the hydrodynamics of quantum gravity’: the classical Friedmann dynamics for homogeneous, isotropic universes, as well as loop quantum cosmology (LQC) corrections to general relativity have been shown to emerge from fundamental quantum gravity. We take one further step towards strengthening the link with LQC and show, in a class of GFT models for gravity coupled to a free massless scalar field and for generic initial conditions, that GFT condensates dynamically reach a low spin phase of many quanta of geometry, in which all but an exponentially small number of quanta are characterised by a single spin j 0 (i.e. by a constant volume per quantum). As the low spin regime is reached, GFT condensates expand to exponentially large volumes, and the dynamics of the total volume follows precisely the classical Friedmann equations. This behaviour follows from a single requirement on the couplings in the GFT model under study. We present one particular simple case in which the dominant spin is the lowest one: {j}0=0 or, if this is excluded, {j}0=1/2. The type of quantum state usually assumed in the derivation of LQC is hence derived from the quantum dynamics of GFT. These results confirm and extend recent results by Oriti, Sindoni and Wilson-Ewing in the same setting.

  5. Singlet exciton condensation and bond-order-wave phase in the extended Hubbard model (United States)

    Hafez-Torbati, Mohsen; Uhrig, Götz S.


    The competition of interactions implies the compensation of standard mechanisms, which leads to the emergence of exotic phases between conventional phases. The extended Hubbard model (EHM) is a fundamental example for the competition of the local Hubbard interaction and the nearest-neighbor density-density interaction, which at half-filling and in one dimension leads to a bond-order wave (BOW) between a charge-density wave (CDW) and a quasi-long-range order Mott insulator. We study the full momentum-resolved excitation spectrum of the one-dimensional EHM in the CDW phase, and we clarify the relation between different elementary energy gaps. We show that the CDW-to-BOW transition is driven by the softening of a singlet exciton at momentum π . The BOW is realized as the condensate of this singlet exciton.

  6. Kinetic multi-layer model of gas-particle interactions in aerosols and clouds (KM-GAP: linking condensation, evaporation and chemical reactions of organics, oxidants and water

    Directory of Open Access Journals (Sweden)

    M. Shiraiwa


    Full Text Available We present a novel kinetic multi-layer model for gas-particle interactions in aerosols and clouds (KM-GAP that treats explicitly all steps of mass transport and chemical reaction of semi-volatile species partitioning between gas phase, particle surface and particle bulk. KM-GAP is based on the PRA model framework (Pöschl-Rudich-Ammann, 2007, and it includes gas phase diffusion, reversible adsorption, surface reactions, bulk diffusion and reaction, as well as condensation, evaporation and heat transfer. The size change of atmospheric particles and the temporal evolution and spatial profile of the concentration of individual chemical species can be modeled along with gas uptake and accommodation coefficients. Depending on the complexity of the investigated system and the computational constraints, unlimited numbers of semi-volatile species, chemical reactions, and physical processes can be treated, and the model shall help to bridge gaps in the understanding and quantification of multiphase chemistry and microphysics in atmospheric aerosols and clouds.

    In this study we demonstrate how KM-GAP can be used to analyze, interpret and design experimental investigations of changes in particle size and chemical composition in response to condensation, evaporation, and chemical reaction. For the condensational growth of water droplets, our kinetic model results provide a direct link between laboratory observations and molecular dynamic simulations, confirming that the accommodation coefficient of water at ~270 K is close to unity (Winkler et al., 2006. Literature data on the evaporation of dioctyl phthalate as a function of particle size and time can be reproduced, and the model results suggest that changes in the experimental conditions like aerosol particle concentration and chamber geometry may influence the evaporation kinetics and can be optimized for efficient probing of specific physical effects and parameters. With regard to oxidative

  7. Investigations on the liquid crystalline phases of cation-induced condensed DNA (United States)

    Pillai, C. K. S.; Sundaresan, Neethu; Radhakrishnan Pillai, M.; Thomas, T.; Thomas, T. J.


    Viral and nonviral condensing agents are used in gene therapy to compact oligonucleotides and plasmid DNA into nanostructures for their efficient transport through the cell membranes. Whereas viral vectors are best by the toxic effects on the immune system, most of the nonviral delivery vehicles are not effective for use in clinical system. Recent investigations indicate that the supramolecular organization of DNA in the condensed state is liquid crystalline. The present level of understanding of the liquid crystalline phase of DNA is inadequate and a thorough investigation is required to understand the nature, stability, texture and the influence of various environmental conditions on the structure of the phase. The present study is mainly concerned with the physico-chemical investigations on the liquid crystalline transitions during compaction of DNA by cationic species such as polyamines and metallic cations. As a preliminary to the above investigation, studies were conducted on the evolution of mesophase transitions of DNA with various cationic counterion species using polarized light microscopy. These studies indicated significant variations in the phase behaviour of DNA in the presence of Li and other ions. Apart from the neutralization of the charges on the DNA molecule, these ions are found to influence selectively the hydration sphere of DNA that in turn influences the induction and stabilization of the LC phases. The higher stability observed with the liquid crystalline phases of Li--DNA system could be useful in the production of nanostructured DNA. In the case of the polyamine, a structural specificity effect depending on the nature, charge and structure of the polyamine used has been found to be favoured in the crystallization of DNA.

  8. Multiple pollutant removal using the condensing heat exchanger: Phase 1 final report, October 1995--July 1997

    Energy Technology Data Exchange (ETDEWEB)

    Bailey, R.T.; Jankura, B.J.; Kudlac, G.A.


    The Integrated Flue Gas Treatment (IFGT) system is a new concept whereby a Teflon{reg_sign} covered condensing heat exchanger is adapted to remove certain flue gas constitutents, both particulate and gaseous, while recovering low level heat. Phase 1 includes two experimental tasks. One task dealt principally with the pollutant removal capabilities of the IFGT at a scale of about 1.2MW{sub t}. The other task studied the durability of the Teflon{reg_sign} covering to withstand the rigors of abrasive wear by fly ash emitted as a result of coal combustion. The pollutant removal characteristics of the IFGT system were measured over a wide range of operating conditions. The coals tested included high, medium and low-sulfur coals. The flue gas pollutants studied included ammonia, hydrogen chloride, hydrogen fluoride, particulate, sulfur dioxide, gas phase and particle phase mercury and gas phase and particle phase trace elements. The particulate removal efficiency and size distribution was investigated. These test results demonstrated that the IFGT system is an effective device for both acid gas absorption and fine particulate collection. The durability of the Teflon{reg_sign} covered heat exchanger tubes was studied on a pilot-scale single-stage condensing heat exchanger (CHX{reg_sign}). Data from the test indicate that virtually no decrease in Teflon{reg_sign} thickness was observed for the coating on the first two rows of heat exchanger tubes, even at high inlet particulate loadings. Evidence of wear was present only at the microscopic level, and even then was very minor in severity.

  9. 2008 Summer Research Institute Interfacial and Condensed Phase Chemical Physics Annual Report

    Energy Technology Data Exchange (ETDEWEB)

    Garrett, Bruce C.; Tonkyn, Russell G.; Avery, Nachael B.


    For the fifth year, the Pacific Northwest National Laboratory in Richland, Washington, invited graduate students, postdoctoral fellows, university faculty, and students entering graduate students from around the world to participate in the Summer Research Institute in Interfacial and Condensed Phase Chemical Physics. The institute offers participants the opportunity to gain hands-on experience in top-notch research laboratories while working along internationally respected mentors. Of the 38 applicants, 20 were accepted for the 8- to 10-week program. The participants came from universities as close as Seattle and Portland and as far away as Germany and Singapore. At Pacific Northwest National Laboratory, the 20 participants were mentored by 13 scientists. These mentors help tailor the participant’s experience to the needs of that person. Further, the mentors provide guidance on experimental and theoretical techniques, research design and completion, and other aspects of scientific careers in interfacial and condensed phase chemical physics. The research conducted at the institute can result in tangible benefits for the participants. For example, many have co-authored papers that have been published in peer-reviewed journals, including top-rated journals such as Science. Also, they have presented their research at conferences, such as the Gordon Research Conference on Dynamics at Surfaces and the AVS national meeting. Beyond that, many of the participants have started building professional connections with researchers at Pacific Northwest National Laboratory, connections that will serve them well during their careers.

  10. Synthesis of 1,5-Benzodiazepine and Its Derivatives by Condensation Reaction Using H-MCM-22 as Catalyst

    Directory of Open Access Journals (Sweden)

    Sheikh Abdul Majid


    Full Text Available A simple and versatile method for the synthesis of 1,5-benzodiazepines is via condensation of o-phenylenediamines (OPDA and ketones in the presence of catalytic amount of H-MCM-22 using acetonitrile as solvent at room temperature. In all the cases, the reactions are highly selective and are completed within 1–3 h. The method is applicable to both cyclic and acyclic ketones without significant differences. The reaction proceeds efficiently under ambient conditions with good-to-excellent yields.

  11. Experiment and Simulation Study on the Special Phase Behavior of Huachang Near-Critical Condensate Gas Reservoir Fluid

    Directory of Open Access Journals (Sweden)

    Dali Hou


    Full Text Available Due to the special phase behavior of near-critical fluid, the development approaches of near-critical condensate gas and near-critical volatile oil reservoirs differ from conventional oil and gas reservoirs. In the near-critical region, slightly reduced pressure may result in considerable change in gas and liquid composition since a large amount of gas or retrograde condensate liquid is generated. It is of significance to gain insight into the composition variation of near-critical reservoir during the depletion development. In our study, we performed a series of PVT experiments on a real near-critical gas condensate reservoir fluid. In addition to the experimental studies, a commercial simulator combined with the PREOS model was utilized to study retrograde condensate characteristics and reevaporation mechanism of condensate oil with CO2 injection based on vapor-liquid phase equilibrium thermodynamic theory. The research shows that when reservoir pressure drops below a certain pressure, the variation of retrograde condensate liquid saturation of the residual reservoir fluid exhibits the phase behavior of volatile oil.

  12. Amine-Functionalized Sugarcane Bagasse: A Renewable Catalyst for Efficient Continuous Flow Knoevenagel Condensation Reaction at Room Temperature. (United States)

    Qiao, Yanhui; Teng, Junjiang; Wang, Shuangfei; Ma, Hao


    A biomass-based catalyst with amine groups (-NH₂), viz., amine-functionalized sugarcane bagasse (SCB-NH₂), was prepared through the amination of sugarcane bagasse (SCB) in a two-step process. The physicochemical properties of the catalyst were characterized through FT-IR, elemental analysis, XRD, TG, and SEM-EDX techniques, which confirmed the -NH₂ group was grafted onto SCB successfully. The catalytic performance of SCB-NH₂ in Knoevenagel condensation reaction was tested in the batch and continuous flow reactions. Significantly, it was found that the catalytic performance of SCB-NH₂ is better in flow system than that in batch system. Moreover, the SCB-NH₂ presented an excellent catalytic activity and stability at the high flow rate. When the flow rate is at the 1.5 mL/min, no obvious deactivation was observed and the product yield and selectivity are more than 97% and 99% after 80 h of continuous reaction time, respectively. After the recovery of solvent from the resulting solution, a white solid was obtained as a target product. As a result, the SCB-NH₂ is a promising catalyst for the synthesis of fine chemicals by Knoevenagel condensation reaction in large scale, and the modification of the renewable SCB with -NH₂ group is a potential avenue for the preparation of amine-functionalized catalytic materials in industry.

  13. Purification and Characterization of OleA from Xanthomonas campestris and Demonstration of a Non-decarboxylative Claisen Condensation Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Frias, JA; Richman, JE; Erickson, JS; Wackett, LP


    OleA catalyzes the condensation of fatty acyl groups in the first step of bacterial long-chain olefin biosynthesis, but the mechanism of the condensation reaction is controversial. In this study, OleA from Xanthomonas campestris was expressed in Escherichia coli and purified to homogeneity. The purified protein was shown to be active with fatty acyl-CoA substrates that ranged from C(8) to C(16) in length. With limiting myristoyl-CoA (C(14)), 1 mol of the free coenzyme A was released/mol of myristoyl-CoA consumed. Using [(14)C] myristoyl-CoA, the other products were identified as myristic acid, 2-myristoylmyristic acid, and 14-heptacosanone. 2-Myristoylmyristic acid was indicated to be the physiologically relevant product of OleA in several ways. First, 2-myristoylmyristic acid was the major condensed product in short incubations, but over time, it decreased with the concomitant increase of 14-heptacosanone. Second, synthetic 2-myristoylmyristic acid showed similar decarboxylation kinetics in the absence of OleA. Third, 2-myristoylmyristic acid was shown to be reactive with purified OleC and OleD to generate the olefin 14-heptacosene, a product seen in previous in vivo studies. The decarboxylation product, 14-heptacosanone, did not react with OleC and OleD to produce any demonstrable product. Substantial hydrolysis of fatty acyl-CoA substrates to the corresponding fatty acids was observed, but it is currently unclear if this occurs in vivo. In total, these data are consistent with OleA catalyzing a non-decarboxylative Claisen condensation reaction in the first step of the olefin biosynthetic pathway previously found to be present in at least 70 different bacterial strains.

  14. A green route to methyl acrylate and acrylic acid by an aldol condensation reaction over H-ZSM-35 zeolite catalysts. (United States)

    Ma, Zhanling; Ma, Xiangang; Liu, Hongchao; He, Yanli; Zhu, Wenliang; Guo, Xinwen; Liu, Zhongmin


    A one-step aldol condensation reaction to produce MA and AA is a green and promising strategy. Here, the aldol condensation reaction was first conducted with DMM and MAc over different types of zeolite catalysts. The H-ZSM-35 zeolite demonstrates excellent catalytic performance with a DMM conversion of 100% and a MA + AA selectivity of up to 86.2% and superior regeneration ability, with great potential for industrial operation.

  15. Heat-transfer enhancement of two-phase closed thermosyphon using a novel cross-flow condenser (United States)

    Aghel, Babak; Rahimi, Masoud; Almasi, Saeed


    The present study reports the heat-transfer performance of a two-phase closed thermosyphon (TPCT) equipped with a novel condenser. Distillated water was used as working fluid, with a volumetric liquid filling ratio of 75 %. An increase in heat flux was used to measure the response of the TPCT, including variations in temperature distribution, thermal resistance, average temperature of each section of TPCT and overall thermal difference. Results show that for various power inputs from 71 to 960 W, the TPCT with the novel condenser had a lower wall-temperature difference between the evaporator and condenser sections than did the unmodified TPCT. Given the experimental data for heat-transfer performance, it was found that the thermal resistance in the TPCT equipped with the proposed condenser was between 10 and 17 % lower than in the one without.

  16. Computational studies of adsorption in metal organic frameworks and interaction of nanoparticles in condensed phases

    Energy Technology Data Exchange (ETDEWEB)

    Annapureddy, HVR; Motkuri, RK; Nguyen, PTM; Truong, TB; Thallapally, PK; McGrail, BP; Dang, LX


    In this review, we describe recent efforts to systematically study nano-structured metal organic frameworks (MOFs), also known as metal organic heat carriers, with particular emphasis on their application in heating and cooling processes. We used both molecular dynamics and grand canonical Monte Carlo simulation techniques to gain a molecular-level understanding of the adsorption mechanism of gases in these porous materials. We investigated the uptake of various gases such as refrigerants R12 and R143a. We also evaluated the effects of temperature and pressure on the uptake mechanism. Our computed results compared reasonably well with available measurements from experiments, thus validating our potential models and approaches. In addition, we investigated the structural, diffusive and adsorption properties of different hydrocarbons in Ni-2(dhtp). Finally, to elucidate the mechanism of nanoparticle dispersion in condensed phases, we studied the interactions among nanoparticles in various liquids, such as n-hexane, water and methanol.


    Directory of Open Access Journals (Sweden)

    W. M. CHIN


    Full Text Available The non-uniformity of two-phase flow rates among the circuits in a heat exchanger reduces its thermal performance. In this work, the effects of a maldistributed condensing two-phase flow profile in an arbitrary cross-flow heat exchanger has been investigated. The results of a discretization numerical analysis shows that the trend of the degradation effect is similar to that found for single phase flows. The thermal performance degradation factor, D, is dependent on the standard deviation and skew of the flow profile and the change of vapour quality along the flow circuits. The magnitude of D varies as the square of normalized standard deviation and liquid Reynolds number, and linearly with the normalized skew. However, the effect of vapour quality is not as significant as compared to that caused by the statistical moments of probability function of the flow maldistribution profile. Flows with low standard deviation and positive skew are preferred to give low magnitudes of D.

  18. Coupled Cluster in Condensed Phase. Part II: Liquid Hydrogen Fluoride from Quantum Cluster Equilibrium Theory. (United States)

    Spickermann, Christian; Perlt, Eva; von Domaros, Michael; Roatsch, Martin; Friedrich, Joachim; Kirchner, Barbara


    Treating the bulk phase with high-level ab initio methods, such as coupled cluster, is a nontrivial task because of the computational costs of these electronic structure methods. In this part of our hydrogen fluoride study we make use of the quantum cluster equilibrium method, which employs electronic structure input of small clusters and combines it with simple statistical mechanics in order to describe condensed phase phenomena. If no parameter adjustment is applied, then the lower quantum chemical methods, such as density functional theory in conjunction with the generalized gradient approximation, provide wrong results in accordance with the description of the strength of the interaction in the clusters. While density functional theory describes the liquid phase too dense due to overbinding of the clusters, the coupled cluster method and the perturbation theory at the complete basis set limit agree well with experimental observations. If we allow the two parameters in the quantum cluster equilibrium method to vary, then these are able to compensate the overbinding, thereby leading to very good agreement with experiment. Correlated methods in combination with small basis sets giving rise to too weakly bound clusters cannot reach this accuracy even if the parameters are flexible. Only at the complete basis set limit, the performance of the correlated methods is again excellent.

  19. Dual phase multiplex polymerase chain reaction

    Energy Technology Data Exchange (ETDEWEB)

    Pemov, Alexander [Charlottesville, VA; Bavykin, Sergei [Darien, IL


    Highly specific and sensitive methods were developed for multiplex amplification of nucleic acids on supports such as microarrays. Based on a specific primer design, methods include five types of amplification that proceed in a reaction chamber simultaneously. These relate to four types of multiplex amplification of a target DNA on a solid support, directed by forward and reverse complex primers immobilized to the support and a fifth type--pseudo-monoplex polymerase chain reaction (PCR) of multiple targets in solution, directed by a single pair of unbound universal primers. The addition of the universal primers in the reaction mixture increases the yield over the traditional "bridge" amplification on a solid support by approximately ten times. Methods that provide multitarget amplification and detection of as little as 0.45-4.5.times.10.sup.-12 g (equivalent to 10.sup.2-10.sup.3 genomes) of a bacterial genomic DNA are disclosed.

  20. Quantum Phases with Bose-Condensed Cesium Atoms in an Optical Lattice (United States)

    Zhang, Xibo; Hung, Chen-Lung; Gemelke, Nathan; Chin, Cheng


    The realization of the Mott-insulator to superfluid phase transition with neutral atoms in an optical lattice provides a tantalizing opportunity to test many-body physics with a high degree of accuracy. We report progress on an experimental and quantitative comparison of the superfluid to Mott-insulator quantum phase boundary with results from the Bose-Hubbard model, using Bose-condensed cesium atoms confined to a thin layer of an optical lattice potential. Feshbach resonances with cesium atoms enable us to scan the on-site interaction over a wide range without modifying the tunneling rate and the overall trapping potential; chemical potential can be adjusted by loading a varied mean atomic density into the lattice. We describe the physical apparatus constructed for this investigation, including novel construction designed to achieve precise and agile control of the magnetic field used in tuning interactions, adiabatic loading and manipulation of the lattice potential, and tight two-dimensional confinement applied to negate the effect of gravity without sacrifice in system homogeneity.

  1. Bose–Einstein condensation and liquid–gas phase transition in strongly interacting matter composed of α particles (United States)

    Satarov, L. M.; Gorenstein, M. I.; Motornenko, A.; Vovchenko, V.; Mishustin, I. N.; Stoecker, H.


    Systems of Bose particles with both repulsive and attractive interactions are studied using the Skyrme-like mean-field model. The phase diagram of such systems exhibits two special lines in the chemical potential-temperature plane: one line which represents the first-order liquid–gas phase transition with the critical end point, and another line which represents the onset of Bose–Einstein condensation. The calculations are made for strongly interacting matter composed of α particles. The phase diagram of this matter is qualitatively similar to that observed for the atomic 4He liquid. The sensitivity of the results to the model parameters is studied. For weak interaction coupling, the critical point is located at the Bose-condensation line.

  2. Thermally activated phase slips of a Bose-Einstein condensate in a ring trap (United States)

    Kunimi, Masaya; Danshita, Ippei


    Recently, the NIST group has experimentally measured the lifetime of the superflow of Bose-Einstein condensates in ring traps and found that it significantly depends on the temperature. If the superflow decays dominantly due to thermally activated phase slips(TAPS), the lifetime is expected to obey the Arrhenius law. They argued that the measured lifetime is inconsistent with the Arrhenius law. However, their estimation of the energy barrier, which determines a dominant contribution to the temperature dependence of the lifetime, is not quantitatively accurate so that more profound theoretical analyses are needed in order to examine the possibility of the superflow decay via TAPS. In this work, we quantitatively calculate the lifetime of the superflow due to TAPS by the Kramers formula combined with the mean-filed theory. Recently, this formalism has been successfully applied to explaining the experiments of the damping of dipole oscillations of 1D Bose gases in optical lattices, in terms of TAPS. We will compare our results with the NIST experiment.

  3. A novel artificial condensed matter lattice and a new platform for one-dimensional topological phases. (United States)

    Belopolski, Ilya; Xu, Su-Yang; Koirala, Nikesh; Liu, Chang; Bian, Guang; Strocov, Vladimir N; Chang, Guoqing; Neupane, Madhab; Alidoust, Nasser; Sanchez, Daniel; Zheng, Hao; Brahlek, Matthew; Rogalev, Victor; Kim, Timur; Plumb, Nicholas C; Chen, Chaoyu; Bertran, François; Le Fèvre, Patrick; Taleb-Ibrahimi, Amina; Asensio, Maria-Carmen; Shi, Ming; Lin, Hsin; Hoesch, Moritz; Oh, Seongshik; Hasan, M Zahid


    Engineered lattices in condensed matter physics, such as cold-atom optical lattices or photonic crystals, can have properties that are fundamentally different from those of naturally occurring electronic crystals. We report a novel type of artificial quantum matter lattice. Our lattice is a multilayer heterostructure built from alternating thin films of topological and trivial insulators. Each interface within the heterostructure hosts a set of topologically protected interface states, and by making the layers sufficiently thin, we demonstrate for the first time a hybridization of interface states across layers. In this way, our heterostructure forms an emergent atomic chain, where the interfaces act as lattice sites and the interface states act as atomic orbitals, as seen from our measurements by angle-resolved photoemission spectroscopy. By changing the composition of the heterostructure, we can directly control hopping between lattice sites. We realize a topological and a trivial phase in our superlattice band structure. We argue that the superlattice may be characterized in a significant way by a one-dimensional topological invariant, closely related to the invariant of the Su-Schrieffer-Heeger model. Our topological insulator heterostructure demonstrates a novel experimental platform where we can engineer band structures by directly controlling how electrons hop between lattice sites.

  4. Rare events and phase transitions in reaction-diffusion systems (United States)

    Elgart, Vlad

    The last decade witnessed a rapid growth of interest in reaction-diffusion models. Such models are employed for the description of phenomena ranging from the kinetics of chemical reactions to the evolution of biological populations. Reaction-diffusion (RD) systems provide a way to translate local assumptions about movement, mortality and reproduction of individuals into global conclusions about the persistence or extinction of populations. Recently, RD models in low dimensions have been investigated extensively with an emphasis on fluctuation-dominated effects, specifically, the breakdown of the standard chemical rate equations which correspond to the "mean-field" approximation of reaction kinetics. Recent interest has been largely focused on the description of dynamical phase transitions in reaction-diffusion systems. An important example is the absorbing phase transitions. Upon such a transition the system goes from an active ("living") state to an absorbing ("dead") state with no escape from it. We explore a broad class of single species models, trying to quantitatively estimate various aspects of reaction kinetics. Among the questions we have been studying are estimates of rare events probabilities and classification of absorbing phase transitions. We develop a rigorous, simple, and efficient method to calculate the rare event statistics in reaction-diffusion systems. To this end, we develop a Hamiltonian formulation of reaction-diffusion dynamics. Although the system is specified by a set of rules, rather than a Hamiltonian, one may nevertheless show that there is a certain canonical Hamiltonian associated with the systems dynamics. As for absorbing phase transitions, we suggest a simple scheme, making it possible to have, at least, an educated guess regarding the universality class of a reaction-diffusion model at hand. The scheme is based on the topology of phase portraits of the system's Hamiltonian.

  5. Models of glycolysis: Glyceraldehyde as a source of energy and monomers for prebiotic condensation reactions (United States)

    Weber, A. L.


    All organisms require energy in a chemical form for maintenance and growth. In contemporary life this chemical energy is obtained by the synthesis of the phosphoanhydride bonds of ATP. Among the biological processes that yield ATP, fermentation is generally considered primitive, because it operates under anaerobic conditions by substrate-level phosphorylation which does not require compartmentation by membranes. Fermentation by the glycolytic pathway, which is found in almost every living cell, is an especially attractive energy source for primitive life. Glycolysis not only produces useful chemical energy (ATP), but intermediates of this pathway are also involved in amino acid synthesis and photosynthetic carbon-fixation. It is believed that energy and substrates needed for the origin of life were provided by nonenzymatic chemical reactions that resemble the enzyme-mediated reactions of glycolysis. These nonenzymatic reactions would have provided a starting point for the evolutionary development of glycolysis.

  6. Reaction engineering of co-condensing (methyl)ethoxysilane mixtures: Kinetic characterization and modeling

    Energy Technology Data Exchange (ETDEWEB)



    Molecular homogeneity frequently plays a decisive role in the effective application of organically modified silicate copolymers. However, methods of directly characterizing copolymerization extent in siloxanes generated from mixed alkoxysilanes are not always available or convenient. The authors present an alternative tool for determining kinetic parameters for models of alkoxysilane hydrolytic copolycondensation. Rather than restricting attention to single step batch reactors, they use a semibatch reactor with varying time of injection of one component. They describe the fitting method and show that all necessary kinetic parameters can be determined from a series of ordinary {sup 29}Si NMR data in a straightforward case study: copolymerization of dimethyldiethoxy silane and trimethylethoxysilane. Under conditions providing no direct {sup 29}Si NMR signature of copolymerization, they find kinetic trends consistent with those previously reported. As further validation, the results of a new series of experiments (varying the ratio of mono-functional to difunctional monomer) are predicted by the semibatch copolymerization model and measured parameters. Based on these results, they are able to calculate the molecular homogeneity in the copolymer products investigated. Even for this relatively simple system, the optimal injection time is a complex function of residence time, but early injection of the faster-condensing monomer gives the best homogeneity at long residence times.

  7. Photoluminescence quenching of porous silicon in gas and liquid phases - the role of dielectric quenching and capillary condensation effects

    Energy Technology Data Exchange (ETDEWEB)

    Dian, Juraj [Department of Chemical Physics and Optics, Faculty of Mathematics and Physics, Charles University Prague, Ke Karlovu 3, 121 16 Prague 2 (Czech Republic); Chvojka, Tomas; Vrkoslav, Vladimir; Jelinek, Ivan [Department of Analytical Chemistry, Faculty of Sciences, Charles University Prague, Hlavova 2030, 128 40 Prague 2 (Czech Republic)


    We present a systematic study of porous silicon photoluminescence quenching in the presence of precisely controlled amounts of linear aliphatic alcohols (from methanol to hexanol) in gas and liquid phases. From the concentration dependence of photoluminescence quenching response we determined sensitivity of porous silicon sensor for studied analytes. The sensor sensitivity revealed nearly monotonous change with the length of alcohol molecule within the homological set of alcohols in both gas and liquid phases. However, while in gas phase the sensor sensitivity rose with the length of alcohol chain, in liquid phase we observed the opposite behaviour. Photoluminescence quenching behaviour in liquid phase is very well explained by exciton dielectric quenching mechanism. In gas phase photoluminescence quenching depends both on analyte dielectric constant and analyte equilibrium concentration inside porous matrix which is controlled by capillary condensation effect. (copyright 2005 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  8. Vapor condensation behind the shock wave in vapor-liquid two-phase media (United States)

    Syoji, Chiharu; Oshiro, Naoto

    Laser extinction, schlieren photography, and in situ pressure measurements are used to characterize vapor condensation behind a shock wave in a diaphragm shock tube with a low-pressure chamber filled with ethanol, water, or freon-11 vapor. The experimental setup is briefly described, and the results are presented graphically and discussed in detail. Condensation, lasting a few hundred microsec before reevaporation sets in, is found to decrease the intensity of the shock front and lower the pressure behind it.

  9. Thermodynamic analysis and synthesis of porous Mo{sub 2}C sponge by vapor-phase condensation and in situ carburization of MoO{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Cetinkaya, S. [Istanbul University, Engineering Faculty, Department of Materials and Metallurgical Engineering, Avcilar, Istanbul (Turkey); Eroglu, S., E-mail: [Istanbul University, Engineering Faculty, Department of Materials and Metallurgical Engineering, Avcilar, Istanbul (Turkey)


    Spongy porous MoO{sub 3} deposits were grown by vaporization, vapor-phase transportation and condensation of MoO{sub 3} in Ar flow. It was observed that increased source temperature ({>=}1200 K) and temperature gradient ({>=}100 K/cm) favor the formation of spongy deposit owing to high supersaturation of the oxide vapor at {approx}900 K. Spongy Mo{sub 2}C deposits consisting of intermingled platelet crystals with thin walls were synthesized by in situ carburization of the condensed MoO{sub 3} using 0.05-0.1 mol of CH{sub 4} and 1 mol of H{sub 2} at 900 K. Thermodynamic analysis in the Mo-O-C-H system was used as a guide to predict the conditions for the formation of Mo{sub 2}C from the MoO{sub 3}-CH{sub 4}-H{sub 2} reactants at 900 K. X-ray diffraction analysis showed that the carburized deposits consisted of single phase Mo{sub 2}C, in agreement with the thermodynamic prediction. The equilibrium analysis was also used to reveal possible reaction pathways to Mo{sub 2}C formation from MoO{sub 3}-CH{sub 4}-H{sub 2} reactants which yielded gaseous products of H{sub 2}O, CO{sub 2}, CO, C{sub 2}H{sub 6} and C{sub 2}H{sub 4}.

  10. Simplified heat transfer modeling for Vapour Phase Soldering based on filmwise condensation for different horizontal Printed Circuit Boards (United States)

    Géczy, Attila; Illés, Balázs; Péter, Zsolt; Illyefalvi-Vitéz, Zsolt


    The paper presents a method for investigating heat transfer during a specific reflow soldering method, Vapour Phase Soldering (VPS), where a horizontal Printed Circuit Board (PCB) is heated in vapour medium. The paper presents refined descriptions of filmwise condensation which were investigated and adjusted for the VPS process. The results show a proper and fast approximation of measurements. The dependence of the PCB characteristic length is also investigated.

  11. Non-Markovian response of ultrafast coherent electronic ring currents in chiral aromatic molecules in a condensed phase (United States)

    Mineo, H.; Lin, S. H.; Fujimura, Y.; Xu, J.; Xu, R. X.; Yan, Y. J.


    Results of a theoretical study on non-Markov response for femtosecond laser-driven coherent ring currents in chiral aromatic molecules embedded in a condensed phase are presented. Coherent ring currents are generated by coherent excitation of a pair of quasi-degenerated π-electronic excited states. The coherent electronic dynamical behaviors are strongly influenced by interactions between the electronic system and phonon bath in a condensed phase. Here, the bath correlation time is not instantaneous but should be taken to be a finite time in ultrashort time-resolved experiments. In such a case, Markov approximation breaks down. A hierarchical master equation approach for an improved semiclassical Drude dissipation model was adopted to examine the non-Markov effects on ultrafast coherent electronic ring currents of (P)-2,2'-biphenol in a condensed phase. Time evolution of the coherent ring current derived in the hierarchical master equation approach was calculated and compared with those in the Drude model in the Markov approximation and in the static limit. The results show how non-Markovian behaviors in quantum beat signals of ring currents depend on the Drude bath damping constant. Effects of temperatures on ultrafast coherent electronic ring currents are also clarified.

  12. Electrochemical reactions on catalyst particles with three-phase boundaries. (United States)

    Zhdanov, V P


    In fuel cells, electrochemical reactions are often assumed to occur on metal catalyst particles contacting simultaneously the ion-conducting electrolyte and gas phase. Our kinetic Monte Carlo simulations demonstrate that in this case the deviations from the Tafel law in the dependence of the reaction rate on the electrode potential may be related to diffusion of one of the adsorbed reactants along catalyst particles.

  13. Sensitive inexpensive spectrophotometric and spectrofluorimetric analysis of ezogabine, levetiracetam and topiramate in tablet formulations using Hantzsch condensation reaction (United States)

    Ibrahim, F. A.; El-Yazbi, A. F.; Wagih, M. M.; Barary, M. A.


    Two highly sensitive, simple and selective spectrophotometric and spectrofluorimetric assays have been investigated for the analysis of ezogabine, levetiracetam and topiramate in their pure and in pharmaceutical dosage forms. The suggested methods depend on the condensation of the primary amino-groups in the three drugs with acetylacetone and formaldehyde according to Hantzsch reaction yielding highly fluorescent yellow colored dihydropyridine derivatives. The reaction products of ezogabine, levetiracetam and topiramate were measured spectrophotometrically at 418, 390 and 380 nm or spectrofluorimetrically at λem/ex of 495/425 nm, 490/415 nm and 488/410 nm, respectively. Various experimental conditions have been carefully studied to maximize the reaction yield. At the optimum reaction conditions, the calibration curves were rectilinear over the concentration ranges of 8-25, 60-180 and 80-200 μg/mL spectrophotometrically and 0.02-0.2, 0.2-1.2 and 0.2-1.5 μg/mL spectrofluorimetrically for ezogabine, levetiracetam and topiramate, respectively with good correlation coefficients. The suggested methods were applied successfully for the analysis of ezogabine, levetiracetam and topiramate in their commercial tablets with high percentage recoveries and negligible interference from various excipients in pharmaceutical dosage forms. The results were statistically analyzed and showed the absence of any significant difference between both developed and published methods. The procedures were validated and evaluated by the ICH guidelines revealing good reproducibility and accuracy. Therefore, the two proposed methods may be considered of high interest for practical and reliable analysis of ezogabine, levetiracetam and topiramate in pharmaceutical dosage forms.

  14. Condensation versus long-range interaction: Competing quantum phases in bosonic optical lattice systems at near-resonant Rydberg dressing (United States)

    Geißler, Andreas; Vasić, Ivana; Hofstetter, Walter


    Recent experiments have shown that (quasi)crystalline phases of Rydberg-dressed quantum many-body systems in optical lattices (OL) are within reach. Rydberg systems naturally possess strong long-range interactions due to the large polarizability of Rydberg atoms. Thus a wide range of quantum phases has been predicted, such as a devil's staircase of lattice-incommensurate density wave phases as well as the more exotic lattice supersolid order for bosonic systems, as considered in our work. Guided by results in the "frozen"-gas limit, we study the ground-state phase diagram at finite hopping amplitudes and in the vicinity of resonant Rydberg driving while fully including the long-range tail of the van der Waals interaction. Simulations within real-space bosonic dynamical mean-field theory yield an extension of the devil's staircase into the supersolid regime where the competition of condensation and interaction leads to a sequence of crystalline phases.

  15. Geometric phase effects in ultracold hydrogen exchange reaction (United States)

    Hazra, Jisha; Kendrick, Brian K.; Balakrishnan, N.


    The role of the geometric phase effect on chemical reaction dynamics is explored by examining the hydrogen exchange process in the fundamental H+HD reaction. Results are presented for vibrationally excited HD molecules in the v = 4 vibrational level and for collision energies ranging from 1 μK to 100 K. It is found that, for collision energies below 3 K, inclusion of the geometric phase leads to dramatic enhancement or suppression of the reaction rates depending on the final quantum state of the HD molecule. The effect was found to be the most prominent for rotationally resolved integral and differential cross sections but it persists to a lesser extent in the vibrationally resolved and total reaction rate coefficients. However, no significant GP effect is present in the reactive channel leading to the D+H2 product or in the D+H2 (v=4,j=0) \\to HD+H reaction. A simple interference mechanism involving inelastic (nonreactive) and exchange scattering amplitudes is invoked to account for the observed GP effects. The computed results also reveal a shape resonance in the H+HD reaction near 1 K and the GP effect is found to influence the magnitude of the resonant part of the cross section. Experimental detection of the resonance may allow a sensitive probe of the GP effect in the H+HD reaction.

  16. Spontaneous Spin Bifurcations and Ferromagnetic Phase Transitions in a Spinor Exciton-Polariton Condensate

    Directory of Open Access Journals (Sweden)

    H. Ohadi


    Full Text Available We observe a spontaneous parity breaking bifurcation to a ferromagnetic state in a spatially trapped exciton-polariton condensate. At a critical bifurcation density under nonresonant excitation, the whole condensate spontaneously magnetizes and randomly adopts one of two elliptically polarized (up to 95% circularly polarized states with opposite handedness of polarization. The magnetized condensate remains stable for many seconds at 5 K, but at higher temperatures, it can flip from one magnetic orientation to another. We optically address these states and demonstrate the inversion of the magnetic state by resonantly injecting 100-fold weaker pulses of opposite spin. Theoretically, these phenomena can be well described as spontaneous symmetry breaking of the spin degree of freedom induced by different loss rates of the linear polarizations.

  17. Formation of new stable pigments from condensation reaction between malvidin 3-glucoside and (-)-epicatechin mediated by acetaldehyde: Effect of tartaric acid concentration. (United States)

    Sun, Baoshan; Barradas, Tania; Leandro, Conceição; Santos, Cláudia; Spranger, Isabel


    The objective of this work was to study the effect of tartaric acid concentration on the condensation reaction between malvidin 3-glucoside (Mv-glc) and flavanols mediated by acetaldehyde in the model solution. The model wine solutions were prepared by 12% ethanol in water (v/v) with two different l-tartaric acid concentrations (5g/l and 25g/l, respectively) and at two different pH values (3.2 and 1.7, respectively). Four new pigments were detected in model wine solutions containing Mv-glc, (-)-epicatechin and acetaldehyde. By reverse-phase HPLC-DAD, ESI-MS and MS(n) fragmentation analysis, the four new pigments were tentatively identified as four isomers of hydroxyethyl malvidin-3-glucoside-ethyl-flavanol. The decrease in the concentration of Mv-glc and (-)-epicatechin and the increase in the concentration of the new identified pigments were more pronounced at higher tartaric acid concentration. At pH 1.7, although the two well-recognized ethyl-linked Mv-glc-flavanol isomers were quantitatively the major pigmented products in the reaction solution throughout the assay period, they appeared less stable than the four new pigments. At pH 3.2, the rate of formation of ethyl-linked Mv-glc-flavanol pigments was much slower than at pH 1.7, whereas the four new pigments were quantitatively the predominant pigmented products at the latter stage of the reaction. Copyright © 2008 Elsevier Ltd. All rights reserved.

  18. Formation of Gas-Phase Formate in Thermal Reactions of Carbon Dioxide with Diatomic Iron Hydride Anions. (United States)

    Jiang, Li-Xue; Zhao, Chongyang; Li, Xiao-Na; Chen, Hui; He, Sheng-Gui


    The hydrogenation of carbon dioxide involves the activation of the thermodynamically very stable molecule CO2 and formation of a C-H bond. Herein, we report that HCO2- and CO can be formed in the thermal reaction of CO2 with a diatomic metal hydride species, FeH- . The FeH- anions were produced by laser ablation, and the reaction with CO2 was analyzed by mass spectrometry and quantum-chemical calculations. Gas-phase HCO2- was observed directly as a product, and its formation was predicted to proceed by facile hydride transfer. The mechanism of CO2 hydrogenation in this gas-phase study parallels similar behavior of a condensed-phase iron catalyst. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Phase collapse and revival of a 1-mode Bose-Einstein condensate induced by an off-resonant optical probe field and superselection rules (United States)

    Arruda, L. G. E.; Prataviera, G. A.; de Oliveira, M. C.


    Phase collapse and revival for Bose-Einstein condensates are nonlinear phenomena appearing due to atomic collisions. While it has been observed in a general setting involving many modes, for one-mode condensates its occurrence is forbidden by the particle number superselection rule (SSR), which arises because there is no phase reference available. We consider a single mode atomic Bose-Einstein condensate interacting with an off-resonant optical probe field. We show that the condensate phase revival time is dependent on the atom-light interaction, allowing optical control on the atomic collapse and revival dynamics. Incoherent effects over the condensate phase are included by considering a continuous photo-detection over the probe field. We consider conditioned and unconditioned photo-counting events and verify that no extra control upon the condensate is achieved by the probe photo-detection, while further inference of the atomic system statistics is allowed leading to a useful test of the SSR on particle number and its imposition on the kind of physical condensate state.

  20. Theoretical and Computational Studies of Condensed-Phase Phenomena: The Origin of Biological Homochirality, and the Liquid-Liquid Phase Transition in Network-Forming Fluids (United States)

    Ricci, Francesco

    This dissertation describes theoretical and computational studies of the origin of biological homochirality, and the existence of a liquid-liquid phase transition in pure-component network-forming fluids. A common theme throughout these studies is the use of sophisticated computer simulation and statistical mechanics techniques to study complex condensed-phase phenomena. In the first part of this dissertation, we use an elementary lattice model with molecular degrees of freedom, and satisfying microscopic reversibility, to investigate the effect of reaction reversibility on the evolution of stochastic symmetry breaking via autocatalysis and mutual inhibition in a closed system. We identify conditions under which the system's evolution towards racemic equilibrium becomes extremely slow, allowing for long-time persistence of a symmetry-broken state. We also identify a "monomer purification" mechanism, due to which a nearly homochiral state can persist for long times, even in the presence of significant reverse reaction rates. Order of magnitude estimates show that with reasonable physical parameters a symmetry broken state could persist over geologically-relevant time scales. In the second part of this dissertation, we study a chiral-symmetry breaking mechanism known as Viedma ripening. We develop a Monte Carlo model to gain further insights into the mechanisms capable of reproducing key experimental signatures associated with this phenomenon. We also provide a comprehensive investigation of how the model parameters impact the system's overall behavior. It is shown that size-dependent crystal solubility alone is insufficient to reproduce most experimental signatures, and that some form of a solid-phase chiral feedback mechanism (e.g., agglomeration) must be invoked in our model. In the third part of this dissertation, we perform rigorous free energy calculations to investigate the possibility of a liquid-liquid phase transition (LLPT) in the Stillinger-Weber (SW

  1. Water interactions with condensed organic phases: a combined experimental and theoretical study of molecular-level processes (United States)

    Johansson, Sofia M.; Kong, Xiangrui; Thomson, Erik S.; Papagiannakopoulos, Panos; Pettersson, Jan B. C.; Lovrić, Josip; Toubin, Céline


    Water uptake on aerosol particles modifies their chemistry and microphysics with important implications for air quality and climate. A large fraction of the atmospheric aerosol consists of organic aerosol particles or inorganic particles with condensed organic components. Here, we combine laboratory studies using the environmental molecular beam (EMB) method1 with molecular dynamics (MD) simulations to characterize water interactions with organic surfaces in detail. The over-arching aim is to characterize the mechanisms that govern water uptake, in order to guide the development of physics-based models to be used in atmospheric modelling. The EMB method enables molecular level studies of interactions between gases and volatile surfaces at near ambient pressure,1 and the technique may provide information about collision dynamics, surface and bulk accommodation, desorption and diffusion kinetics. Molecular dynamics simulations provide complementary information about the collision dynamics and initial interactions between gas molecules and the condensed phase. Here, we focus on water interactions with condensed alcohol phases that serve as highly simplified proxies for systems in the environment. Gas-surface collisions are in general found to be highly inelastic and result in efficient surface accommodation of water molecules. As a consequence, surface accommodation of water can be safely assumed to be close to unity under typical ambient conditions. Bulk accommodation is inefficient on solid alcohol and the condensed materials appear to produce hydrophobic surface structures, with limited opportunities for adsorbed water to form hydrogen bonds with surface molecules. Accommodation is significantly more efficient on the dynamic liquid alcohol surfaces. The results for n-butanol (BuOH) are particularly intriguing where substantial changes in water accommodation taking place over a 10 K interval below and above the BuOH melting point.2 The governing mechanisms for the

  2. Identification of liquid-phase decomposition species and reactions for guanidinium azotetrazolate

    Energy Technology Data Exchange (ETDEWEB)

    Kumbhakarna, Neeraj R.; Shah, Kaushal J.; Chowdhury, Arindrajit; Thynell, Stefan T., E-mail:


    Highlights: • Guanidinium azotetrazolate (GzT) is a high-nitrogen energetic material. • FTIR spectroscopy and ToFMS spectrometry were used for species identification. • Quantum mechanics was used to identify transition states and decomposition pathways. • Important reactions in the GzT liquid-phase decomposition process were identified. • Initiation of decomposition occurs via ring opening, releasing N{sub 2}. - Abstract: The objective of this work is to analyze the decomposition of guanidinium azotetrazolate (GzT) in the liquid phase by using a combined experimental and computational approach. The experimental part involves the use of Fourier transform infrared (FTIR) spectroscopy to acquire the spectral transmittance of the evolved gas-phase species from rapid thermolysis, as well as to acquire spectral transmittance of the condensate and residue formed from the decomposition. Time-of-flight mass spectrometry (ToFMS) is also used to acquire mass spectra of the evolved gas-phase species. Sub-milligram samples of GzT were heated at rates of about 2000 K/s to a set temperature (553–573 K) where decomposition occurred under isothermal conditions. N{sub 2}, NH{sub 3}, HCN, guanidine and melamine were identified as products of decomposition. The computational approach is based on using quantum mechanics for confirming the identity of the species observed in experiments and for identifying elementary chemical reactions that formed these species. In these ab initio techniques, various levels of theory and basis sets were used. Based on the calculated enthalpy and free energy values of various molecular structures, important reaction pathways were identified. Initiation of decomposition of GzT occurs via ring opening to release N{sub 2}.

  3. Understanding the aqueous phase ozonolysis of isoprene: distinct product distribution and mechanism from the gas phase reaction

    Directory of Open Access Journals (Sweden)

    H. L. Wang


    Full Text Available The aqueous phase reaction of volatile organic compounds (VOCs has not been considered in most analyses of atmospheric chemical processes. However, some experimental evidence has shown that, compared to the corresponding gas phase reaction, the aqueous chemical processes of VOCs in the bulk solutions and surfaces of ambient wet particles (cloud, fog, and wet aerosols may potentially contribute to the products and formation of secondary organic aerosol (SOA. In the present study, we performed a laboratory experiment of the aqueous ozonolysis of isoprene at different pHs (3–7 and temperatures (4–25 °C. We detected three important kinds of products, including carbonyl compounds, peroxide compounds, and organic acids. Our results showed that the molar yields of these products were nearly independent of the investigated pHs and temperatures, those were (1 carbonyls: 56.7 ± 3.7 % formaldehyde, 42.8 ± 2.5 % methacrolein (MAC, and 57.7 ± 3.4 % methyl vinyl ketone (MVK; (2 peroxides: 53.4 ± 4.1 % hydrogen peroxide (H2O2 and 15.1 ± 3.1 % hydroxylmethyl hydroperoxide (HMHP; and (3 organic acids: undetectable (<1 % estimated by the detection limit. Based on the amounts of products formed and the isoprene consumed, the total carbon yield was estimated to be 94.8 ± 4.1 %. This implied that most of the products in the reaction system were detected. The combined yields of both MAC + MVK and H2O2 + HMHP in the aqueous isoprene ozonolysis were much higher than those observed in the corresponding gas phase reaction. We suggest that these unexpected high yields of carbonyls and peroxides are related to the greater capability of condensed water, compared to water vapor, to stabilize energy-rich Criegee radicals. This aqueous ozonolysis of isoprene (and possibly other biogenic VOCs could potentially occur on the surfaces of ambient wet particles and plants. Moreover, the high-yield carbonyl and peroxide products

  4. Gas Phase Reactions of Ions Derived from Anionic Uranyl Formate and Uranyl Acetate Complexes (United States)

    Perez, Evan; Hanley, Cassandra; Koehler, Stephen; Pestok, Jordan; Polonsky, Nevo; Van Stipdonk, Michael


    The speciation and reactivity of uranium are topics of sustained interest because of their importance to the development of nuclear fuel processing methods, and a more complete understanding of the factors that govern the mobility and fate of the element in the environment. Tandem mass spectrometry can be used to examine the intrinsic reactivity (i.e., free from influence of solvent and other condensed phase effects) of a wide range of metal ion complexes in a species-specific fashion. Here, electrospray ionization, collision-induced dissociation, and gas-phase ion-molecule reactions were used to create and characterize ions derived from precursors composed of uranyl cation (UVIO2 2+) coordinated by formate or acetate ligands. Anionic complexes containing UVIO2 2+ and formate ligands fragment by decarboxylation and elimination of CH2=O, ultimately to produce an oxo-hydride species [UVIO2(O)(H)]-. Cationic species ultimately dissociate to make [UVIO2(OH)]+. Anionic complexes containing acetate ligands exhibit an initial loss of acetyloxyl radical, CH3CO2•, with associated reduction of uranyl to UVO2 +. Subsequent CID steps cause elimination of CO2 and CH4, ultimately to produce [UVO2(O)]-. Loss of CH4 occurs by an intra-complex H+ transfer process that leaves UVO2 + coordinated by acetate and acetate enolate ligands. A subsequent dissociation step causes elimination of CH2=C=O to leave [UVO2(O)]-. Elimination of CH4 is also observed as a result of hydrolysis caused by ion-molecule reaction with H2O. The reactions of other anionic species with gas-phase H2O create hydroxyl products, presumably through the elimination of H2.

  5. Geometric phase effects in the ultracold H + H2 reaction. (United States)

    Kendrick, B K; Hazra, Jisha; Balakrishnan, N


    The H3 system has served as a prototype for geometric phase (GP) effects in bimolecular chemical reactions for over three decades. Despite a large number of theoretical and experimental efforts, no conclusive evidence of GP effects in the integral cross section or reaction rate has been presented until recently [B. Kendrick et al., Phys. Rev. Lett. 115, 153201 (2015)]. Here we report a more detailed account of GP effects in the H + H2(v = 4, j = 0) → H + H2(v', j') (para-para) reaction rate coefficients for temperatures between 1 μK (8.6 × 10(-11) eV) and 100 K (8.6 × 10(-3) eV). The GP effect is found to persist in both vibrationally resolved and total rate coefficients for collision energies up to about 10 K. The GP effect also appears in rotationally resolved differential cross sections leading to a very different oscillatory structure in both energy and scattering angle. It is shown to suppress a prominent shape resonance near 1 K and enhance a shape resonance near 8 K, providing new experimentally verifiable signatures of the GP effect in the fundamental hydrogen exchange reaction. The GP effect in the D + D2 and T + T2 reactions is also examined in the ultracold limit and its sensitivity to the potential energy surface is explored.

  6. Geometric Phase Appears in the Ultracold Hydrogen Exchange Reaction. (United States)

    Kendrick, B K; Hazra, Jisha; Balakrishnan, N


    Quantum reactive scattering calculations for the hydrogen exchange reaction H+H_{2}(v=4,j=0)→H+H_{2}(v^{'}, j^{'}) and its isotopic analogues are reported for ultracold collision energies. Because of the unique properties associated with ultracold collisions, it is shown that the geometric phase effectively controls the reactivity. The rotationally resolved rate coefficients computed with and without the geometric phase are shown to differ by up to 4 orders of magnitude. The effect is also significant in the vibrationally resolved and total rate coefficients. The dynamical origin of the effect is discussed and the large geometric phase effect reported here might be exploited to control the reactivity through the application of external fields or by the selection of a particular nuclear spin state.

  7. Phase transitions at electrochemical interfaces:. Evaluation of critical exponents for condensation of organic adsorbates (United States)

    Pushpalatha, K.; Sangaranarayanan, M. V.


    The surface pressure exerted by a monolayer of organic compounds condensing at electrochemical interfaces is evaluated using a two-dimensional nearest-neighbor Ising model formalism. The experimental critical temperature data of organic adsorbates are employed to obtain the composite short-range interaction energy using Onsager's exact solution. The methodology of obtaining the critical exponents ` δ' and ` γ' pertaining to surface pressure and isothermal compressibility is discussed. These values are consistent with the exponents postulated in other contexts, thereby demonstrating the universality hypothesis.

  8. Microwave-Assisted Condensation Reactions of Acetophenone Derivatives and Activated Methylene Compounds with Aldehydes Catalyzed by Boric Acid under Solvent-Free Conditions. (United States)

    Brun, Elodie; Safer, Abdelmounaim; Carreaux, François; Bourahla, Khadidja; L'helgoua'ch, Jean-Martial; Bazureau, Jean-Pierre; Villalgordo, Jose Manuel


    We here disclosed a new protocol for the condensation of acetophenone derivatives and active methylene compounds with aldehydes in the presence of boric acid under microwave conditions. Implementation of the reaction is simple, healthy and environmentally friendly owing to the use of a non-toxic catalyst coupled to a solvent-free procedure. A large variety of known or novel compounds have thus been prepared, including with substrates bearing acid or base-sensitive functional groups.

  9. Microwave-Assisted Condensation Reactions of Acetophenone Derivatives and Activated Methylene Compounds with Aldehydes Catalyzed by Boric Acid under Solvent-Free Conditions

    Directory of Open Access Journals (Sweden)

    Elodie Brun


    Full Text Available We here disclosed a new protocol for the condensation of acetophenone derivatives and active methylene compounds with aldehydes in the presence of boric acid under microwave conditions. Implementation of the reaction is simple, healthy and environmentally friendly owing to the use of a non-toxic catalyst coupled to a solvent-free procedure. A large variety of known or novel compounds have thus been prepared, including with substrates bearing acid or base-sensitive functional groups.

  10. Local Nucleation of Microtubule Bundles through Tubulin Concentration into a Condensed Tau Phase

    Directory of Open Access Journals (Sweden)

    Amayra Hernández-Vega


    Full Text Available Non-centrosomal microtubule bundles play important roles in cellular organization and function. Although many diverse proteins are known that can bundle microtubules, biochemical mechanisms by which cells could locally control the nucleation and formation of microtubule bundles are understudied. Here, we demonstrate that the concentration of tubulin into a condensed, liquid-like compartment composed of the unstructured neuronal protein tau is sufficient to nucleate microtubule bundles. We show that, under conditions of macro-molecular crowding, tau forms liquid-like drops. Tubulin partitions into these drops, efficiently increasing tubulin concentration and driving the nucleation of microtubules. These growing microtubules form bundles, which deform the drops while remaining enclosed by diffusible tau molecules exhibiting a liquid-like behavior. Our data suggest that condensed compartments of microtubule bundling proteins could promote the local formation of microtubule bundles in neurons by acting as non-centrosomal microtubule nucleation centers and that liquid-like tau encapsulation could provide both stability and plasticity to long axonal microtubule bundles.

  11. Local Nucleation of Microtubule Bundles through Tubulin Concentration into a Condensed Tau Phase. (United States)

    Hernández-Vega, Amayra; Braun, Marcus; Scharrel, Lara; Jahnel, Marcus; Wegmann, Susanne; Hyman, Bradley T; Alberti, Simon; Diez, Stefan; Hyman, Anthony A


    Non-centrosomal microtubule bundles play important roles in cellular organization and function. Although many diverse proteins are known that can bundle microtubules, biochemical mechanisms by which cells could locally control the nucleation and formation of microtubule bundles are understudied. Here, we demonstrate that the concentration of tubulin into a condensed, liquid-like compartment composed of the unstructured neuronal protein tau is sufficient to nucleate microtubule bundles. We show that, under conditions of macro-molecular crowding, tau forms liquid-like drops. Tubulin partitions into these drops, efficiently increasing tubulin concentration and driving the nucleation of microtubules. These growing microtubules form bundles, which deform the drops while remaining enclosed by diffusible tau molecules exhibiting a liquid-like behavior. Our data suggest that condensed compartments of microtubule bundling proteins could promote the local formation of microtubule bundles in neurons by acting as non-centrosomal microtubule nucleation centers and that liquid-like tau encapsulation could provide both stability and plasticity to long axonal microtubule bundles. Copyright © 2017 The Authors. Published by Elsevier Inc. All rights reserved.

  12. PRR11 regulates late-S to G2/M phase progression and induces premature chromatin condensation (PCC)

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Chundong; Zhang, Ying; Li, Yi; Zhu, Huifang; Wang, Yitao; Cai, Wei [Department of Biochemistry and Molecular Biology, Chongqing Medical University, Chongqing 400016 (China); Molecular Medicine and Cancer Research Center, Chongqing Medical University, Chongqing 400016 (China); Zhu, Jiang [Molecular Medicine and Cancer Research Center, Chongqing Medical University, Chongqing 400016 (China); Ozaki, Toshinori [Laboratory of DNA Damage Signaling, Chiba Cancer Center Research Institute, 666-2 Nitona, Chuohku, Chiba 260-8717 (Japan); Bu, Youquan, E-mail: [Department of Biochemistry and Molecular Biology, Chongqing Medical University, Chongqing 400016 (China); Molecular Medicine and Cancer Research Center, Chongqing Medical University, Chongqing 400016 (China)


    Recently, we have demonstrated that proline-rich protein 11 (PRR11) is a novel tumor-related gene product likely implicated in the regulation of cell cycle progression as well as lung cancer development. However, its precise role in cell cycle progression remains unclear. In the present study, we have further investigated the expression pattern and functional implication of PRR11 during cell cycle in detail in human lung carcinoma-derived H1299 cells. According to our immunofluorescence study, PRR11 was expressed largely in cytoplasm, the amount of PRR11 started to increase in the late S phase, and was retained until just before mitotic telophase. Consistent with those observations, siRNA-mediated knockdown of PRR11 caused a significant cell cycle arrest in the late S phase. Intriguingly, the treatment with dNTPs further augmented PRR11 silencing-mediated S phase arrest. Moreover, knockdown of PRR11 also resulted in a remarkable retardation of G2/M progression, and PRR11-knockdown cells subsequently underwent G2 phase cell cycle arrest accompanied by obvious mitotic defects such as multipolar spindles and multiple nuclei. In addition, forced expression of PRR11 promoted the premature Chromatin condensation (PCC), and then proliferation of PRR11-expressing cells was massively attenuated and induced apoptosis. Taken together, our current observations strongly suggest that PRR11, which is strictly regulated during cell cycle progression, plays a pivotal role in the regulation of accurate cell cycle progression through the late S phase to mitosis. - Highlights: • PRR11 started to increase in the late S phase and was retained until just before mitotic telophase. • PRR11-knockdown caused a significant cell cycle arrest in the late S phase and G2 phase. • The treatment with dNTPs further augmented PRR11 silencing-mediated S phase arrest. • PRR11-knockdown led to multipolar spindles and multiple nuclei. • Forced expression of PRR11 promoted the PCC and inhibited

  13. One-Pot Synthesis of N-(α-Peroxy)Indole/Carbazole via Chemoselective Three-Component Condensation Reaction in Open Atmosphere

    KAUST Repository

    Wang, Xinbo


    A facile one-pot synthesis of N-(α-peroxy)indole and N-(α-peroxy)carbazole has been developed using metal-free, organo-acid-catalyzed three-component condensation reactions of indole/carbazole, aldehyde, and peroxide. Based on the reaction discovered, a new synthetic proposal for Fumitremorgin A and Verruculogen is introduced. Such a protocol could be easily handled and scaled up in an open atmosphere with a wide substrate scope, enabling the construction of a new molecule library.

  14. Silica functionalized Cu(II) acetylacetonate Schiff base complex: An efficient catalyst for the oxidative condensation reaction of benzyl alcohol with amines (United States)

    Anbarasu, G.; Malathy, M.; Karthikeyan, P.; Rajavel, R.


    Silica functionalized Cu(II) acetylacetonate Schiff base complex via the one pot reaction of silica functionalized 3-aminopropyltriethoxysilane with acetyl acetone and copper acetate has been reported. The synthesized material was well characterized by analytical techniques such as FT-IR, UV-DRS, XRD, SEM-EDX, HR-TEM, EPR, ICP-AES and BET analysis. The characterization results confirmed the grafting of Cu(II) Schiff base complex on the silica surface. The catalytic activity of synthesized silica functionalized Cu(II) acetylacetonate Schiff base complex was evaluated through the oxidative condensation reaction of benzyl alcohol to imine.

  15. Cyclization of N-arylcyclopropanecarboxamides into N-arylpyrrolidin-2-ones under electron ionization and in the condensed phase. (United States)

    Lebedev, A T; Mazur, D M; Kudelin, A I; Fedotov, A N; Gloriozov, I P; Ustynyuk, Yu A; Artaev, V B


    Mass spectrometry is known as an excellent method to predict the behavior of organic compounds in solution. The behavior of organic compounds in the gas phase inside the ion source of a mass spectrometer allows their intrinsic properties to be defined, avoiding the influence of intermolecular interactions, counter ions and solvent effects. Arylpyrrolidin-2-ones were obtained by condensed-phase synthesis from the corresponding N-arylcyclopropanecarboxamides. Electron ionization (EI) with accurate mass measurements by high-resolution time-of-flight mass-spectrometry and quantum chemical calculations were used to understand the behavior of the molecular radical cations of N-arylcyclopropanecarboxamides and N-arylpyrrolidin-2-ones in the ion source of a mass spectrometer. The geometries of the molecules, transition states, and intermediates were fully optimized using DFT-PBE calculations. Fragmentation schemes, ion structures, and possible mechanisms of primary isomerisation were proposed for isomeric N-arylcyclopropanecarboxamides and N-arylpyrrolidin-2-ones. Based on the fragmentation pattern of the N-arylcyclopropanecarboxamides, isomerisation of the original M +• ions into the M +• ions of the N-arylpyrrolidin-2-ones was shown to be only a minor process. In contrast, this cyclization proceeds easily in the condensed phase in the presence of Brønsted acids. Based on the experimental data and quantum chemical calculations the principal mechanism of decomposition of the molecular ions of N-arylcyclopropanecarboxamides involves their direct fragmentation without any rearrangements. An alternative mechanism is responsible for the isomerisation of a small portion of the higher energy molecular ions into the corresponding N-arylpyrrolidin-2-one ions. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  16. Pentanidium-catalyzed enantioselective phase-transfer conjugate addition reactions

    KAUST Repository

    Ma, Ting


    A new chiral entity, pentanidium, has been shown to be an excellent chiral phase-transfer catalyst. The enantioselective Michael addition reactions of tert-butyl glycinate-benzophenone Schiff base with various α,β- unsaturated acceptors provide adducts with high enantioselectivities. A successful gram-scale experiment at a low catalyst loading of 0.05 mol % indicates the potential for practical applications of this methodology. Phosphoglycine ester analogues can also be utilized as the Michael donor, affording enantioenriched α-aminophosphonic acid derivatives and phosphonic analogues of (S)-proline. © 2011 American Chemical Society.

  17. Reactions homogenes en phase gazeuse dans les lits fluidises (United States)

    Laviolette, Jean-Philippe

    This thesis presents a study on homogeneous gas-phase reactions in fluidized beds. The main objective is to develop new tools to model and characterize homogeneous gas-phase reactions in this type of reactor. In the first part of this work, the non-premixed combustion of C 1 to C4 n-alkanes with air was investigated inside a bubbling fluidized bed of inert sand particles at intermediate temperatures: 923 K ≤ TB ≤ 1123 K. For ethane, propane and n-butane, combustion occurred mainly in the freeboard region at bed temperatures below T1 = 923 K. On the other hand, complete conversion occurred within 0.2 m of the injector at: T2 = 1073 K. For methane, the measured values of T1 and T2 were significantly higher at 1023 K and above 1123 K, respectively. The fluidized bed combustion was accurately modeled with first-order global kinetics and two one-phase PFR models in series: one PFR to model the region close to the injector and another to represent the main fluidized bed body. The measured global reaction rates for C2 to C4 n-alkanes were characterized by a uniform Arrhenius expression, while the global reaction rate for methane was significantly slower. Reactions in the injector region either led to significant conversion in that zone or an autoignition delay inside the main fluidized bed body. The conversion in the injector region increased with rising fluidized bed temperature and decreased with increasing jet velocity. To account for the promoting and inhibiting effects, an analogy was made with the concept of induction time: the PFR length (bi) of the injector region was correlated to the fluidized bed temperature and jet velocity using an Arrhenius expression. In the second part of this work, propane combustion experiments were conducted in the freeboard of a fluidized bed of sand particles at temperatures between 818 K and 923 K and at superficial gas velocity twice the minimum fluidization velocity. The freeboard region was characterized by simultaneous

  18. The Role of Metal Oxides in Nanothermite Reactions: Evidence of Condensed Phase Initiation (United States)


    oxygen diffusion through the alumina shell[6], pressure build up due to melting of the aluminum, which ruptures the shell allowing Al to leak out[7] and...extreme pressure build up causing eruption of the alumina shell that spallates the molten aluminum[8]. Regardless of the argument, it can be agreed...each of these materials we investigated the decomposition of the thermite, as well as decomposition of the metal oxide and aluminum nanopowders

  19. Oliver E. Buckley Condensed Matter Prize: Quantum-topological phases of matter (United States)

    Wen, Xiao-Gang

    For a long time, we thought that symmetry breaking patterns describe all phases and phase transitions. The featureless disordered liquids correspond to trivial phase. But in fact disordered liquids have very rich features, with amazing emergent phenomena, such as fractional quantum numbers, fractional and non-abelian statistics, perfect conducting boundary even in presence of magnetic impurities, etc. All those are due to many-body entanglement. In this talk, I will first discuss topological phases that have topological order (ie with long range entanglement). Then I will cover topological phases that have no topological order (ie with only short-range entanglement). I will stress on how to understand and describe many-body entanglement, which is a very new phenomenon. This research is supported by NSF Grant No. DMR-1506475.

  20. The Influence of Mixing in High Temperature Gas Phase Reactions

    DEFF Research Database (Denmark)

    Østberg, Martin


    The objective of this thesis is to describe the mixing in high temperature gas phase reactions.The Selective Non-Catalytic Reduction of NOx (referred as the SNR process) using NH3 as reductant was chosen as reaction system. This in-furnace denitrification process is made at around 1200 - 1300 K b....... For temperatures below 1200 K the NO outlet concentration is unaffected because of lower reaction rates.The droplet diffusion model is used to model the experimental results and it can describe the influence of the carrier gas flow with a successful result....... to the injected gas as well.The effects of the NH3 flow and natural gas addition were as expected from earlier studies in laboratory reactors and pilot plants.The experiments indicates that the SNR process was only dependent on the O2 concentration in the flue gas without any effect due to variation of the O2...... concentrations in the injected gas between 0 - 20 vol%.Using a nozzle with a diameter of 1.9 mm the reduction of NO is dependent on the carrier gas flow for temperatures above 1200 K (1100 K when natural gas is added).It is shown that this effect can not be described by macromixing using a simple reactor model...

  1. Heterogeneous phase reactions of Martian volatiles with putative regolith minerals (United States)

    Clark, B. C.; Kenley, S. L.; Obrien, D. L.; Huss, G. R.; Mack, R.; Baird, A. K.


    The chemical reactivity of several minerals thought to be present in Martian fines is tested with respect to gases known in the Martian atmosphere. In these experiments, liquid water is excluded from the system, environmental temperatures are maintained below 0 C, and the solar illumination spectrum is stimulated in the visible and UV using a xenon arc lamp. Reactions are detected by mass spectrometric analysis of the gas phase over solid samples. No reactions were detected for Mars nominal gas over sulfates, nitrates, chloride, nontronite clay, or magnetite. Oxidation was not observed for basaltic glass, nontronite, and magnetite. However, experiments incorporating SO2 gas an expected product of volcanism and intrusive volatile release - gave positive results. Displacement of CO2 by SO2 occurred in all four carbonates tested. These reactions are catalyzed by irradiation with the solar simulator. A calcium nitrate hydrate released NO2 in the presence of SO2. These results have implications for the cycling of atmospheric CO2, H2O, and N2 through the regolith.

  2. Effect of the collective motions of molecules inside a condensed phase on fluctuations in the density of small bodies (United States)

    Tovbin, Yu. K.


    An approach to calculating the effects of fluctuations in density that considers the collective motions of molecules in small condensed phases (e.g., droplets, microcrystals, adsorption at microcrystal faces) is proposed. Statistical sums of the vibrational, rotational, and translational motions of molecules are of a collective character expressed in the dependences of these statistical sums on the local configurations of neighboring molecules. This changes their individual contributions to the free energy and modifies fluctuations in density in the inner homogeneous regions of small bodies. Interactions between nearest neighbors are considered in a quasi-chemical approximation that reflects the effects of short-range direct correlations. Expressions for isotherms relating the densities of mixture components to the chemical potentials in a thermostat are obtained, along with equations for pair distribution functions.

  3. Phase-equilibria for design of coal-gasification processes: dew points of hot gases containing condensible tars. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Prausnitz, J.M.


    This research is concerned with the fundamental physical chemistry and thermodynamics of condensation of tars (dew points) from the vapor phase at advanced temperatures and pressures. Fundamental quantitative understanding of dew points is important for rational design of heat exchangers to recover sensible heat from hot, tar-containing gases that are produced in coal gasification. This report includes essentially six contributions toward establishing the desired understanding: (1) Characterization of Coal Tars for Dew-Point Calculations; (2) Fugacity Coefficients for Dew-Point Calculations in Coal-Gasification Process Design; (3) Vapor Pressures of High-Molecular-Weight Hydrocarbons; (4) Estimation of Vapor Pressures of High-Boiling Fractions in Liquefied Fossil Fuels Containing Heteroatoms Nitrogen or Sulfur; and (5) Vapor Pressures of Heavy Liquid Hydrocarbons by a Group-Contribution Method.

  4. Organization and Function of Non-dynamic Biomolecular Condensates. (United States)

    Woodruff, Jeffrey B; Hyman, Anthony A; Boke, Elvan


    Cells compartmentalize biochemical reactions using organelles. Organelles can be either membrane-bound compartments or supramolecular assemblies of protein and ribonucleic acid known as 'biomolecular condensates'. Biomolecular condensates, such as nucleoli and germ granules, have been described as liquid like, as they have the ability to fuse, flow, and undergo fission. Recent experiments have revealed that some liquid-like condensates can mature over time to form stable gels. In other cases, biomolecular condensates solidify into amyloid-like fibers. Here we discuss the assembly, organization, and physiological roles of these more stable condensates in cells, focusing on Balbiani bodies, centrosomes, nuclear pores, and amyloid bodies. We discuss how the material properties of these condensates can be explained by the principles of liquid-liquid phase separation and maturation. Copyright © 2017 Elsevier Ltd. All rights reserved.


    Energy Technology Data Exchange (ETDEWEB)

    Heaven, Michael C.; Gibson, John K.; Marcalo, Joaquim


    temperature or below. For many spectroscopic measurements, low temperatures have been achieved by co-condensing the actinide vapor in rare gas or inert molecule host matrices. Spectra recorded in matrices are usually considered to be minimally perturbed. Trapping the products from gas-phase reactions that occur when trace quantities of reactants are added to the inert host gas has resulted in the discovery of many new actinide species. Selected aspects of the matrix isolation data were discussed in chapter 17. In the present chapter we review the spectroscopic matrix data in terms of its relationship to gas-phase measurements, and update the description of the new reaction products found in matrices to reflect the developments that have occurred during the past two years. Spectra recorded in matrix environments are usually considered to be minimally perturbed, and this expectation is borne out for many closed shell actinide molecules. However, there is growing evidence that significant perturbations can occur for open shell molecules, resulting in geometric distortions and/or electronic state reordering. Studies of actinide reactions in the gas phase provide an opportunity to probe the relationship between electronic structure and reactivity. Much of this work has focused on the reactions of ionic species, as these may be selected and controlled using various forms of mass spectrometry. As an example of the type of insight derived from reaction studies, it has been established that the reaction barriers for An+ ions are determined by the promotion energies required to achieve the 5fn6d7s configuration. Gas-phase reaction studies also provide fundamental thermodynamic properties such as bond dissociation and ionization energies. In recent years, an increased number of gas-phase ion chemistry studies of bare (atomic) and ligated (molecular) actinide ions have appeared, in which relevant contributions to fundamental actinide chemistry have been made. These studies were initiated

  6. A complete equation of state for non-ideal condensed phase explosives


    Wilkinson, Simon David; Braithwaite, Martin; Nikiforakis, Nikolaos; Michael, Louisa


    The objective of this work is to improve the robustness and accuracy of numerical simulations of both ideal and non-ideal explosives by introducing temperature dependence in mechanical equations of state for reactants and products. To this end, we modify existing mechanical equations of state to appropriately approximate the temperature in the reaction zone. Mechanical equations of state of Mie-Gr\\"{u}neisen form are developed with extensions, which allow the temperature to be evaluated appro...

  7. A smart device for label-free and real-time detection of gene point mutations based on the high dark phase contrast of vapor condensation. (United States)

    Zhang, Junqi; Fu, Rongxin; Xie, Liping; Li, Qi; Zhou, Wenhan; Wang, Ruliang; Ye, Jiancheng; Wang, Dong; Xue, Ning; Lin, Xue; Lu, Ying; Huang, Guoliang


    A smart device for label-free and real-time detection of gene point mutation-related diseases was developed based on the high dark phase contrast of vapor condensation. The main components of the device included a Peltier cooler and a mini PC board for image processing. Heat from the hot side of the Peltier cooler causes the fluid in a copper chamber to evaporate, and the vapor condenses on the surface of a microarray chip placed on the cold side of the cooler. The high dark phase contrast of vapor condensation relative to the analytes on the microarray chip was explored. Combined with rolling circle amplification, the device visualizes less-to-more hydrophilic transitions caused by gene trapping and DNA amplification. A lung cancer gene point mutation was analysed, proving the high selectivity and multiplex analysis capability of this low-cost device.

  8. Condensation Polymerization

    Indian Academy of Sciences (India)

    chain polyester by a process termed as polycondensation – 'poly' implying that several such events occur, and 'condensation' im- plies that there is a condensate that is formed. The condensate formed in this case, as you would have guessed, is H2O. Such re- actions would be classified as AA + BB type condensation, anal ...

  9. Reactions of molecular dications in the gas phase

    CERN Document Server

    Tafadar, N N


    This thesis presents the results from a series of experiments investigating the reactivity of gas phase molecular dications with neutral collision partners, at collision energies between 3 and 13 eV in the laboratory frame using a crossed-beam apparatus. The experiments involve measurement of product ion intensities, which are determined by means of time of flight mass spectrometry. The experimental methodology, together with relevant theory is described in the thesis. The relative intensities of product ions formed are a powerful probe of the reaction mechanism. Where appropriate, the reactions are examined for isotope effects by using the isotopic analogue of the neutral collision partner. Our investigation of the CF sub 3 sup 2 sup + /Ar collision system shows neutral loss and electron transfer dominating the product ion yield. The variation of the neutral loss ion yield with collision energy provides a first estimate of the bond energy of the weak CF sub 2 sup 2 sup + -F bond. Ab initio calculations indic...

  10. Condensed-phase biogenic-anthropogenic interactions with implications for cold cloud formation. (United States)

    Charnawskas, Joseph C; Alpert, Peter A; Lambe, Andrew T; Berkemeier, Thomas; O'Brien, Rachel E; Massoli, Paola; Onasch, Timothy B; Shiraiwa, Manabu; Moffet, Ryan C; Gilles, Mary K; Davidovits, Paul; Worsnop, Douglas R; Knopf, Daniel A


    Anthropogenic and biogenic gas emissions contribute to the formation of secondary organic aerosol (SOA). When present, soot particles from fossil fuel combustion can acquire a coating of SOA. We investigate SOA-soot biogenic-anthropogenic interactions and their impact on ice nucleation in relation to the particles' organic phase state. SOA particles were generated from the OH oxidation of naphthalene, α-pinene, longifolene, or isoprene, with or without the presence of sulfate or soot particles. Corresponding particle glass transition (Tg) and full deliquescence relative humidity (FDRH) were estimated using a numerical diffusion model. Longifolene SOA particles are solid-like and all biogenic SOA sulfate mixtures exhibit a core-shell configuration (i.e. a sulfate-rich core coated with SOA). Biogenic SOA with or without sulfate formed ice at conditions expected for homogeneous ice nucleation, in agreement with respective Tg and FDRH. α-pinene SOA coated soot particles nucleated ice above the homogeneous freezing temperature with soot acting as ice nuclei (IN). At lower temperatures the α-pinene SOA coating can be semisolid, inducing ice nucleation. Naphthalene SOA coated soot particles acted as ice nuclei above and below the homogeneous freezing limit, which can be explained by the presence of a highly viscous SOA phase. Our results suggest that biogenic SOA does not play a significant role in mixed-phase cloud formation and the presence of sulfate renders this even less likely. However, anthropogenic SOA may have an enhancing effect on cloud glaciation under mixed-phase and cirrus cloud conditions compared to biogenic SOA that dominate during pre-industrial times or in pristine areas.

  11. Changes in electronic states of molecules resulted from interactions in the condensed phase (United States)

    Morisawa, Yusuke; Ueno, Nami; Tachibana, Shin; Ehara, Masahiro; Ozaki, Yukihiro


    The wavelength region shorter than 200 nm, far-ultraviolet (FUV) region, is very rich in information about the electronic states and structure of a molecule. We have recently developed a totally new UV spectrometer based on attenuated total reflection (ATR) that enables us to measure spectra of liquid and solid samples in the 140-280 nm region. This paper shows the studies by the attenuated total reflection far-ultraviolet (ATR-FUV) spectroscopy. Intermolecular interactions between alkyl chains such as CH--HC should be reflected in the phase behavior of organic compounds. We measured the attenuated total reflectance spectra in the far-UV region (145-300 nm) of n-tetradecane (Tm = 5.9 °C) from 15 to -38 °C to determine its temperature dependency. With decreasing temperature, the absorption band at 153 nm in the liquid phase becomes weaker and new bands appear at around 200 and 230 nm. These results suggest that an unusually compressed structure might be generated at the surface at low temperatures, and this phase change, which is reversible, is responsible for the unusual absorption observed in the ATR-FUV spectra. We have also investigated composite polymer electrolytes (CPE). ATR-FUV spectra of CPEs composed of Poly(ethylene oxide) (PEO) and Li salt were observed and its variation of anions for the CPEs are studied.

  12. A complete equation of state for non-ideal condensed phase explosives (United States)

    Wilkinson, S. D.; Braithwaite, M.; Nikiforakis, N.; Michael, L.


    The objective of this work is to improve the robustness and accuracy of numerical simulations of both ideal and non-ideal explosives by introducing temperature dependence in mechanical equations of state for reactants and products. To this end, we modify existing mechanical equations of state to appropriately approximate the temperature in the reaction zone. Mechanical equations of state of the Mie-Grüneisen form are developed with extensions, which allow the temperature to be evaluated appropriately and the temperature equilibrium condition to be applied robustly. Furthermore, the snow plow model is used to capture the effect of porosity on the reactant equation of state. We apply the methodology to predict the velocity of compliantly confined detonation waves. Once reaction rates are calibrated for unconfined detonation velocities, simulations of confined rate sticks and slabs are performed, and the experimental detonation velocities are matched without further parameter alteration, demonstrating the predictive capability of our simulations. We apply the same methodology to both ideal (PBX9502, a high explosive with principal ingredient TATB) and non-ideal (EM120D, an ANE or ammonium nitrate based emulsion) explosives.

  13. Method and apparatus for maintaining condensable constituents of a gas in a vapor phase during sample transport (United States)

    Felix, Larry Gordon; Farthing, William Earl; Irvin, James Hodges; Snyder, Todd Robert


    A system for fluid transport at elevated temperatures having a conduit having a fluid inlet end and a fluid outlet end and at least one heating element disposed within the conduit providing direct heating of a fluid flowing through the conduit. The system is particularly suited for preventing condensable constituents of a high temperature fluid from condensing out of the fluid prior to analysis of the fluid. In addition, operation of the system so as to prevent the condensable constituents from condensing out of the fluid surprisingly does not alter the composition of the fluid.

  14. Learning Kinetic Monte Carlo Models of Condensed Phase High Temperature Chemistry from Molecular Dynamics (United States)

    Yang, Qian; Sing-Long, Carlos; Chen, Enze; Reed, Evan


    Complex chemical processes, such as the decomposition of energetic materials and the chemistry of planetary interiors, are typically studied using large-scale molecular dynamics simulations that run for weeks on high performance parallel machines. These computations may involve thousands of atoms forming hundreds of molecular species and undergoing thousands of reactions. It is natural to wonder whether this wealth of data can be utilized to build more efficient, interpretable, and predictive models. In this talk, we will use techniques from statistical learning to develop a framework for constructing Kinetic Monte Carlo (KMC) models from molecular dynamics data. We will show that our KMC models can not only extrapolate the behavior of the chemical system by as much as an order of magnitude in time, but can also be used to study the dynamics of entirely different chemical trajectories with a high degree of fidelity. Then, we will discuss three different methods for reducing our learned KMC models, including a new and efficient data-driven algorithm using L1-regularization. We demonstrate our framework throughout on a system of high-temperature high-pressure liquid methane, thought to be a major component of gas giant planetary interiors.

  15. A DFT study on the aldol condensation reaction on MgO in the process of ethanol to 1,3-butadiene: understanding the structure-activity relationship. (United States)

    Fan, Dan; Dong, Xiuqin; Yu, Yingzhe; Zhang, Minhua


    Using periodic density functional theory calculations, the aldol condensation of acetaldehyde to 3-hydroxybutanal over dehydroxylated MgO surfaces with and without structure defects was investigated. Compared with the C-C coupling step, the enolization step via proton transfer of the α-hydrogen of acetaldehyde to the MgO surface or the proton back-transfer step to form the desired 3-hydroxybutanal has a higher energy barrier, indicating that the proton transfer process is the key step for the aldol condensation on MgO. To highlight the effect of water, we also calculated the proton transfer steps in the presence of water and studied the reaction pathways over the partially hydroxylated MgO surface. The results show that water can participate in the proton back-transfer step by donating a proton to the alkoxide anion to form the 3-hydroxybutanal, thus reducing the activation energy; the surface OH groups induce a lowering of the activation energy barriers for the overall reaction. The results of the electronic structure analysis indicate that a strong Lewis acid-weak/medium base pair may have the best performance for aldol condensation, such as Mg3C-O4C-D produced by divacancy defects and Mg4C-O2CH produced by the dissociative adsorption of water. A strong Lewis acid generated by low-coordinated Mg2+ can adsorb and stabilize the acetaldehyde molecule near the catalyst surface which is beneficial for the abstraction of an α-proton from an acetaldehyde molecule, and a medium or weak Brønsted base is favorable for the proton back-transfer step.

  16. The Effects of a Macromolecular Charring Agent with Gas Phase and Condense Phase Synergistic Flame Retardant Capability on the Properties of PP/IFR Composites. (United States)

    Chen, Hongda; Wang, Jihui; Ni, Aiqing; Ding, Anxin; Han, Xia; Sun, Ziheng


    In order to improve the efficiency of intumescent flame retardants (IFRs), a novel macromolecular charring agent named poly(ethanediamine-1,3,5-triazine-p-4-amino-2,2,6,6-tetramethylpiperidine) (PETAT) with gas phase and condense phase synergistic flame-retardant capability was synthesized and subsequently dispersed into polypropylene (PP) in combination with ammonium polyphosphate (APP) via a melt blending method. The chemical structure of PETAT was investigated by Fourier transform infrared spectroscopy (FTIR), and ¹H nuclear magnetic resonance (NMR) spectroscopy. Thermal properties of the PETAT and IFR systems were tested by thermogravimetric-derivative thermogravimetric analysis (TGA-DTG) and thermogravimetry-Fourier transform infrared spectroscopy (TG-FTIR). The mechanical properties, thermal stability, flame-retardant properties, water resistance, and structures of char residue in flame-retardant composites were characterized using tensile and flexural strength property tests, TGA, limiting oxygen index (LOI) values before and after soaking, underwritten laboratory-94 (UL-94) vertical burning test, cone calorimetric test (CCT), scanning electron microscopy with energy dispersive X-ray spectrometry (SEM-EDXS), and FTIR. The results indicated that PETAT was successfully synthesized, and when the ratio of APP to PETAT was 2:1 with 25 wt % loading, the novel IFR system could reduce the deterioration of tensile strength and enhance the flexural strength of composites. Meanwhile, the flame-retardant composite was able to pass the UL-94 V-0 rating with an LOI value of 30.3%, and the peak of heat release rate (PHRR), total heat release (THR), and material fire hazard values were considerably decreased compared with others. In addition, composites also exhibited excellent water resistance properties compared with traditional IFR composites. SEM-EDXS and FTIR analyses of the char residues, as well as TG-FTIR analyses of IFR were used to investigate the flame

  17. The Effects of a Macromolecular Charring Agent with Gas Phase and Condense Phase Synergistic Flame Retardant Capability on the Properties of PP/IFR Composites (United States)

    Chen, Hongda; Wang, Jihui; Ding, Anxin; Han, Xia; Sun, Ziheng


    In order to improve the efficiency of intumescent flame retardants (IFRs), a novel macromolecular charring agent named poly(ethanediamine-1,3,5-triazine-p-4-amino-2,2,6,6-tetramethylpiperidine) (PETAT) with gas phase and condense phase synergistic flame-retardant capability was synthesized and subsequently dispersed into polypropylene (PP) in combination with ammonium polyphosphate (APP) via a melt blending method. The chemical structure of PETAT was investigated by Fourier transform infrared spectroscopy (FTIR), and 1H nuclear magnetic resonance (NMR) spectroscopy. Thermal properties of the PETAT and IFR systems were tested by thermogravimetric-derivative thermogravimetric analysis (TGA-DTG) and thermogravimetry–Fourier transform infrared spectroscopy (TG-FTIR). The mechanical properties, thermal stability, flame-retardant properties, water resistance, and structures of char residue in flame-retardant composites were characterized using tensile and flexural strength property tests, TGA, limiting oxygen index (LOI) values before and after soaking, underwritten laboratory-94 (UL-94) vertical burning test, cone calorimetric test (CCT), scanning electron microscopy with energy dispersive X-ray spectrometry (SEM-EDXS), and FTIR. The results indicated that PETAT was successfully synthesized, and when the ratio of APP to PETAT was 2:1 with 25 wt % loading, the novel IFR system could reduce the deterioration of tensile strength and enhance the flexural strength of composites. Meanwhile, the flame-retardant composite was able to pass the UL-94 V-0 rating with an LOI value of 30.3%, and the peak of heat release rate (PHRR), total heat release (THR), and material fire hazard values were considerably decreased compared with others. In addition, composites also exhibited excellent water resistance properties compared with traditional IFR composites. SEM-EDXS and FTIR analyses of the char residues, as well as TG-FTIR analyses of IFR were used to investigate the flame

  18. Defining Condensed Phase Reactive Force Fields from ab Initio Molecular Dynamics Simulations: The Case of the Hydrated Excess Proton. (United States)

    Knight, Chris; Maupin, C Mark; Izvekov, Sergei; Voth, Gregory A


    In this report, a general methodology is presented for the parametrization of a reactive force field using data from a condensed phase ab initio molecular dynamics (AIMD) simulation. This algorithm allows for the creation of an empirical reactive force field that accurately reproduces the underlying ab initio reactive surface while providing the ability to achieve long-time statistical sampling for large systems not possible with AIMD alone. In this work, a model for the hydrated excess proton is constructed where the hydronium cation and proton hopping portions of the model are statistically force-matched to the results of Car-Parrinello Molecular Dynamics (CPMD) simulations. The flexible nature of the algorithm also allows for the use of the more accurate classical simple point-charge flexible water (SPC/Fw) model to describe the water-water interactions while utilizing the ab initio data to create an overall multistate molecular dynamics (MS-MD) reactive model of the hydrated excess proton in water. The resulting empirical model for the system qualitatively reproduces thermodynamic and dynamic properties calculated from the ab initio simulation while being in good agreement with experimental results and previously developed multistate empirical valence bond (MS-EVB) models. The present methodology, therefore, bridges the AIMD technique with the MS-MD modeling of reactive events, while incorporating key strengths of both.

  19. Two types of phase diagrams for two-species Bose-Einstein condensates and the combined effect of the parameters (United States)

    Li, Z. B.; Liu, Y. M.; Yao, D. X.; Bao, C. G.


    Under the Thomas-Fermi approximation, an approach is proposed to solve the coupled Gross-Pitaevskii equations (CGP) for the two-species Bose-Einstein condensate analytically. The essence of this approach is to find out the building blocks to build the solution. By introducing the weighted strengths, relatively simpler analytical solutions have been obtained. A number of formulae have been deduced to relate the parameters when the system is experimentally tuned at various status. These formulae demonstrate the combined effect of the parameters, and are useful for the evaluation of their magnitudes. The whole parameter space is divided into zones, where each supports a specific phase. All the boundaries separating these zones have analytical expressions. Based on the division, the phase diagrams against any set of parameters can be plotted. In addition, by introducing a model for the asymmetric states, the total energies of the lowest symmetric and asymmetric states have been compared. Thereby, in which case the former will be replaced by the latter has been evaluated. The CGP can be written in a matrix form. For repulsive inter-species interaction V AB , when the parameters vary and cross over the singular point of the matrix, a specific state transition will happen and the total energy of the lowest symmetric state will increase remarkably. This provides an excellent opportunity for the lowest asymmetric state to emerge as the ground state. For attractive V AB , when the parameters tend to a singular point, the system will tend to collapse. The effects caused by the singular points have been particularly studied.

  20. The propagation of detonation waves in non-ideal condensed-phase explosives confined by high sound-speed materials (United States)

    Schoch, Stefan; Nikiforakis, Nikolaos; Lee, Bok Jik


    Highly non-ideal condensed-phase explosives used by the mining industry have a strong detonation velocity dependence on the charge dimension. Detonation velocities can be as low as one third of the theoretically calculated ideal detonation velocity in charge radii close to the failure radius. Under these detonation conditions the flow in the confiner can become subsonic, a flow condition under which classical shock-polar analysis is not applicable. This restriction prohibits the use of popular engineering models like detonation shock dynamics and Wood-Kirkwood type models under these confinement conditions. In addition, it has been found in the literature that subsonic flow in the confiner will increase the influence of the confining material on the detonation performance. In this work, we use a multi-phase model coupled to an elastic-plastic model (for the representation of a confiner) to explore the interaction of detonations under these confiner conditions. An ammonium nitrate based mining emulsion is investigated in aluminium and steel confinement of finite and infinite thickness representing the confiner as either a fluid or an elastic-plastic material. It is found that the presence of elastic waves is negligible close to ideal detonation conditions, but is important close to the failure radius and in detonation conditions with subsonic flow in the confiner. High sound-speed confiners support the detonation through energy transport ahead of the detonation front if desensitisation effects are negligible. The detonation front profiles are found to remain convex even in the most non-ideal detonation conditions, and the detonation front curvature only becomes concave in a localised region close to the confiner edge.

  1. Freeze-Tolerant Condensers (United States)

    Crowley, Christopher J.; Elkouhk, Nabil


    Two condensers designed for use in dissipating heat carried by working fluids feature two-phase, self-adjusting configurations such that their working lengths automatically vary to suit their input power levels and/or heat-sink temperatures. A key advantage of these condensers is that they can function even if the temperatures of their heat sinks fall below the freezing temperatures of their working fluids and the fluids freeze. The condensers can even be restarted from the frozen condition. The top part of the figure depicts the layout of the first condenser. A two-phase (liquid and vapor) condenser/vapor tube is thermally connected to a heat sink typically, a radiatively or convectively cooled metal panel. A single-phase (liquid) condensate-return tube (return artery) is also thermally connected to the heat sink. At intervals along their lengths, the condenser/vapor tube and the return artery are interconnected through porous plugs. This condenser configuration affords tolerance of freezing, variable effective thermal conductance (such that the return temperature remains nearly constant, independently of the ultimate sink temperature), and overall pressure drop smaller than it would be without the porous interconnections. An additional benefit of this configuration is that the condenser can be made to recover from the completely frozen condition either without using heaters, or else with the help of heaters much smaller than would otherwise be needed. The second condenser affords the same advantages and is based on a similar principle, but it has a different configuration that affords improved flow of working fluid, simplified construction, reduced weight, and faster recovery from a frozen condition.

  2. Vortices and hysteresis in a rotating Bose-Einstein condensate with anharmonic confinement

    DEFF Research Database (Denmark)

    Jackson, A.D.; Kavoulakis, G.M.


    Vortices; Bose-Einstein condensation; phase diagrams; phase transformation Udgivelsesdato: 4 August......Vortices; Bose-Einstein condensation; phase diagrams; phase transformation Udgivelsesdato: 4 August...


    Directory of Open Access Journals (Sweden)

    Monica Sabrina Widiapranolo


    Full Text Available Abstract: Analog of curcumin in forms of enone and dienone aromatic is known for their activity as an NF-κB inhibitor. In this study, will be synthesize 2-(4'-N, N-dimethylamino benzilidine cyclohexane-1,3-dione as an analog that predicted has an activity as an NF-κB inhibitor. This research was conducted based on the crossed aldol condensation reaction by reacting 3 mmole pN,N-dimethylamino benzaldehide and 6 mmole cyclohexane-1,3-dione with hydrochloric acid as the catalyst using solid phase reaction method. Based on computational analysis, 2-(4'-N,Ndimethylamino benzilidine cyclohexane-1,3-dione showed a better interaction with NF-κB protein with PLANTSPLP score was -69,7895. The outcome of the reaction was yellow colored powder, no odor and soluble in hydrochloric acid 3N. The yield value was 78.8%. Liquid chromatography showed 100% purity. The melting point range was 237.5-240.3°C. The results of structure elucidation by 1H-NMR, infrared and mass spectroscopy tests indicated the compound was 2-(4-(dimetilaminobenzilidena-4-(3-oksosiklohex-1-enil sikloheksana-1,3-dion. Key words: 2-(4'-N, N-dimethylamino benzilidine cyclohexane-1,3-dione, crossed aldol condensation, solid phase reaction.

  4. Condensation Reactions of 3-Oxo-2-arylhydrazonopropanals with Active Methylene Reagents: Formation of 2-Hydroxy- and 2-Amino-6-substituted-5-arylazonicotinates and Pyrido[3,2-c]cinnolines via 6π-Electrocyclization Reactions

    Directory of Open Access Journals (Sweden)

    Saleh M. Al-Mousawi


    Full Text Available 3-Oxo-3-phenyl-2-(p-tolylhydrazonopropanal (1a undergoes condensation with ethyl cyanoacetate in acetic acid in the presence of ammonium acetate to yield either 2-hydroxy-6-phenyl-5-p-tolylazonicotinic acid ethyl ester (6a or 2-amino-6-phenyl-5-p-tolyl-azonicotinic acid ethyl ester (8, depending on the reaction conditions. Similarly, other 3-oxo-3-aryl-2-arylhydrazonopropanals 1a,b condense with active methylene nitriles 2c,d to yield arylazonicotinates 6b,c. In contrast, 2-[(4-nitrophenyl-hydrazono]-3-oxo-3-phenyl-propanal (1c reacts with ethyl cyanoacetate to yield ethyl 6-(4-nitrophenyl-2-oxo-2,6-dihydropyrido[3,2–c]cinnoline-3-carboxylate (11, via a novel 6π-electrocyclization pathway. Finally, 3-oxo-2-(phenylhydrazono-3-p-tolylpropanal (1d condenses with 2a–c to yield pyridazinones 13a–c.

  5. Preparation of neuroprotective condensed 1,4-benzoxazepines by regio- and diastereoselective domino Knoevenagel–[1,5]-hydride shift cyclization reaction

    Directory of Open Access Journals (Sweden)

    László Tóth


    Full Text Available Condensed O,N-heterocycles containing tetrahydro-1,4-benzoxazepine and tetrahydroquinoline moieties were prepared by a regio- and diastereoselective domino Knoevenagel–[1,5]-hydride shift cyclization reaction of a 4-aryl-2-phenyl-1,4-benzoxazepine derivative obtained from flavanone. The relative configuration of products were determined by the correlation of 3JH,H coupling data with the geometry of major conformers accessed by DFT conformational analysis. Separated enantiomers of the products were characterized by HPLC-ECD data, which allowed their configurational assignment on the basis of TDDFT-ECD calculation of the solution conformers. Two compounds showed neuroprotective activities against hydrogen peroxide (H2O2 or β-amyloid25–35 (Aβ25–35-induced cellular injuries in human neuroblastoma SH-SY5Y cells in the range of those of positive controls.

  6. Phosphonium salts as chiral phase-transfer catalysts: asymmetric Michael and Mannich reactions of 3-aryloxindoles. (United States)

    He, Rongjun; Ding, Changhua; Maruoka, Keiji


    It's a PTC: A highly efficient reaction of 3-aryloxindoles in an asymmetric Michael addition was achieved by using a quaternary tetraalkylphosphonium salt as a chiral phase-transfer catalyst (PTC). The products were obtained in quantitative yields high ee values. The reaction of 3-aryloxindoles in an asymmetric Mannich reaction using the same catalyst also proved to be feasible.

  7. The Pictet-Spengler reaction in solid-phase combinatorial chemistry

    DEFF Research Database (Denmark)

    Nielsen, Thomas E; Diness, Frederik; Meldal, Morten


    The Pictet-Spengler reaction is an important reaction for the generation of tetrahydro-beta-carbolines and tetrahydroisoquinoline ring systems, which exhibit a range of biological and pharmacological properties. This review covers the solid-phase Pictet-Spengler reaction, as employed in solid...

  8. Multiple pollutant removal using the condensing heat exchanger: Phase 1 final report, November 1995--June 1997. Addendum 2: Task 3 topical report -- Long term wear test

    Energy Technology Data Exchange (ETDEWEB)

    Kudlac, G.A.


    Long-term operation of a condensing heat exchanger under typical coal-fired flue gas conditions was investigated in Phase 1, Task 3 of the Multiple Pollutant Removal Using the Condensing Heat Exchanger test program. The specific goal of this task was to determine the amount of wear, if any, on the Teflon{reg_sign}-covered heat transfer tubes in a condensing heat exchanger. A pilot-scale single-stage condensing heat exchanger (CHX{reg_sign}) was operated under typical coal-fired flue gas conditions on a continuous basis for a period of approximately 10 months. Operating conditions and particulate loadings for the test unit were monitored, Teflon{reg_sign} film thickness measurements were conducted, and surface replications (which duplicate the surface finish at the microscopic level) were taken at various times during the test. Data from the test indicate that virtually no decrease in Teflon{reg_sign} thickness was observed for the coating on the first two rows of heat exchanger tubes, even at high inlet particulate loadings (400 mg/dscm [0.35 lb/10{sup 6} Btu]). Evidence of wear was present only at the microscopic level, and even then was very minor in severity. Operation at high inlet particulate loadings resulted in accumulated ash deposits within the heat exchanger. Installation of a modified (higher flow rate) wash nozzle manifold substantially reduced subsequent deposit formation.

  9. Gas-Phase Ion-Molecule Reactions in Tetrahydrothiophene

    National Research Council Canada - National Science Library

    HIRAOKA, Kenzo; SHODA, Takashi; YAMABE, Shinichi; IGNACIO, Edgar W


    .... The proton affinity (PA) of tetrahydrothiophene (THT), C4H8S, has been newly determined to be 205.4 kcal mol-1 by measuring the equilibria of the proton transfer reaction between 2-methyltetrahydrofuran and THT...

  10. CONDENSATION CAN (United States)

    Booth, E.T. Jr.; Pontius, R.B.; Jacobsohn, B.A.; Slade, C.B.


    An apparatus is designed for condensing a vapor to a solid at relatively low back pressures. The apparatus comprises a closed condensing chamber, a vapor inlet tube extending to the central region of the chamber, a co-axial tubular shield surrounding the inlet tube, means for heating the inlet tube at a point outside the condensing chamber, and means for refrigeratirg the said chamber. (AEC)

  11. Energetics of intermolecular HONO formation in condensed-phase octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) (United States)

    Lewis, James P.


    We present preliminary work on the formation of HONO in condensed-phase HMX for the three pure polymorphic phases. Our results show that the energetics of the intermolecular hydrogen transfer (to form HONO on an adjacent molecule) is more favorable in δ-HMX than in α-HMX and β-HMX. The energetics of this intermolecular hydrogen transfer process follow the same trends of HMX sensitivity, where δ-HMX is found to be more sensitive to explosion compared to β-HMX.

  12. Water Condensation

    DEFF Research Database (Denmark)

    Jensen, Kasper Risgaard; Fojan, Peter; Jensen, Rasmus Lund


    The condensation of water is a phenomenon occurring in multiple situations in everyday life, e.g., when fog is formed or when dew forms on the grass or on windows. This means that this phenomenon plays an important role within the different fields of science including meteorology, building physics......, and chemistry. In this review we address condensation models and simulations with the main focus on heterogeneous condensation of water. The condensation process is, at first, described from a thermodynamic viewpoint where the nucleation step is described by the classical nucleation theory. Further, we address...

  13. Condensed tannins: The formation of a diarylpropanol-catechinic acid dimer from base-catalyzed reactions of (+)-catechin (United States)

    Seiji Ohara; Richard W. Hemingway


    Reaction of (+ )-catechin at pH 12 and 40 DC results in the stereoselective (if not stereospecific) formation of an enolic form of 1-[6-(3',4'-dihydroxyphenyl)-7-hydroxybicyclo[3.3.1]nonane-2,4,9-trione-3-yl]-1-(3,4-dihyroxyphenyl)-3-(2,-4,6-trihydroxyphenyl)-propan-2-ol. The n.m.r. chemical shift assignments determined by a variety of two-dimensional...

  14. A route to hydroxylfluorenes: TsOH-mediated condensation reactions of 1,3-diketones with propargylic alcohols

    KAUST Repository

    Yao, Liangfeng


    An efficient method of preparing hydroxylfluorenes by TsOH-mediated tandem alkylation/rearrangements of propargylic alcohols with 1,3-diketones is described. These reactions are accomplished in moderate to good yields under mild conditions to offer a straightforward and convenient one step synthetic route to hydroxylfluorene derivatives through a plausible mechanism involving a sequence of dehydration, addition, rearrangement and aromatization. This journal is © The Royal Society of Chemistry 2012.

  15. The Phase Behavior Effect on the Reaction Engineering of Transesterification Reactions and Reactor Design for Continuous Biodiesel Production (United States)

    Csernica, Stephen N.

    The demand for renewable forms of energy has increased tremendously over the past two decades. Of all the different forms of renewable energy, biodiesel, a liquid fuel, has emerged as one of the more viable possibilities. This is in large part due to the fact that biodiesel can readily be used in modern day diesel engines with nearly no engine modifications. It is commonly blended with conventional petroleum-derived diesel but it can also be used neat. As a result of the continued growth of the industry, there has been a correspondingly large increase in the scientific and technical research conducted on the subject. Much of the research has been conducted on the feasibility of using different types of feedstocks, which generally vary with respect to geographic locale, as well as different types of catalysts. Much of the work of the present study was involved with the investigation of the binary liquid-liquid nature of the system and its effects on the reaction kinetics. Initially, the development of an analytical method for the analysis of the compounds present in transesterification reaction mixtures using high performance liquid chromatography (HPLC) was developed. The use of UV(205 nm) as well as refractive index detection (RID) were shown capable to detect the various different types of components associated with transesterification reactions. Reversed-phase chromatography with isocratic elution was primarily used. Using a unique experimental apparatus enabling the simultaneous analysis of both liquid phases throughout the reaction, an experimental method was developed for measuring the reaction rate under both mass transfer control and reaction control. The transesterification reaction rate under each controlling mechanism was subsequently evaluated and compared. It was determined that the reaction rate is directly proportional to the concentration of triglycerides in the methanol phase. Furthermore, the reaction rate accelerates rapidly as the system

  16. How accurate is Density Functional Theory in Predicting Reaction Energies Relevant to Phase Stability? (United States)

    Hautier, Geoffroy; Ong, Shyue Ping; Jain, Anubhav; Moore, Charles J.; Ceder, Gerbrand


    Density Functional Theory (DFT) computations can be used to build computational phase diagrams that are used to understand the stability of known phases but also to assess the stability of novel, predicted compounds. The quality and predictive power of those phase diagrams rely on the accuracy of DFT in modeling reaction energies and we will present in this talk the results of a large scale comparison between experimentally measured and DFT computed reaction energies. For starters, we will show that only certain reaction energies are directly relevant to phase stability of multicomponent systems and that very often those reaction energies are not the commonly studied reactions from the elements. Using data from different experimental thermochemical tables and DFT high-throughput computing, we will present the results of a statistical study based on more than 130 reaction energies relevant to phase stability and from binary oxides to ternary oxides. We will show that the typical error are around 30 meV/at and therefore an order of magnitude lower than the errors in reaction energies from the elements. Finally, we will discuss the broad implications of our results on the evaluation of ab initio phase diagrams and on the computational prediction of new solid phases.

  17. Iron Oxide-Supported Copper Oxide Nanoparticles (Nanocat-Fe-CuO): Magnetically Recyclable Catalysts for the Synthesis of Pyrazole Derivatives, 4-Methoxyaniline, and Ullmann-type Condensation Reactions (United States)

    An efficient and benign protocol is reported for the synthesis of 4-methoxyaniline, medicinally important pyrazole derivatives, and Ullmann-type condensation reaction using magnetically separable and reusable magnetite-supported copper (nanocat-Fe-CuO) nanoparticles under mild co...

  18. Analysis of reaction products formed in the gas phase reaction of E,E-2,4-hexadienal with atmospheric oxidants: Reaction mechanisms and atmospheric implications (United States)

    Colmenar, I.; Martin, P.; Cabañas, B.; Salgado, S.; Martinez, E.


    An analysis of reaction products for the reaction of E,E-2,4-hexadienal with chlorine atoms (Cl) and OH and NO3 radicals has been carried out at the first time with the aim of obtaining a better understanding of the tropospheric reactivity of α,β-unsaturated carbonyl compounds. Fourier Transform Infrared (FTIR) spectroscopy and Gas Chromatography-Mass Spectrometry with a Time of Flight detector (GC-TOFMS) were used to carry out the qualitative and/or quantitative analyses. Reaction products in gas and particulate phase were observed from the reactions of E,E-2,4- hexadienal with all oxidants. E/Z-Butenedial and maleic anhydride were the main products identified in gas phase. E-butenedial calculated molar yield ranging from 4 to 10%. A significant amount of multifunctional compounds (chloro and hydroxy carbonyls) was identified. These compounds could be formed in particulate phase explaining the ∼90% of unaccounted carbon in gas phase. The reaction with Cl atoms in the presence of NOx with a long reaction time gave Peroxy Acetyl Nitrate (PAN) as an additional product, which is known for being an important specie in the generation of the photochemical smog. Nitrated compounds were the major organic products from the reaction with the NO3 radical. Based on the identified products, the reaction mechanisms have been proposed. In these mechanisms a double bond addition of the atmospheric oxidant at C4/C5 of E,E-2,4-hexadienal is the first step for tropospheric degradation.

  19. Gas phase studies of the Pesci decarboxylation reaction: synthesis, structure, and unimolecular and bimolecular reactivity of organometallic ions. (United States)

    O'Hair, Richard A J; Rijs, Nicole J


    CONSPECTUS: Decarboxylation chemistry has a rich history, and in more recent times, it has been recruited in the quest to develop cheaper, cleaner, and more efficient bond-coupling reactions. Thus, over the past two decades, there has been intense investigation into new metal-catalyzed reactions of carboxylic substrates. Understanding the elementary steps of metal-mediated transformations is at the heart of inventing new reactions and improving the performance of existing ones. Fortunately, during the same time period, there has been a convergence in mass spectrometry (MS) techniques, which allows these catalytic processes to be examined efficiently in the gas phase. Thus, electrospray ionization (ESI) sources have been combined with ion-trap mass spectrometers, which in turn have been modified to either accept radiation from tunable OPO lasers for spectroscopy based structural assignment of ions or to allow the study of ion-molecule reactions (IMR). The resultant "complete" gas-phase chemical laboratories provide a platform to study the elementary steps of metal-catalyzed decarboxylation reactions in exquisite detail. In this Account, we illustrate how the powerful combination of ion trap mass spectrometry experiments and DFT calculations can be systematically used to examine the formation of organometallic ions and their chemical transformations. Specifically, ESI-MS allows the transfer of inorganic carboxylate complexes, [RCO2M(L)n](x), (x = charge) from the condensed to the gas phase. These mass selected ions serve as precursors to organometallic ions [RM(L)n](x) via neutral extrusion of CO2, accessible by slow heating in the ion trap using collision induced dissociation (CID). This approach provides access to an array of organometallic ions with well-defined stoichiometry. In terms of understanding the decarboxylation process, we highlight the role of the metal center (M), the organic group (R), and the auxiliary ligand (L), along with cluster nuclearity, in

  20. Enhanced Hydrothermal Stability and Catalytic Activity of La x Zr y O z Mixed Oxides for the Ketonization of Acetic Acid in the Aqueous Condensed Phase

    Energy Technology Data Exchange (ETDEWEB)

    Lopez-Ruiz, Juan A. [Energy and Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99352, United States; Cooper, Alan R. [Energy and Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99352, United States; Li, Guosheng [Energy and Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99352, United States; Albrecht, Karl O. [Energy and Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99352, United States


    Common ketonization catalysts such as ZrO2, CeO2, CexZryOz, and TiO2-based catalysts have been reported to lose surface area, undergo phase-transformation, and lose catalytic activity when utilized in the condensed aqueous phase. In this work, we synthesized and tested a series of LaxZryOz mixed metal oxides with different La:Zr atomic ratios with the goal of enhancing the catalytic activity and stability for the ketonization of acetic acid in condensed aqueous media at 568 K. We synthesized a hydrothermally stable LaxZryOz mixed-metal oxide catalyst with enhanced ketonization activities 360 and 40 times more active than La2O3 and ZrO2, respectively. Catalyst characterization techniques suggest that the formation of a hydrothermally stable catalyst which is isomorphic with tetragonal-ZrO2 under hydrothermal reaction conditions.

  1. Pressure induced reactions amongst calcium aluminate hydrate phases

    KAUST Repository

    Moon, Ju-hyuk


    The compressibilities of two AFm phases (strätlingite and calcium hemicarboaluminate hydrate) and hydrogarnet were obtained up to 5 GPa by using synchrotron high-pressure X-ray powder diffraction with a diamond anvil cell. The AFm phases show abrupt volume contraction regardless of the molecular size of the pressure-transmitting media. This volume discontinuity could be associated to a structural transition or to the movement of the weakly bound interlayer water molecules in the AFm structure. The experimental results seem to indicate that the pressure-induced dehydration is the dominant mechanism especially with hygroscopic pressure medium. The Birch-Murnaghan equation of state was used to compute the bulk modulus of the minerals. Due to the discontinuity in the pressure-volume diagram, a two stage bulk modulus of each AFm phase was calculated. The abnormal volume compressibility for the AFm phases caused a significant change to their bulk modulus. The reliability of this experiment is verified by comparing the bulk modulus of hydrogarnet with previous studies. © 2011 Elsevier Ltd. All rights reserved.

  2. Synthesis and Reactions of Five-Membered Heterocycles Using Phase Transfer Catalyst (PTC Techniques

    Directory of Open Access Journals (Sweden)

    Ahmed M. El-Sayed


    Full Text Available Phase transfer catalysts (PTCs have been widely used for the synthesis of organic compounds particularly in both liquid-liquid and solid-liquid heterogeneous reaction mixtures. They are known to accelerate reaction rates by facilitating formation of interphase transfer of species and making reactions between reagents in two immiscible phases possible. Application of PTC instead of traditional technologies for industrial processes of organic synthesis provides substantial benefits for the environment. On the basis of numerous reports it is evident that phase-transfer catalysis is the most efficient way for generation and reactions of many active intermediates. In this review we report various uses of PTC in syntheses and reactions of five-membered heterocycles compounds and their multifused rings.

  3. Organobase-catalyzed three-component reactions for the synthesis of 4H-2-aminopyrans, condensed pyrans and polysubstituted benzenes

    Directory of Open Access Journals (Sweden)

    Moustafa Sherief Moustafa


    Full Text Available Novel routes for the preparation of 2-amino-4H-pyran-3-carbonitrile 9, amino-arylbenzoic acid ester derivatives 13a,b, 2-aminotetrahydro-4H-chromene-3-carbonitrile 18, 3-amino-4-cyanotetrahydronaphthalene-2-carboxylic acid ester 26 and 4-amino-3,5-dicyanophthalic acid ester derivatives 37a–c were developed. The synthetic methods utilize one-pot reactions of acetylene carboxylic acid esters, α,β-unsaturated nitriles and/or active methylenenitriles in the presence of L-proline or DABCO. Plausible mechanisms are suggested for the formation of the products. Finally, these compounds were used for the efficient synthesis of 6-amino-5-cyanonicotinic acid ester derivatives 31a,b, ethyl 4-amino-5H-pyrano[2,3-d]pyrimidine-6-carboxylates 33a,b, 4-amino-6H-pyrrolo[3,4-g]quinazoline-9-carbonitrile 39, and 1,7-diamino-6-(N'-hydroxycarbamimidoyl-3-oxo-5-phenyl-3H-isoindole-4-carboxylate (40.

  4. Organobase-catalyzed three-component reactions for the synthesis of 4H-2-aminopyrans, condensed pyrans and polysubstituted benzenes. (United States)

    Moustafa, Moustafa Sherief; Al-Mousawi, Saleh Mohammed; Selim, Maghraby Ali; Mosallam, Ahmed Mohamed; Elnagdi, Mohamed Hilmy


    Novel routes for the preparation of 2-amino-4H-pyran-3-carbonitrile 9, amino-arylbenzoic acid ester derivatives 13a,b, 2-aminotetrahydro-4H-chromene-3-carbonitrile 18, 3-amino-4-cyanotetrahydronaphthalene-2-carboxylic acid ester 26 and 4-amino-3,5-dicyanophthalic acid ester derivatives 37a-c were developed. The synthetic methods utilize one-pot reactions of acetylene carboxylic acid esters, α,β-unsaturated nitriles and/or active methylenenitriles in the presence of L-proline or DABCO. Plausible mechanisms are suggested for the formation of the products. Finally, these compounds were used for the efficient synthesis of 6-amino-5-cyanonicotinic acid ester derivatives 31a,b, ethyl 4-amino-5H-pyrano[2,3-d]pyrimidine-6-carboxylates 33a,b, 4-amino-6H-pyrrolo[3,4-g]quinazoline-9-carbonitrile 39, and 1,7-diamino-6-(N'-hydroxycarbamimidoyl)-3-oxo-5-phenyl-3H-isoindole-4-carboxylate (40).

  5. Pilot scale experiments of magnesia hydration under gas-liquid-solid (three-phase) reaction system (United States)

    Tang, Xiaojia; Lv, Qiwei; Yin, Lin; Nie, Yixing; Jin, Qi; Ji, Yangyuan; Zhu, Yimin


    Pilot scale experiments were conducted to prepare magnesium hydroxide by magnesia hydration under gas-liquid-solid (three-phase) reaction system. The effect of reaction pressure, reactivity and particle size of magnesia and the concentration of the pulp on the degree of hydration was investigated. The results indicated that the hydration reaction occurred at the first 30min mainly. During the set reaction condition, degree of hydration of 68% could be obtained at the reaction pressure of 0.2MPa, concentration of pulp of 5%w/w with high reactivity and fine powder. The promotion effect on the degree of hydration caused by the three-phase reaction system was mostly attributed to the exfoliation of steam.

  6. Synthesis of TiO2 Nanoparticles from Ilmenite Through the Mechanism of Vapor-Phase Reaction Process by Thermal Plasma Technology (United States)

    Samal, Sneha


    Synthesis of nanoparticles of TiO2 was carried out by non-transferred arc thermal plasma reactor using ilmenite as the precursor material. The powder ilmenite was vaporized at high temperature in plasma flame and converted to a gaseous state of ions in the metastable phase. On cooling, chamber condensation process takes place on recombination of ions for the formation of nanoparticles. The top-to-bottom approach induces the disintegration of complex ilmenite phases into simpler compounds of iron oxide and titanium dioxide phases. The vapor-phase reaction mechanism was carried out in thermal plasma zone for the synthesis of nanoparticles from ilmenite compound in a plasma reactor. The easy separation of iron particles from TiO2 was taken place in the plasma chamber with deposition of light TiO2 particles at the top of the cooling chamber and iron particles at the bottom. The dissociation and combination process of mechanism and synthesis are studied briefly in this article. The product TiO2 nanoparticle shows the purity with a major phase of rutile content. TiO2 nanoparticles produced in vapor-phase reaction process shows more photo-induced capacity.

  7. Preparation of molybdenum borides by combustion synthesis involving solid-phase displacement reactions

    Energy Technology Data Exchange (ETDEWEB)

    Yeh, C.L. [Department of Mechanical and Automation Engineering, Da-Yeh University, 112 Shan-Jiau Rd., Da-Tsuen, Changhua 51505, Taiwan (China)], E-mail:; Hsu, W.S. [Department of Mechanical and Automation Engineering, Da-Yeh University, 112 Shan-Jiau Rd., Da-Tsuen, Changhua 51505, Taiwan (China)


    Preparation of molybdenum borides of five different phases in the Mo-B binary system (including Mo{sub 2}B, MoB, MoB{sub 2}, Mo{sub 2}B{sub 5}, and MoB{sub 4}) was performed by self-propagating high-temperature synthesis (SHS) with two kinds of the reactant samples. When elemental powder compacts with an exact stoichiometry corresponding to the boride phase were employed, self-sustaining reaction was only achieved in the sample with Mo:B = 1:1 and nearly single-phase MoB was yielded. Therefore, the other four boride compounds were prepared from the reactant compacts composed of MoO{sub 3}, Mo, and B powders, within which the displacement reaction of MoO{sub 3} with boron was involved in combustion synthesis. Experimental evidence shows that the extent of displacement reaction in the overall reaction has a significant impact on sustainability of the synthesis reaction, combustion temperature, reaction front velocity, and composition of the end product. An increase in the solid-phase displacement reaction taking place during the SHS process contributes more heat flux to the synthesis reaction, thus resulting in the increase of combustion temperature and enhancement of the reaction front velocity. Based upon the XRD analysis, formation of Mo{sub 2}B, MoB{sub 2}, and Mo{sub 2}B{sub 5} as the dominant boride phase in the end product was successful through the SHS reaction with powder compacts under appropriate stoichiometries between MoO{sub 3}, Mo, and B. However, a poor conversion was observed in the synthesis of MoB{sub 4}. The powder compact prepared for the production of MoB{sub 4} yielded mostly Mo{sub 2}B{sub 5}.

  8. Positronium in a Liquid Phase: Formation, Bubble State and Chemical Reactions

    Directory of Open Access Journals (Sweden)

    Sergey V. Stepanov


    Full Text Available The present approach describes the e+ fate since its injection into a liquid until its annihilation. Several stages of the e+ evolution are discussed: (1 energy deposition and track structure of fast positrons: ionization slowing down, number of ion-electron pairs, typical sizes, thermalization, electrostatic interaction between e+ and the constituents of its blob, and effect of local heating; (2 positronium formation in condensed media: the Ore model, quasifree Ps state, intratrack mechanism of Ps formation; (3 fast intratrack diffusion-controlled reactions: Ps oxidation and ortho-paraconversion by radiolytic products, reaction rate constants, and interpretation of the PAL spectra in water at different temperatures; (4 Ps bubble models. Inner structure of positronium (wave function, energy contributions, relationship between the pick-off annihilation rate and the bubble radius.

  9. Two-phase (bio)catalytic reactions in a table-top centrifugal contact separator

    NARCIS (Netherlands)

    Kraai, Gerard N.; Zwol, Floris van; Schuur, Boelo; Heeres, Hero J.; Vries, Johannes G. de


    A new spin on catalysis: A table-top centrifugal contact separator allows for fast continuous two-phase reactions to be performed by intimately mixing two immiscible phases and then separating them. Such a device has been used to produce biodiesel from sunflower oil and MeOH/NaOMe. A

  10. Radical Reactions in the Gas Phase: Recent Development and Application in Biomolecules

    Directory of Open Access Journals (Sweden)

    Yang Gao


    Full Text Available This review summarizes recent literature describing the use of gas phase radical reactions for structural characterization of complex biomolecules other than peptides. Specifically, chemical derivatization, in-source chemical reaction, and gas phase ion/ion reactions have been demonstrated as effective ways to generate radical precursor ions that yield structural informative fragments complementary to those from conventional collision-induced dissociation (CID. Radical driven dissociation has been applied to a variety of biomolecules including peptides, nucleic acids, carbohydrates, and phospholipids. The majority of the molecules discussed in this review see limited fragmentation from conventional CID, and the gas phase radical reactions open up completely new dissociation channels for these molecules and therefore yield high fidelity confirmation of the structures of the target molecules. Due to the extensively studied peptide fragmentation, this review focuses only on nonpeptide biomolecules such as nucleic acids, carbohydrates, and phospholipids.

  11. Supersymmetry is afraid of condensates

    Directory of Open Access Journals (Sweden)

    G. Domokos


    Full Text Available Supersymmetry is never broken by pair condensates of chiral superfields: the supersymmetry breaking part of Green's functions satisfies an equation which always has an identically vanishing solution. Hence any phase containing pair condensates is unstable due to its positive vacuum energy.

  12. A study of aqueous phase reactions relevant for atmospheric chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Loegager, T.


    The subject of this thesis being aqueous phase atmospheric chemistry, species of atmospheric relevance such ad ozone (O{sub 3}) ferrous ion (Fe{sup 2+}), the ferryl ion (FeO{sup 2+}), hydrogen perioxide (H{sub 2}O{sub 2}), the nitrite and nitrate ion and their acids, peroxynitrous acid (ONOOH), peroxynitric acid (O{sub 2}NOOH), and the radicals {sub a}{sup -}{sub q}, H, OH, HO{sub 2}/O{sub 2}{sup -}, NO{sub 2}, NO{sub 3}, NO{sub 3}{sup =}, and SO{sub 4}{sup -}, have all been studied. The ai has been to study spectra, extinction coefficients, specific rate constants, kinetic mechanisms, and pK`s using the stopped-flow and pulse radiolysis techniques, combined with an indispensable chemical kinetics simulations program. (au).

  13. Developing ab initio quality force fields from condensed phase quantum-mechanics/molecular-mechanics calculations through the adaptive force matching method. (United States)

    Akin-Ojo, Omololu; Song, Yang; Wang, Feng


    A new method called adaptive force matching (AFM) has been developed that is capable of producing high quality force fields for condensed phase simulations. This procedure involves the parametrization of force fields to reproduce ab initio forces obtained from condensed phase quantum-mechanics/molecular-mechanics (QM/MM) calculations. During the procedure, the MM part of the QM/MM is iteratively improved so as to approach ab initio quality. In this work, the AFM method has been tested to parametrize force fields for liquid water so that the resulting force fields reproduce forces calculated using the ab initio MP2 and the Kohn-Sham density functional theory with the Becke-Lee-Yang-Parr (BLYP) and Becke three-parameter LYP (B3LYP) exchange correlation functionals. The AFM force fields generated in this work are very simple to evaluate and are supported by most molecular dynamics (MD) codes. At the same time, the quality of the forces predicted by the AFM force fields rivals that of very expensive ab initio calculations and are found to successfully reproduce many experimental properties. The site-site radial distribution functions (RDFs) obtained from MD simulations using the force field generated from the BLYP functional through AFM compare favorably with the previously published RDFs from Car-Parrinello MD simulations with the same functional. Technical aspects of AFM such as the optimal QM cluster size, optimal basis set, and optimal QM method to be used with the AFM procedure are discussed in this paper.

  14. From Rate Measurements to Mechanistic Data for Condensed Matter Reactions: A Case Study Using the Crystallization of [Zn(OH26][ZnCl4

    Directory of Open Access Journals (Sweden)

    Berkley G. Hillis


    Full Text Available The kinetics of crystallization of the R = 3 hydrate of zinc chloride, [Zn(OH26][ZnCl4], is measured by time-resolved synchrotron x-ray diffraction, time-resolved neutron diffraction, and by differential scanning calorimetry. It is shown that analysis of the rate data using the classic Kolmogorov, Johnson, Mehl, Avrami (KJMA kinetic model affords radically different rate constants for equivalent reaction conditions. Reintroducing the amount of sample measured by each method into the kinetic model, using our recently developed modified-KJMA model (M-KJMA, it is shown that each of these diverse rate measurement techniques can give the intrinsic, material specific rate constant, the velocity of the phase boundary, vpb. These data are then compared to the velocity of the crystallization front directly measured optically. The time-resolved diffraction methods uniquely monitor the loss of the liquid reactant and formation of the crystalline product demonstrating that the crystallization of this hydrate phase proceeds through no intermediate phases. The temperature dependent vpb data are then well fit to transition zone theory to extract activation parameters. These demonstrate that the rate-limiting component to this crystallization reaction is the ordering of the waters (or protons of hydration into restricted positions of the crystalline lattice resulting in large negative entropy of activation.

  15. Multiple pollutant removal using the condensing heat exchanger: Phase 1 final report, November 1995--May 1997. Addendum 1: Task 2 topical report -- Pollutant removal tests

    Energy Technology Data Exchange (ETDEWEB)

    Bailey, R.T.; Jankura, B.J.


    Integrated Flue Gas Treatment (IFGT) uses two Condensing Heat Exchangers (CHXs{reg_sign}) in series to recover waste heat from the flue gas and remove a variety of pollutants from the flue gas. The Teflon{reg_sign}-covered internals of the condensing heat exchanger permit heat recovery at temperatures below the acid dew-point of the flue gas. The pollutant removal characteristics of the IFGT system were measured over a wide range of operating conditions in a pilot Integrated Flue Gas Treatment System rated at 1.2 MW{sub t} (4 million Btu/hr) using a wide range of coals. The coals tested included a high-sulfur coal, a medium-sulfur coal and a low-sulfur coal. The flue gas pollutants investigated included ammonia, hydrogen chloride, hydrogen fluoride, particulate, sulfur dioxide, gas phase and particle phase mercury and gas phase and particle phase trace elements. The particulate removal efficiency and size distribution was also investigated. Soda ash, lime and magnesium-lime scrubbing reagents were investigated. The test results show that the IFGT system can remove greater than 95% removal of acid gases with a liquid-to-gas ratio less than 1.34 l/m{sup 3} (10 gal/1,000 ft{sup 3}), and that lime reagents show promise as a substitute for soda ash. Particulate and ammonia gas removal was also very high. Ionic mercury removal averaged 80%, while elemental mercury removal was very low. Trace metals were found to be concentrated in the fine particulate with removal efficiencies in the range of 50% to 80%. The data measured in this task provides the basis for predictions of the performance of an IFGT system for both utility and industrial applications.

  16. Condensed matter physics

    CERN Document Server

    Marder, Michael P


    This Second Edition presents an updated review of the whole field of condensed matter physics. It consolidates new and classic topics from disparate sources, teaching not only about the effective masses of electrons in semiconductor crystals and band theory, but also about quasicrystals, dynamics of phase separation, why rubber is more floppy than steel, granular materials, quantum dots, Berry phases, the quantum Hall effect, and Luttinger liquids.

  17. Quantum Phases and Collective Excitations of a Spin-Orbit-Coupled Bose-Einstein Condensate in a One-Dimensional Optical Lattice (United States)

    Martone, G. I.


    The ground state of a spin-orbit-coupled Bose gas in a one-dimensional optical lattice is known to exhibit a mixed regime, where the condensate wave function is given by a superposition of multiple Bloch-wave components, and an unmixed one, in which the atoms occupy a single Bloch state. The unmixed regime features two unpolarized Bloch-wave phases, having quasimomentum at the center or at the edge of the first Brillouin zone, and a polarized Bloch-wave phase at intermediate quasimomenta. By calculating the critical values of the Raman coupling and of the lattice strength at the transitions among the various phases, we show the existence of a tricritical point where the mixed, the polarized and the edge-quasimomentum phases meet, and whose appearance is a consequence of the spin-dependent interaction. Furthermore, we evaluate the excitation spectrum in the unmixed regime and we characterize the behavior of the phonon and the roton modes, pointing out the instabilities occurring when a phase transition is approached.

  18. Tuning Catalytic Performance through a Single or Sequential Post-Synthesis Reaction(s) in a Gas Phase

    Energy Technology Data Exchange (ETDEWEB)

    Shan, Junjun [Department; Department; Zhang, Shiran [Department; Department; Choksi, Tej [Department; Nguyen, Luan [Department; Department; Bonifacio, Cecile S. [Department; Li, Yuanyuan [Department; Zhu, Wei [Department; Department; College; Tang, Yu [Department; Department; Zhang, Yawen [College; Yang, Judith C. [Department; Greeley, Jeffrey [Department; Frenkel, Anatoly I. [Department; Tao, Franklin [Department; Department


    Catalytic performance of a bimetallic catalyst is determined by geometric structure and electronic state of the surface or even the near-surface region of the catalyst. Here we report that single and sequential postsynthesis reactions of an as-synthesized bimetallic nanoparticle catalyst in one or more gas phases can tailor surface chemistry and structure of the catalyst in a gas phase, by which catalytic performance of this bimetallic catalyst can be tuned. Pt–Cu regular nanocube (Pt–Cu RNC) and concave nanocube (Pt–Cu CNC) are chosen as models of bimetallic catalysts. Surface chemistry and catalyst structure under different reaction conditions and during catalysis were explored in gas phase of one or two reactants with ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) and extended X-ray absorption fine structure (EXAFS) spectroscopy. The newly formed surface structures of Pt–Cu RNC and Pt–Cu CNC catalysts strongly depend on the reactive gas(es) used in the postsynthesis reaction(s). A reaction of Pt–Cu RNC-as synthesized with H2 at 200 °C generates a near-surface alloy consisting of a Pt skin layer, a Cu-rich subsurface, and a Pt-rich deep layer. This near-surface alloy of Pt–Cu RNC-as synthesized-H2 exhibits a much higher catalytic activity in CO oxidation in terms of a low activation barrier of 39 ± 4 kJ/mol in contrast to 128 ± 7 kJ/mol of Pt–Cu RNC-as synthesized. Here the significant decrease of activation barrier demonstrates a method to tune catalytic performances of as-synthesized bimetallic catalysts. A further reaction of Pt–Cu RNC-as synthesized-H2 with CO forms a Pt–Cu alloy surface, which exhibits quite different catalytic performance in CO oxidation. It suggests the capability of generating a different surface by using another gas. The capability of tuning surface chemistry and structure of bimetallic catalysts was also demonstrated in restructuring of Pt–Cu CNC-as synthesized.

  19. Benzoin Condensation

    Indian Academy of Sciences (India)


    Roots of cassava (tapioca), an important food crop in many countries of the world, including India, contain acetone cyanohy- drin glucoside called linamarin. ..... The replacement of cyanide by the harmless thiazolium salts as catalysts for benzoin condensation is one of the finest examples of Green Chemistry in action. S. N.

  20. Chemical Characterization of Secondary Organic Aerosol Formed from Atmospheric Aqueous-phase Reactions of Phenolic Compounds (United States)

    Yu, L.; Smith, J.; Anastasio, C.; Zhang, Q.


    Phenolic compounds, which are released in significant amounts from biomass burning, may undergo fast aqueous-phase reactions to form secondary organic aerosol (SOA) in the atmosphere. Understanding the aqueous-phase reaction mechanisms of these compounds and the composition of their reaction products is thus important for constraining SOA sources and predicting organic aerosol properties in models. In this study, we investigate the aqueous-phase reactions of three phenols (phenol, guaiacol and syringol) with two oxidants - excited triplet states (3C*) of non-phenolic aromatic carbonyls and hydroxyl radical (OH). By employing four analytical methods including high-resolution aerosol mass spectrometry, total organic carbon analysis, ion chromatography, and liquid chromatography-mass spectrometry, we thoroughly characterize the chemical compositions of the low volatility reaction products of phenols and propose formation mechanisms based on this information. Our results indicate that phenolic SOA is highly oxygenated, with O/C ratios in the range of 0.83-1.03, and that the SOA of phenol is usually more oxidized than those of guaiacol and syringol. Among the three precursors, syringol generates the largest fraction of higher molecular weight (MW) products. For the same precursor, the SOA formed via reaction with 3C* is less oxidized than that formed via reaction with OH. In addition, oxidation by 3C* enhances the formation of higher MW species, including phenolic dimers, higher oligomers and hydroxylated products, compared to reactions initiated by OH, which appear to favor the formation of organic acids. However, our results indicate that the yields of small organic acids (e.g., formate, acetate, oxalate, and malate) are low for both reaction pathways, together accounting for less than 5% of total SOA mass.

  1. Phase-Reduction Approach to Synchronization of Spatiotemporal Rhythms in Reaction-Diffusion Systems (United States)

    Nakao, Hiroya; Yanagita, Tatsuo; Kawamura, Yoji


    Reaction-diffusion systems can describe a wide class of rhythmic spatiotemporal patterns observed in chemical and biological systems, such as circulating pulses on a ring, oscillating spots, target waves, and rotating spirals. These rhythmic dynamics can be considered limit cycles of reaction-diffusion systems. However, the conventional phase-reduction theory, which provides a simple unified framework for analyzing synchronization properties of limit-cycle oscillators subjected to weak forcing, has mostly been restricted to low-dimensional dynamical systems. Here, we develop a phase-reduction theory for stable limit-cycle solutions of reaction-diffusion systems with infinite-dimensional state space. By generalizing the notion of isochrons to functional space, the phase-sensitivity function—a fundamental quantity for phase reduction—is derived. For illustration, several rhythmic dynamics of the FitzHugh-Nagumo model of excitable media are considered. Nontrivial phase-response properties and synchronization dynamics are revealed, reflecting their complex spatiotemporal organization. Our theory will provide a general basis for the analysis and control of spatiotemporal rhythms in various reaction-diffusion systems.

  2. Contrasting the excited state reaction pathways of phenol and para-methylthiophenol in the gas and liquid phases. (United States)

    Zhang, Yuyuan; Oliver, Thomas A A; Ashfold, Michael N R; Bradforth, Stephen E


    To explore how the solvent influences primary aspects of bond breaking, the gas and solution phase photochemistries of phenol and ofpara-methylthiophenol are directly compared using, respectively, H (Rydberg) atom photofragment translation spectroscopy and femtosecond transient absorption spectroscopy. Approaches are demonstrated that allow explicit comparisons of the nascent product energy disposals and dissociation mechanisms in the two phases. It is found, at least for the case of the weakly perturbing cyclohexane environment, that most aspects of the primary reaction dynamics of the isolated molecule are reproduced in solution. Specifically, in the gas phase, both molecules can undergo fast X-H (X = O, S) bond dissociation upon excitation with short wavelengths (193 sigma*)) state. Product electronic branching, vibrational and translational energy disposals are determined. Photolysis of phenol and para-methylthiophenol in solution at 200 nm results in formation of vibrationally excited radicals on a timescale shorter than 200 fs. Excitation of para-methylthiophenol at 267 nm reaches close to the S1 (1 1(pipi*))/S2 (11(pi sigma*)) conical intersection (CI): ultrafast dissociation is observed in both the isolated and solution systems-again indicating direct dissociation on the S2 potential energy surface. Comparing results for this precursor at different excitation energies, the extent of geminate recombination and the derived H-atom ejection lengths in the condensed phase photolyses are in qualitative agreement with the translational energy release measured in the gas phase studies. Conversely, excitation of phenol at 267 nm prepares the system in its S1 state at an energy well below its S1/S2 CI; the slow O-H bond fission inferred in the gas phase experiments is observed directly in the time-resolved studies in cyclohexane solution via the appearance of phenoxyl radical absorption after -1 ns, with only S1 excited state absorption discernible at earlier delay

  3. LSENS, a general chemical kinetics and sensitivity analysis code for gas-phase reactions: User's guide (United States)

    Radhakrishnan, Krishnan; Bittker, David A.


    A general chemical kinetics and sensitivity analysis code for complex, homogeneous, gas-phase reactions is described. The main features of the code, LSENS, are its flexibility, efficiency and convenience in treating many different chemical reaction models. The models include static system, steady, one-dimensional, inviscid flow, shock initiated reaction, and a perfectly stirred reactor. In addition, equilibrium computations can be performed for several assigned states. An implicit numerical integration method, which works efficiently for the extremes of very fast and very slow reaction, is used for solving the 'stiff' differential equation systems that arise in chemical kinetics. For static reactions, sensitivity coefficients of all dependent variables and their temporal derivatives with respect to the initial values of dependent variables and/or the rate coefficient parameters can be computed. This paper presents descriptions of the code and its usage, and includes several illustrative example problems.

  4. Insight into organic reactions from the direct random phase approximation and its corrections

    Energy Technology Data Exchange (ETDEWEB)

    Ruzsinszky, Adrienn [Department of Physics, Temple University, Philadelphia, Pennsylvania 19122 (United States); Zhang, Igor Ying; Scheffler, Matthias [Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin (Germany)


    The performance of the random phase approximation (RPA) and beyond-RPA approximations for the treatment of electron correlation is benchmarked on three different molecular test sets. The test sets are chosen to represent three typical sources of error which can contribute to the failure of most density functional approximations in chemical reactions. The first test set (atomization and n-homodesmotic reactions) offers a gradually increasing balance of error from the chemical environment. The second test set (Diels-Alder reaction cycloaddition = DARC) reflects more the effect of weak dispersion interactions in chemical reactions. Finally, the third test set (self-interaction error 11 = SIE11) represents reactions which are exposed to noticeable self-interaction errors. This work seeks to answer whether any one of the many-body approximations considered here successfully addresses all these challenges.

  5. Random-lattice models and simulation algorithms for the phase equilibria in two-dimensional condensed systems of particles with coupled internal and translational degrees of freedom

    DEFF Research Database (Denmark)

    Nielsen, Morten; Miao, Ling; Ipsen, John Hjorth


    In this work we concentrate on phase equilibria in two-dimensional condensed systems of particles where both translational and internal degrees of freedom are present and coupled through microscopic interactions, with a focus on the manner of the macroscopic coupling between the two types...... where the spin degrees of freedom are slaved by the translational degrees of freedom and develop a first-order singularity in the order-disorder transition that accompanies the lattice-melting transition. The internal degeneracy of the spin states in model III implies that the spin order...... transitional properties for model III are discussed in relation to experiments on planar bilayers of lipid-chain molecules whose properties are determined by a subtle coupling between the translational variables and the intrachain conformational states....

  6. Comparisons in the behavior of stable copper(II), silver(II), and gold(II) complexes in the gas phase: are there implications for condensed-phase chemistry? (United States)

    Walker, N R; Wright, R R; Barran, P E; Murrell, J N; Stace, A J


    Experiments conducted in the gas phase have led to the formation of a series of stable gold(II) complexes with nitrogen- and oxygen-containing ligands. Such complexes are very rare in condensed-phase chemistry. However, there is also a significant group of potential ligands, for example, H2O and NH3, for which stable complexes could not be formed. There are strong similarities between these observations and earlier results presented for silver(II), but both metal ions behave markedly different from copper(II). As a group the majority of successful gold(II) ligands are characterized by being good sigma donor-pi acceptor molecules; however, it is also possible to understand the ability of individual ligands to stabilize the metal ion in terms of a simple electrostatic model. Application of the latter reveals a semiquantitative trend between the physical properties of a ligand, e.g. ionization energy, dipole moment, and polarizability, and the ligand's ability to stabilize either Cu(II), Ag(II), or Au(II). The model successfully accounts for the preference of Cu(II) for aqueous chemistry, in comparison to the complete absence of such behavior on the part of Ag(II) and Au(II). Ligands from recent examples of stable condensed-phase gold(II) complexes appear to meet at least one of the criteria identified from the model.

  7. Photochemistry of a photosynthetic reaction center immobilized in lipidic cubic phases

    Energy Technology Data Exchange (ETDEWEB)

    Hochkoeppler, A.; Venturoli, G.; Zannoni, D. [Univ. of Bologna (Italy). Dept. of Biology; Landau, E.M.; Luisi, P.L. [ETH Zentrum, Zuerich (Switzerland). Inst. fuer Polymere; Feick, R. [Max-Planck Inst. fuer Biochemie, Martinsried (Germany)


    Photosynthetic reaction centers, isolated and purified from the facultative phototrophic bacterium Chloroflexus aurantiacus, were immobilized in optically transparent lipidic cubic phases composed of 42% (w/w) 1-palmitoyl-2-hydroxy-sn-glycero-3-phosphocholine and 58% (w/w) water. The immobilized photosynthetic protein retains its native properties, as indicated by visible and circular dichroic spectra. The ground state visible spectrum of the immobilized reaction centers is very similar to the corresponding spectrum in aqueous solution, indicating that the protein pigments are not extracted into the lipidic regions of the cubic phase. The secondary structure of the protein is maintained in the immobilized state, as determined by far-UV circular dichroism spectroscopy in the 200- to 250-nm range. Moreover, immobilized reaction centers retain their photochemical activity: a reversible photo-oxidation of the primary electron donor (P) is seen upon continuous illumination. Furthermore, the entrapment of reaction centers does not affect the kinetics of charge recombination between the photo-oxidized primary donor (P{sup +}) and the photoreduced primary quinone acceptor, generated by a short flash of light. Reaction centers devoided of the secondary quinone acceptor can be easily reconstituted in cubic phases by means of their coimmobilization with 1,4-naphthoquinone.

  8. Gas phase polymerization of propylene. Reaction kinetics and molecular weight distribution

    NARCIS (Netherlands)

    Meier, G.B.; Weickert, G.; van Swaaij, Willibrordus Petrus Maria


    Gas-phase polymerizations have been executed at different temperatures, pressures, and hydrogen concentrations using Me2Si[Ind]2ZrCl2 / methylaluminoxane / SiO2(Pennsylvania Quarts) as a catalyst. The reaction rate curves have been described by a kinetic model, which takes into account the initially

  9. DFT study of the reactions of Mo and Mo with CO 2 in gas phase

    Indian Academy of Sciences (India)

    Density functional theory (DFT) calculations have been performed to explore the potential energy surfaces of C-O bond activation in CO2 molecule by gas-phase Mo+ cation and Mo atom, in order to better understanding the mechanism of second-row metal reacting with CO2. The minimum energy reaction path is found to ...

  10. Analysis of coupled mass transfer and sol-gel reaction in a two-phase system

    NARCIS (Netherlands)

    Castelijns, H.J.; Huinink, H.P.; Pel, L.; Zitha, P.L.J.


    The coupled mass transfer and chemical reactions of a gel-forming compound in a two-phase system were studied in detail. Tetra-methyl-ortho-silicate (TMOS) is often used as a precursor in sol-gel chemistry to produce silica gels in aqueous systems. TMOS can also be mixed with many hydrocarbons

  11. Process Intensification. Continuous Two-Phase Catalytic Reactions in a Table-Top Centrifugal Contact Separator

    NARCIS (Netherlands)

    Kraai, Gerard N.; Schuur, Boelo; van Zwol, Floris; Haak, Robert M.; Minnaard, Adriaan J.; Feringa, Ben L.; Heeres, Hero J.; de Vries, Johannes G.; Prunier, ML


    Production of fine chemicals is mostly performed in batch reactors. Use of continuous processes has many advantages which may reduce the cost of production. We have developed the use of centrifugal contact separators (CCSs) for continuous two-phase catalytic reactions. This equipment has previously

  12. Laser-induced photochemical gas-phase reactions of vibrationally excited triplet molecules (United States)

    Zalesskaya, G. A.; Yakovlev, D. L.; Sambor, E. G.


    Mechanisms and rates of laser-induced gas-phase reactions of vibrationally excited triplet ketones were studied after adding electron and hydrogen donors using time-resolved delayed fluorescence. The influence of various bimolecular competing processes on DF quenching was analyzed.

  13. Non-stationary filtration mode during chemical reactions with the gas phase (United States)

    Zavialov, Ivan; Konyukhov, Andrey; Negodyaev, Sergey


    An experimental and numerical study of filtration accompanied by chemical reactions between displacing fluid and solid skeleton is considered. Glass balls (400-500 μm in diameter) were placed in 1 cm gap between two glass sheets and were used as model porous medium. The baking soda was added to the glass balls. The 70% solution of acetic acid was used as the displacer. The modeling porous medium was saturated with a mineral oil, and then 70% solution of colored acetic acid was pumped through the medium. The glass balls and a mineral oil have a similar refractive index, so the model porous medium was optically transparent. During the filtration, the gas phase was generated by the chemical reactions between the baking soda and acetic acid, and time-dependent displacement of the chemical reaction front was observed. The front of the chemical reaction was associated with the most intensive gas separation. The front moved, stopped, and then moved again to the area where it had been already. We called this process a secondary oxidation wave. To describe this effect, we added to the balance equations a term associated with the formation and disappearance of phases due to chemical reactions. The equations were supplemented by Darcy's law for multiphase filtration. Nonstationarity front propagation of the chemical reaction in the numerical experiment was observed at Damköhler numbers greater than 100. The mathematical modelling was agreed well with the experimental results.

  14. Refrigeration. Heat Transfer. Part I: Evaporators and Condensers

    DEFF Research Database (Denmark)

    Knudsen, Hans-Jørgen Høgaard


    The note gives an introduction to heat transfer with phase shift. Pool Boiling, Flow Boiling, Condensation.......The note gives an introduction to heat transfer with phase shift. Pool Boiling, Flow Boiling, Condensation....

  15. The geometric phase in quantum systems foundations, mathematical concepts, and applications in molecular and condensed matter physics

    CERN Document Server

    Böhm, Arno; Koizumi, Hiroyasu; Niu, Qian; Zwanziger, Joseph


    Aimed at graduate physics and chemistry students, this is the first comprehensive monograph covering the concept of the geometric phase in quantum physics from its mathematical foundations to its physical applications and experimental manifestations It contains all the premises of the adiabatic Berry phase as well as the exact Anandan-Aharonov phase It discusses quantum systems in a classical time-independent environment (time dependent Hamiltonians) and quantum systems in a changing environment (gauge theory of molecular physics) The mathematical methods used are a combination of differential geometry and the theory of linear operators in Hilbert Space As a result, the monograph demonstrates how non-trivial gauge theories naturally arise and how the consequences can be experimentally observed Readers benefit by gaining a deep understanding of the long-ignored gauge theoretic effects of quantum mechanics and how to measure them

  16. The analysis of magnesium oxide hydration in three-phase reaction system (United States)

    Tang, Xiaojia; Guo, Lin; Chen, Chen; Liu, Quan; Li, Tie; Zhu, Yimin


    In order to investigate the magnesium oxide hydration process in gas-liquid-solid (three-phase) reaction system, magnesium hydroxide was prepared by magnesium oxide hydration in liquid-solid (two-phase) and three-phase reaction systems. A semi-empirical model and the classical shrinking core model were used to fit the experimental data. The fitting result shows that both models describe well the hydration process of three-phase system, while only the semi-empirical model right for the hydration process of two-phase system. The characterization of the hydration product using X-Ray diffraction (XRD) and scanning electron microscope (SEM) was performed. The XRD and SEM show hydration process in the two-phase system follows common dissolution/precipitation mechanism. While in the three-phase system, the hydration process undergo MgO dissolution, Mg(OH)2 precipitation, Mg(OH)2 peeling off from MgO particle and leaving behind fresh MgO surface.

  17. Transport diphasique de gaz et de condensat. Aspects techniques et économiques Technical and Economic Aspects of Two-Phase Pipelining of Gas and Condensate

    Directory of Open Access Journals (Sweden)

    Bourgeois T.


    Full Text Available L'évacuation diphasique de la production d'un gisement de gaz à condensat présente des avantages importants, en particulier sur le plan économique. Les caractéristiques des écoulements diphasiques sont exposées, avec les conséquences principales sur la définition d'un schéma d'exploitation. Une comparaison économique est ensuite présentée, pour illustrer la réduction des investissements qui peut être apportée par l'évacuation diphasique de la production. Enfin, les recherches françaises sur les écoulements diphasiques dans les conduites pétrolières sont brièvement décrites, ainsi qu'un exemple de calcul sur une conduite de gaz à condensat en exploitation diphasique. The two-phase pipelining of a wet gas field production presents many advantages, especially from an economic point of view. The characteristics of two-phase flow are described, together with their main consequences on the operational scheme. Then an economic comparison is made to illustrate the reduction in investment costs that can by achieved with two-phase pipelining. Research in France on two-phase flow in gas and condensate pipelines is briefly described, and an example is given of the designing of a wet-gas pipeline currently being operated in the two-phase mode.

  18. Thermal decomposition of energetic materials. 2. Deuterium isotope effects and isotopic scrambling in condensed-phase decomposition of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine. Technical report

    Energy Technology Data Exchange (ETDEWEB)

    Behrens, R.; Bulusu, S.


    The products formed in the thermal decomposition of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) have been traced to using mixtures of different isotopically labeled analogues of HMX. The isotopic analogues of HMX used in the experiments include 2H, 13C, 15NO2, 15N sub ring, and 18O. The fraction of isotopic scrambling and the extent of the deuterium kinetic isotope effect (DKIE) are reported for the different thermal decomposition products. Isotopic scrambling is not observed for the N-N bond in N2O and the C-H bonds in CH2O. Only one of the C-N bonds in N-methylformamide (NMFA) undergoes isotopic scrambling. The lack of complete isotopic scrambling of the N-NO bond in 1-nitroso-3,5,7-trinitro-1,3,5,7-tetrazocine (ONTNTA) is shown to imply that some HMX decomposition occurs in the lattice. The behavior of the DKIE in different mixtures of isotopic analogues of HMX suggests that water probably acts as a catalyst in the decomposition. The results demonstrate that decomposition of HMX in the condensed phase has several reaction branches.... DKIE, Isotope effect, Isotopic scrambling, HMX, NMFA, ONTNTA, Thermal decomposition.

  19. Thermal decomposition of energetic materials. 2. Deuterium isotope effects and isotopic scrambling in condensed-phase decomposition of octahydro-1,3,5,7-tetranitro- 1,3,5,7-tetrazocine. (Reannouncement with new availability information)

    Energy Technology Data Exchange (ETDEWEB)

    Behrens, R.; Bulusu, S.


    The products formed in the thermal decomposition of octahydro-1,3,5,7-tetranitro- 1,3,5,7-tetrazocine (HMX) have been traced by using mixtures of different isotopically labeled analogues of HMX. The fraction of isotropic scrambling and the extent of the deuterium kinetic isotope effect (DKIE) are reported for the different thermal decomposition products. Isotropic scrambling is not observed for the N-Nbond in N2O and the C-H bonds in CH2O. Only one of the C-N bonds in N-methylformamide (NMFA) undergoes isotropic scrambling. The lack of complete isotopic scrambling of the N-NO bond in 1-nitroso-3,5-7-trinitro- 1,3,5,7-tetrazocine (ONTNTA) is shown to imply that some HMX decomposition occurs in the lattice. The behavior of the DKIE in different mixtures of isotopic analogues of HMX suggests that water probably acts as a catalyst in the decomposition. The results demonstrate that decomposition of HMX in the condensed phase has several reaction branches.

  20. Dynamic evolutions of electron properties: A theoretical study for condensed-phase β-HMX under shock loading (United States)

    He, Zheng-Hua; Chen, Jun; Wu, Qiang; Ji, Guang-Fu


    We present the density functional theory (DFT) calculations for microscopic electron properties of β-HMX under shock loading. The metallization pressure is determined to be within 30-55 GPa. The frontier molecular orbitals mainly localize on N-NO2 groups initially and disperse with pressure increase, while HOMO and LUMO orbitals trend to aggregate with each other. The deformation of N-NO2 groups and enhanced hydrogen-bonding interactions cause the electron delocalization and lower the band gap, inducing the reaction initiation finally. Our results show that using the electron properties can reliably predict the initial decomposition of energetic materials under shock loading.

  1. Condensed Matter Physics (United States)

    Marder, Michael P.


    A modern, unified treatment of condensed matter physics This new work presents for the first time in decades a sweeping review of the whole field of condensed matter physics. It consolidates new and classic topics from disparate sources, teaching "not only about the effective masses of electrons in semiconductor crystals and band theory, but also about quasicrystals, dynamics of phase separation, why rubber is more floppy than steel, electron interference in nanometer-sized channels, and the quantum Hall effect." Six major areas are covered---atomic structure, electronic structure, mechanical properties, electron transport, optical properties, and magnetism. But rather than defining the field in terms of particular materials, the author focuses on the way condensed matter physicists approach physical problems, combining phenomenology and microscopic arguments with information from experiments. For graduate students and professionals, researchers and engineers, applied mathematicians and materials scientists, Condensed Matter Physics provides: * An exciting collection of new topics from the past two decades. * A thorough treatment of classic topics, including band theory, transport theory, and semiconductor physics. * Over 300 figures, incorporating many images from experiments. * Frequent comparison of theory and experiment, both when they agree and when problems are still unsolved. * More than 50 tables of data and a detailed index. * Ample end-of-chapter problems, including computational exercises. * Over 1000 references, both recent and historically significant.

  2. Increased alloimmunisation and transfusion reaction reporting in patients with solid-phase panreactivity. (United States)

    Olofson, Andrea M; Chandler, Rachael M; Marx-Wood, Cynthia R; Babcock, Craig A; Dunbar, Nancy M


    Automated solid-phase antibody screening uses red blood cell (RBC) membranes immobilised on polystyrene test wells to detect RBC specific antibodies. Despite its time-saving and labour-saving benefits, this method produces a higher rate of nonspecific reactivity compared with manual screening. Solid-phase panreactivity (SPP) is characterised by panreactivity (ie, all test cells reacting) in solid-phase testing accompanied by a negative autocontrol and a lack of reactivity when the same screening cells are tested in tube. The mechanisms underlying SPP and its clinical significance remain unclear. The goals of this study were to describe the prevalence of SPP at our institution and determine the alloimmunisation and transfusion reaction rates within this population. Data were collected on all patients undergoing type and screen testing over a 6-year period. Study patients undergoing subsequent transfusion were evaluated for reported transfusion reactions and development of new alloantibodies. Of the 76 051 patients studied, 0.7% demonstrated SPP of which 11% developed new alloantibodies. The transfusion reaction reporting rate among patients with SPP was 2%. Our data suggest that patients with SPP have higher rates of reported transfusion reactions and alloantibody development compared with those without SPP. Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to

  3. Pressureless Reaction Sintering of AlON using Aluminum Orthophosphate as a Transient Liquid Phase

    Energy Technology Data Exchange (ETDEWEB)

    Michael Bakas; Henry Chu


    Use of aluminum oxynitride (AlON) in transparent armor systems has been difficult due to the expense and limitations of the processing methods currently necessary to achieve transparency. Development of a pressureless processing method based on direct reaction sintering of alumina and aluminum nitride powders would reduce costs and provide a more flexible and practical manufacturing method. It may be possible to develop such a processing method using liquid phase sintering; as long as the liquid phase does not remain in the final sample. AlPO4 forms a liquid phase with Al2O3 and AlN at the temperatures required to sinter AlON, and slowly decomposes into P2O5 and alumina. Therefore, it was investigated as a possible transient liquid phase for reaction-sintered AlON. Small compacts of alumina and aluminum nitride with up to of 15wt% AlPO4 additive were pressed and sintered. It was found that AlPO4 formed the requisite transient liquid phase, and it was possible to adjust the process to produce AlON samples with good transmission and densities of 3.66-3.67 g/cc. XRD confirmed the samples formed were AlON, with no trace of any remaining phosphate phases or excess alumina or aluminum nitride. Based on the results, it was concluded that AlPO4 could be utilized as a transient liquid phase to improve the density and transmission of AlON produced by pressureless reaction sintering.

  4. MEMS Lubrication by In-Situ Tribochemical Reactions From the Vapor Phase.

    Energy Technology Data Exchange (ETDEWEB)

    Dugger, Michael Thomas; Asay, David B.; Kim, Seong H.


    Vapor Phase Lubrication (VPL) of silicon surfaces with pentanol has been demonstrated. Two potential show stoppers with respect to application of this approach to real MEMS devices have been investigated. Water vapor was found to reduce the effectiveness of VPL with alcohol for a given alcohol concentration, but the basic reaction mechanism observed in water-free environments is still active, and devices operated much longer in mixed alcohol and water vapor environments than with chemisorbed monolayer lubricants alone. Complex MEMS gear trains were successfully lubricated with alcohol vapors, resulting in a factor of 104 improvement in operating life without failure. Complex devices could be made to fail if operated at much higher frequencies than previously used, and there is some evidence that the observed failure is due to accumulation of reaction products at deeply buried interfaces. However, if hypothetical reaction mechanisms involving heated surfaces are valid, then the failures observed at high frequency may not be relevant to operation at normal frequencies. Therefore, this work demonstrates that VPL is a viable approach for complex MEMS devices in conventional packages. Further study of the VPL reaction mechanisms are recommended so that the vapor composition may be optimized for low friction and for different substrate materials with potential application to conventionally fabricated, metal alloy parts in weapons systems. Reaction kinetics should be studied to define effective lubrication regimes as a function of the partial pressure of the vapor phase constituent, interfacial shear rate, substrate composition, and temperature.


    Energy Technology Data Exchange (ETDEWEB)

    Garrison, S; James Becnel, J


    Density Functional Theory and small-core, relativistic pseudopotentials were used to look for symmetric and asymmetric transitions states of the gas-phase hydrolysis reaction of uranium hexafluoride, UF{sub 6}, with water. At the B3LYP/6-31G(d,p)/SDD level, an asymmetric transition state leading to the formation of a uranium hydroxyl fluoride, U(OH)F{sub 5}, and hydrogen fluoride was found with an energy barrier of +77.3 kJ/mol and an enthalpy of reaction of +63.0 kJ/mol (both including zero-point energy corrections). Addition of diffuse functions to all atoms except uranium led to only minor changes in the structure and relative energies of the reacting complex and transition state. However, a significant change in the product complex structure was found, significantly reducing the enthalpy of reaction to +31.9 kJ/mol. Similar structures and values were found for PBE0 and MP2 calculations with this larger basis set, supporting the B3LYP results. No symmetric transition state leading to the direct formation of uranium oxide tetrafluoride, UOF{sub 4}, was found, indicating that the reaction under ambient conditions likely includes several more steps than the mechanisms commonly mentioned. The transition state presented here appears to be the first published transition state for the important gas-phase reaction of UF{sub 6} with water.

  6. Gas phase reaction of allyl alcohol (2-propen-1-ol) with OH radicals and ozone. (United States)

    Le Person, A; Solignac, G; Oussar, F; Daële, V; Mellouki, A; Winterhalter, R; Moortgat, G K


    The gas phase reactions of allyl alcohol with OH radicals and ozone have been investigated using different experimental systems. The rate coefficient for the OH reaction is reported in the temperature range 231-373 K, k(OH) = (5.7 +/- 0.2) x 10(-12) exp[(650 +/- 52)/T] cm3 molecule(-1) s(-1). This reaction is found to be pressure independent between 33 and 760 Torr. Rate coefficient (k(O3)) and gas phase products of the ozone reaction with allyl alcohol are reported at atmospheric pressure and 298 K. The obtained k(O3) = (1.8 +/- 0.2) x 10(-17) cm3 molecule(-1) s(-1) is in good agreement with the single measurement reported in the literature. The reaction of 03 with allyl alcohol is found to lead to the formation of formaldehyde and glycolaldehyde as the main products. Other products such as CH3OH, CO and CO2 have also been observed in low yield. Aerosol formation has been detected in the ozonolysis of allyl alcohol and its size distribution investigated.

  7. A new electron spectroscopy system for measuring electron emission from fast ion interactions with atomic, molecular, and condensed phase targets (United States)

    Hawkins, Wilson L.

    Ultrasonic powder consolidation (UPC) is a novel, low-temperature, rapid powder consolidation process, capable of producing full-density materials from powders in a few seconds. The objective of this work was to investigate the phase evolution in a Cu-Zn powder mixture subjected to UPC in comparison with that in other high-strain rate materials processing methods such as ball milling. Systematic UPC experiments were performed with a Cu-48 wt% Zn powder mixture at nominal consolidation temperatures of 25 °C to 300 °C, using 20 kHz, 9 microm-amplitude ultrasonic vibration applied to the powder compact for a duration of 1 to 4 s. Optical microscopy and X-ray diffraction revealed the formation of gamma-brass at the interface of Cu and Zn powder particles in the samples consolidated at or above 200 °C. The gamma-brass formation increased with increasing consolidation temperature and vibration time and approached 70 vol% in a sample consolidated at 300 °C for 4 s. No new phase formed in a reference sample made at 300 °C but with no vibration, despite the close contact between Cu and Zn achieved in the reference sample. The gamma-brass formation in the UPC samples is contrasted by the direct formation of beta-brass in ball-milled composite powders of the Cu-48 wt% Zn composition. The phase selection in UPC is governed by the local state at the Cu-Zn interface. The high excess vacancies generated at the Cu-Zn interface enhance the interdiffusion at the Cu-Zn interface by many orders of magnitude, allowing the interfacial Cu and Zn concentrations to exceed the normal solubility limits before a new phase can nucleate. This, in turn, increases the driving force for the nucleation of gamma-brass at the Cu-Zn interface. The driving for beta-brass nucleation does not increase as much because of the large solubility of Zn in Cu. Adding a pre-UPC step, such as a heat treatment or ball milling for a very short time (before any new phase formation is detectable), facilities

  8. Noise-and delay-induced phase transitions of the dimer-monomer surface reaction model

    Energy Technology Data Exchange (ETDEWEB)

    Zeng Chunhua, E-mail: [Faculty of Science, Kunming University of Science and Technology, Kunming 650093 (China) and Center of Metallurgical Energy Conservation and Emission Reduction, Ministry of Education, Kunming University of Science and Technology, Kunming 650093 (China); Wang Hua, E-mail: [Center of Metallurgical Energy Conservation and Emission Reduction, Ministry of Education, Kunming University of Science and Technology, Kunming 650093 (China)


    Highlights: Black-Right-Pointing-Pointer We study the dimer-monomer surface reaction model. Black-Right-Pointing-Pointer We show that noise induces first-order irreversible phase transition (IPT). Black-Right-Pointing-Pointer Combination of noise and time-delayed feedback induce first- and second-order IPT. Black-Right-Pointing-Pointer First- and second-order IPT is viewed as noise-and delay-induced phase transitions. - Abstract: The effects of noise and time-delayed feedback in the dimer-monomer (DM) surface reaction model are investigated. Applying small delay approximation, we construct a stochastic delayed differential equation and its Fokker-Planck equation to describe the state evolution of the DM reaction model. We show that the noise can only induce first-order irreversible phase transition (IPT) characteristic of the DM model, however the combination of the noise and time-delayed feedback can simultaneously induce first- and second-order IPT characteristics of the DM model. Therefore, it is shown that the well-known first- and second-order IPT characteristics of the DM model may be viewed as noise-and delay-induced phase transitions.

  9. Humidity independent mass spectrometry for gas phase chemical analysis via ambient proton transfer reaction. (United States)

    Zhu, Hongying; Huang, Guangming


    In this work, a humidity independent mass spectrometric method was developed for rapid analysis of gas phase chemicals. This method is based upon ambient proton transfer reaction between gas phase chemicals and charged water droplets, in a reaction chamber with nearly saturate humidity under atmospheric pressure. The humidity independent nature enables direct and rapid analysis of raw gas phase samples, avoiding time- and sample-consuming sample pretreatments in conventional mass spectrometry methods to control sample humidity. Acetone, benzene, toluene, ethylbenzene and meta-xylene were used to evaluate the analytical performance of present method. The limits of detection for benzene, toluene, ethylbenzene and meta-xylene are in the range of ∼0.1 to ∼0.3 ppbV; that of benzene is well below the present European Union permissible exposure limit for benzene vapor (5 μg m(-3), ∼1.44 ppbV), with linear ranges of approximately two orders of magnitude. The majority of the homemade device contains a stainless steel tube as reaction chamber and an ultrasonic humidifier as the source of charged water droplets, which makes this cheap device easy to assemble and facile to operate. In addition, potential application of this method was illustrated by the real time identification of raw gas phase chemicals released from plants at different physiological stages. Copyright © 2015 Elsevier B.V. All rights reserved.

  10. Electron flow generated by gas phase exothermic catalytic reactions using a platinum-gallium nitride nanodiode. (United States)

    Ji, Xiaozhong; Zuppero, Anthony; Gidwani, Jawahar M; Somorjai, Gabor A


    We report steady-state conversion of chemical reaction energy into hot electrons by ballistic injection into a platinum-gallium nitride (Pt/GaN) nanodiode during the platinum-catalyzed oxidation of carbon monoxide. Surface catalytic reactions of molecules from the gas phase generated continuous steady-state hot electron currents with energies at least that of Schottky barrier energy ( approximately 1 eV). These hot electron currents were observed on two different nanodiodes (Pt/TiO2 and Pt/GaN) and represent a new method of chemical energy conversion.

  11. Comparison of TiO2 photocatalysis, electrochemically assisted Fenton reaction and direct electrochemistry for simulation of phase I metabolism reactions of drugs

    NARCIS (Netherlands)

    Ruokolainen, Miina; Gül, Turan; Permentier, Hjalmar; Sikanen, Tiina; Kostiainen, Risto; Kotiaho, Tapio


    The feasibility of titanium dioxide (TiO2) photocatalysis, electrochemically assisted Fenton reaction (EC-Fenton) and direct electrochemical oxidation (EC) for simulation of phase I metabolism of drugs was studied by comparing the reaction products of buspirone, promazine, testosterone and

  12. Final Technical Report for Quantum Embedding for Correlated Electronic Structure in Large Systems and the Condensed Phase

    Energy Technology Data Exchange (ETDEWEB)

    Chan, Garnet Kin-Lic [Princeton Univ., NJ (United States)


    This is the final technical report. We briefly describe some selected results below. Developments in density matrix embedding. DMET is a quantum embedding theory that we introduced at the beginning of the last funding period, around 2012-2013. Since the first DMET papers, which demonstrated proof-of- principle calculations on the Hubbard model and hydrogen rings, we have carried out a number of different developments, including: Extending the DMET technology to compute broken symmetry phases, including magnetic phases and super- conductivity (Pub. 13); Calibrating the accuracy of DMET and its cluster size convergence against other methods, and formulation of a dynamical cluster analog (Pubs. 4, 10) (see Fig. 1); Implementing DMET for ab-initio molecular calculations, and exploring different self-consistency criteria (Pubs. 9, 14); Using embedding to defi ne quantum classical interfaces Pub. 2; Formulating DMET for spectral functions (Pub. 7) (see Fig. 1); Extending DMET to coupled fermion-boson problems (Pub. 12). Together with these embedding developments, we have also implemented a wide variety of impurity solvers within our DMET framework, including DMRG (Pub. 3), AFQMC (Pub. 10), and coupled cluster theory (CC) (Pub. 9).

  13. Humidity independent mass spectrometry for gas phase chemical analysis via ambient proton transfer reaction

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Hongying; Huang, Guangming, E-mail:


    Graphical abstract: Direct and humidity independent mass spectrometry analysis of gas phase chemicals could be achieved via ambient proton transfer ionization, ion intensity was found to be stable with humidity ranged from ∼10% to ∼100%. - Highlights: • A humidity independent mass spectrometric method for gas phase samples analysis. • A universal and good sensitivity method. • The method can real time identify plant released raw chemicals. - Abstract: In this work, a humidity independent mass spectrometric method was developed for rapid analysis of gas phase chemicals. This method is based upon ambient proton transfer reaction between gas phase chemicals and charged water droplets, in a reaction chamber with nearly saturate humidity under atmospheric pressure. The humidity independent nature enables direct and rapid analysis of raw gas phase samples, avoiding time- and sample-consuming sample pretreatments in conventional mass spectrometry methods to control sample humidity. Acetone, benzene, toluene, ethylbenzene and meta-xylene were used to evaluate the analytical performance of present method. The limits of detection for benzene, toluene, ethylbenzene and meta-xylene are in the range of ∼0.1 to ∼0.3 ppbV; that of benzene is well below the present European Union permissible exposure limit for benzene vapor (5 μg m{sup −3}, ∼1.44 ppbV), with linear ranges of approximately two orders of magnitude. The majority of the homemade device contains a stainless steel tube as reaction chamber and an ultrasonic humidifier as the source of charged water droplets, which makes this cheap device easy to assemble and facile to operate. In addition, potential application of this method was illustrated by the real time identification of raw gas phase chemicals released from plants at different physiological stages.

  14. Hydrophobically assisted switching phase synthesis: the flexible combination of solid-phase and solution-phase reactions employed for oligosaccharide preparation. (United States)

    Bauer, Jörg; Rademann, Jörg


    Hydrophobically assisted switching phase (HASP) synthesis is a concept that allows the choice between the advantages of solid-supported chemistry and those of solution-phase synthesis. Starting from the examination of adsorption and desorption properties of hydrophobic molecules to and from reversed-phase silica, we designed a dilipid as a quantitative and fully reversible HASP anchor, permitting final product release. The utility of this new tool in synthetic organic chemistry was demonstrated on oligosaccharide preparation. The synthesis of a pentarhamnoside was accomplished by repetitive glycosylation reactions. Glycosylations were conducted preferably in solution, whereas all protecting group manipulations were performed on solid support. Without the need for chromatographic purification of intermediates, the HASP system furnished the final product after 12 linear steps with average yields of 94% per step at a scale of 0.1 mmol, thus overcoming several of the limitations encountered in the solid-phase synthesis of complex carbohydrates.

  15. UV spectra and kinetics of radicals produced in the gas phase reactions of Cl, F and OH with toluene

    DEFF Research Database (Denmark)

    Markert, F.; Pagsberg, P.


    The gas phase reactions of Cl, F and OH with toluene have been studied by pulse radiolysis combined with time-resolved UV spectroscopy. The formation of benzyl radicals via the abstraction reactions C6H5-CH3 + X --> C6H5-CH2 + HX was observed with X = Cl, F and OH. In the reaction with chlorine...

  16. Effects of cloud condensation nuclei and ice nucleating particles on precipitation processes and supercooled liquid in mixed-phase orographic clouds

    Energy Technology Data Exchange (ETDEWEB)

    Fan, Jiwen; Leung, L. Ruby; Rosenfeld, Daniel; DeMott, Paul J.


    How orographic mixed-phase clouds respond to the change in cloud condensation nuclei (CCN) and ice nucleating particles (INPs) are highly uncertain. The main snow production mechanism in warm and cold mixed-phase orographic clouds (referred to as WMOCs and CMOCs, respectively, distinguished here as those having cloud tops warmer and colder than -20°C) could be very different. We quantify the CCN and INP impacts on supercooled water content, cloud phases, and precipitation for a WMOC case and a CMOC case, with sensitivity tests using the same CCN and INP concentrations between the WMOC and CMOC cases. It was found that deposition plays a more important role than riming for forming snow in the CMOC case, while the role of riming is dominant in the WMOC case. As expected, adding CCN suppresses precipitation, especially in WMOCs and low INPs. However, this reverses strongly for CCN of 1000 cm-3 and larger. We found a new mechanism through which CCN can invigorate mixed-phase clouds over the Sierra Nevada and drastically intensify snow precipitation when CCN concentrations are high (1000 cm-3 or higher). In this situation, more widespread shallow clouds with a greater amount of cloud water form in the Central Valley and foothills west of the mountain range. The increased latent heat release associated with the formation of these clouds strengthens the local transport of moisture to the windward slope, invigorating mixed-phase clouds over the mountains, and thereby producing higher amounts of snow precipitation. Under all CCN conditions, increasing the INPs leads to decreased riming and mixed-phase fraction in the CMOC as a result of liquid-limited conditions, but has the opposite effects in the WMOC as a result of ice-limited conditions. However, precipitation in both cases is increased by increasing INPs due to an increase in deposition for the CMOC but enhanced riming and deposition in the WMOC. Increasing the INPs dramatically reduces

  17. Coupled Enzyme Reactions Performed in Heterogeneous Reaction Media: Experiments and Modeling for Glucose Oxidase and Horseradish Peroxidase in a PEG/Citrate Aqueous Two-Phase System (United States)


    The intracellular environment in which biological reactions occur is crowded with macromolecules and subdivided into microenvironments that differ in both physical properties and chemical composition. The work described here combines experimental and computational model systems to help understand the consequences of this heterogeneous reaction media on the outcome of coupled enzyme reactions. Our experimental model system for solution heterogeneity is a biphasic polyethylene glycol (PEG)/sodium citrate aqueous mixture that provides coexisting PEG-rich and citrate-rich phases. Reaction kinetics for the coupled enzyme reaction between glucose oxidase (GOX) and horseradish peroxidase (HRP) were measured in the PEG/citrate aqueous two-phase system (ATPS). Enzyme kinetics differed between the two phases, particularly for the HRP. Both enzymes, as well as the substrates glucose and H2O2, partitioned to the citrate-rich phase; however, the Amplex Red substrate necessary to complete the sequential reaction partitioned strongly to the PEG-rich phase. Reactions in ATPS were quantitatively described by a mathematical model that incorporated measured partitioning and kinetic parameters. The model was then extended to new reaction conditions, i.e., higher enzyme concentration. Both experimental and computational results suggest mass transfer across the interface is vital to maintain the observed rate of product formation, which may be a means of metabolic regulation in vivo. Although outcomes for a specific system will depend on the particulars of the enzyme reactions and the microenvironments, this work demonstrates how coupled enzymatic reactions in complex, heterogeneous media can be understood in terms of a mathematical model. PMID:24517887

  18. Condensed Matter Nuclear Science (United States)

    Biberian, Jean-Paul


    1. General. A tribute to gene Mallove - the "Genie" reactor / K. Wallace and R. Stringham. An update of LENR for ICCF-11 (short course, 10/31/04) / E. Storms. New physical effects in metal deuterides / P. L. Hagelstein ... [et al.]. Reproducibility, controllability, and optimization of LENR experiments / D. J. Nagel -- 2. Experiments. Electrochemistry. Evidence of electromagnetic radiation from Ni-H systems / S. Focardi ... [et al.]. Superwave reality / I. Dardik. Excess heat in electrolysis experiments at energetics technologies / I. Dardik ... [et al.]. "Excess heat" during electrolysis in platinum/K[symbol]CO[symbol]/nickel light water system / J. Tian ... [et al.]. Innovative procedure for the, in situ, measurement of the resistive thermal coefficient of H(D)/Pd during electrolysis; cross-comparison of new elements detected in the Th-Hg-Pd-D(H) electrolytic cells / F. Celani ... [et al.]. Emergence of a high-temperature superconductivity in hydrogen cycled Pd compounds as an evidence for superstoihiometric H/D sites / A. Lipson ... [et al.]. Plasma electrolysis. Calorimetry of energy-efficient glow discharge - apparatus design and calibration / T. B. Benson and T. O. Passell. Generation of heat and products during plasma electrolysis / T. Mizuno ... [et al.]. Glow discharge. Excess heat production in Pd/D during periodic pulse discharge current in various conditions / A. B. Karabut. Beam experiments. Accelerator experiments and theoretical models for the electron screening effect in metallic environments / A. Huke, K. Czerski, and P. Heide. Evidence for a target-material dependence of the neutron-proton branching ratio in d+d reactions for deuteron energies below 20keV / A. Huke ... [et al.]. Experiments on condensed matter nuclear events in Kobe University / T. Minari ... [et al.]. Electron screening constraints for the cold fusion / K. Czerski, P. Heide, and A. Huke. Cavitation. Low mass 1.6 MHz sonofusion reactor / R. Stringham. Particle detection. Research

  19. Characterization of ionic liquid‐based biocatalytic two‐phase reaction system for production of biodiesel

    DEFF Research Database (Denmark)

    Prabhavathi Devi, Bethala Lakshmi Anu; Guo, Zheng; Xu, Xuebing


    The property of a variety of ionic liquids (ILs) as reaction media was evaluated for the production of biodiesel by enzymatic methanolysis of rapeseed oil. The IL Ammoeng 102, containing tetraaminum cation with C18 acyl and oligoethyleneglycol units, was found to be capable of forming oil....../IL biphasic reaction system by mixing with substrates, which is highly effective for the production of biodiesel with more than 98% biodiesel yield and nearly 100% conversion of oil. Conductor‐like screening model for real solvent (COSMO‐RS) in silico prediction of substrate solubility and simulation...... of partition coefficient change vs. reaction evolution indicated that the amphiphilic property of Ammoeng 102 might be responsible for creating efficient interaction of immiscible substrates; while big difference of partition coefficients of generated biodiesel and glycerol between the two phases suggests...

  20. Sinterable Ceramic Powders from Laser Heated Gas Phase Reactions and Rapidly Solidified Ceramic Materials. (United States)


    Gattuso, T. R., Meunier, M., Adler, D., and Haggerty, J. S., "IR Laser- Induced Deposition of Silicon Thin Films ", to be published in the Proceedings of...and Thin Films by Laser Induced Gas Phase Reactions", presented at the Nineteenth University Conference on Ceramic Science, Emergent Process Methods... Silicon Carbonitrides from Monomeric Organosilicon Precursors". To be presented at the 1983 Annual Meeting of the American Ceramic Society, April 1983

  1. Reaction pathways for catalytic gas-phase oxidation of glycerol over mixed metal oxides

    Energy Technology Data Exchange (ETDEWEB)

    Suprun, W.; Glaeser, R.; Papp, H. [Leipzig Univ. (Germany). Inst. of Chemical Technology


    Glycerol as a main by-product from bio-diesel manufacture is a cheap raw material with large potential for chemical or biochemical transformations to value-added C3-chemicals. One possible way of glycerol utilization involves its catalytic oxidation to acrylic acid as an alternative to petrochemical routes. However, this catalytic conversion exhibits various problems such as harsh reaction conditions, severe catalyst coking and large amounts of undesired by-products. In this study, the reaction pathways for gas-phase conversion of glycerol over transition metal oxides (Mo, V und W) supported on TiO{sub 2} and SiO{sub 2} were investigated by two methods: (i) steady state experiments of glycerol oxidation and possible reactions intermediates, i.e., acrolein, 3-hydroxy propionaldehyde and acetaldehyde, and (ii) temperature-programmed surface reaction (TPSR) studies of glycerol conversion in the presence and in the absence of gas-phase oxygen. It is shown that the supported W-, V and Mo-oxides possess an ability to catalyze the oxidation of glycerol to acrylic acid. These investigations allowed us to gain a deeper insight into the reaction mechanism. Thus, based on the obtained results, three possible reactions pathways for the selective oxidation of glycerol to acrylic acid on the transition metal-containing catalysts are proposed. The major pathways in presence of molecular oxygen are a fast successive destructive oxidation of glycerol to CO{sub x} and the dehydration of glycerol to acrolein which is a rate-limiting step. (orig.)

  2. Systematic Search for Chemical Reactions in Gas Phase Contributing to Methanol Formation in Interstellar Space. (United States)

    Gamez-Garcia, Victoria G; Galano, Annia


    A massive search for chemical routes leading to methanol formation in gas phase has been conducted using computational chemistry, at the CBS-QB3 level of theory. The calculations were performed at five different temperatures (100, 80, 50, 20, and 10 K) and at three pressures (0.1, 0.01, and 0.001 atm) for each temperature. The search was focused on identifying reactions with the necessary features to be viable in the interstellar medium (ISM). A searching strategy was applied to that purpose, which allowed to reduce an initial set of 678 possible reactions to a subset of 11 chemical routes that are recommended, for the first time, as potential candidates for contributing to methanol formation in the gas phase of the ISM. They are all barrier-less, and thus they are expected to take place at collision rates. Hopefully, including these reactions in the currently available models, for the gas-phase methanol formation in the ISM, would help improving the predicted fractional abundance of this molecule in dark clouds. Further investigations, especially those dealing with grain chemistry and electronic excited states, would be crucial to get a complete picture of the methanol formation in the ISM.

  3. Applying ion-molecule reactions to studies of gas-phase protein structure

    Energy Technology Data Exchange (ETDEWEB)

    Ogorzalek Loo, R.R.; Loo, J.A.; Smith, R.D.


    Whether solution phase differences in protein higher order structure persist in the gas phase, is examined by means of proton transfer reactions on ions generated by electrospray ionization of different solution conformations. Ion-molecule reactions were carried out in the atmosphere-vacuum interface of a quadrupole mass spectrometer with a Y-shaped capillary inlet-reactor. An amine (dimethyl-, trimethyl-, or diethyl-) were delivered to one inlet arm. Reactivities of bovine cytochrome c ions sprayed from denatured and native solutions were determined; the ions generated shifted to about the same charge states. Addition of equal amounts of amine to ions generated from different solution conformations of bovine ubiquitin also yielded similar final charge states; however, the average charge state increased with temperature. Myoglobin and apomyoglobin also yielded similar final charge states. The results suggest that for the non-disulfide linked proteins, either there are not significant differences in gas phase higher order structure, or proton transfer reactions are not sensitive enough to detect higher order structural differences arising from noncovalent interactions. 2 refs, 2 figs. (DLC)

  4. Manipulation of a Bose-Einstein condensate by a time-averaged orbiting potential using phase jumps of the rotating field

    NARCIS (Netherlands)

    Cleary, P.W.; Hijmans, T.W.; Walraven, J.T.M.


    We report on the manipulation of the center-of-mass motion ("sloshing") of a Bose-Einstein condensate in a time-averaged orbiting potential (TOP) trap. We start with a condensate at rest in the center of a static trapping potential. When suddenly replacing the static trap with a TOP trap centered

  5. Calcium carbonate phase transformations during the carbonation reaction of calcium heavy alkylbenzene sulfonate overbased nanodetergents preparation. (United States)

    Chen, Zhaocong; Xiao, Shan; Chen, Feng; Chen, Dongzhong; Fang, Jianglin; Zhao, Min


    The preparation and application of overbased nanodetergents with excess alkaline calcium carbonate is a good example of nanotechnology in practice. The phase transformation of calcium carbonate is of extensive concern since CaCO(3) serves both as an important industrial filling material and as the most abundant biomineral in nature. Industrially valuable overbased nanodetergents have been prepared based on calcium salts of heavy alkylbenzene sulfonate by a one-step process under ambient pressure, the carbonation reaction has been monitored by the instantaneous temperature changes and total base number (TBN). A number of analytical techniques such as TGA, DLS, SLS, TEM, FTIR, and XRD have been utilized to explore the carbonation reaction process and phase transformation mechanism of calcium carbonate. An enhanced understanding on the phase transformation of calcium carbonate involved in calcium sulfonate nanodetergents has been achieved and it has been unambiguously demonstrated that amorphous calcium carbonate (ACC) transforms into the vaterite polymorph rather than calcite, which would be of crucial importance for the preparation and quality control of lubricant additives and greases. Our results also show that a certain amount of residual Ca(OH)(2) prevents the phase transformation from ACC to crystalline polymorphs. Moreover, a vaterite nanodetergent has been prepared for the first time with low viscosity, high base number, and uniform particle size, nevertheless a notable improvement on its thermal stability is required for potential applications. Copyright © 2011 Elsevier Inc. All rights reserved.

  6. Condensed-phase relaxation of multilevel quantum systems. II. Comparison of path integral calculations and second-order relaxation theory for a nondegenerate three-level system. (United States)

    Peter, Simone; Evans, Deborah G; Coalson, Rob D


    An exactly solvable model of multisite condensed-phase vibrational relaxation was studied in Paper I (Peter, S.; Evans, D. G.; Coalson, R. D. J. Phys. Chem. B 2006, 110, 18758.), where it was shown that long-time steady-state site populations of a degenerate N-level system are not equal (hence, they are non-Boltzmann) and depend on the initial preparation of the system and the number of sites that it comprises. Here we consider a generalization of the model to the case of a nondegenerate three-level system coupled to a high-dimensional bath: such a model system has direct relevance to a large class of donor-bridge-acceptor electron transfer processes. Because the quantum dynamics of this system cannot be computed analytically, we compare numerically exact path integral calculations to the predictions of second-order time-local relaxation theory. For modest system-bath coupling strengths, the two sets of results are in excellent agreement. They show that non-Boltzmann long-time steady-state site populations are obtained when the level splitting is small but nonzero, whereas at larger values of the system bias (asymmetry) these populations become Boltzmann distributed.

  7. Coupled-cluster based approach for core-level states in condensed phase: Theory and application to different protonated forms of aqueous glycine (United States)

    Sadybekov, Arman; Krylov, Anna I.


    A theoretical approach for calculating core-level states in condensed phase is presented. The approach is based on the equation-of-motion coupled-cluster (EOM-CC) theory and effective fragment potential (EFP) method. By introducing approximate treatment of double excitations in the EOM-CC with single and double substitutions ansatz, we address poor convergence issues that are encountered for the core-level states and significantly reduce computational costs. While the approximations introduce relatively large errors in the absolute values of transition energies, the errors are systematic. Consequently, chemical shifts, changes in ionization energies relative to reference systems, are reproduced reasonably well. By using different protonation forms of solvated glycine as a benchmark system, we show that our protocol is capable of reproducing the experimental chemical shifts with a quantitative accuracy. The results demonstrate that chemical shifts are very sensitive to the solvent interactions and that explicit treatment of a solvent, such as within EFP framework, is essential for achieving quantitative accuracy.

  8. Formation of ultrathin Ni germanides: solid-phase reaction, morphology and texture (United States)

    van Stiphout, K.; Geenen, F. A.; De Schutter, B.; Santos, N. M.; Miranda, S. M. C.; Joly, V.; Detavernier, C.; Pereira, L. M. C.; Temst, K.; Vantomme, A.


    The solid-phase reaction of ultrathin (⩽10 nm) Ni films with different Ge substrates (single-crystalline (1 0 0), polycrystalline, and amorphous) was studied. As thickness goes down, thin film texture becomes a dominant factor in both the film’s phase formation and morphological evolution. As a consequence, certain metastable microstructures are epitaxially stabilized on crystalline substrates, such as the ɛ-Ni5Ge3 phase or a strained NiGe crystal structure on the single-crystalline substrates. Similarly, the destabilizing effect of axiotaxial texture on the film’s morphology becomes more pronounced as film thicknesses become smaller. These effects are contrasted by the evolution of germanide films on amorphous substrates, on which neither epitaxy nor axiotaxy can form, i.e. none of the (de)stabilizing effects of texture are observed. The crystallization of such amorphous substrates however, drives the film breakup.

  9. In-Space technology experiments program. A high efficiency thermal interface (using condensation heat transfer) between a 2-phase fluid loop and heatpipe radiator: Experiment definition phase (United States)

    Pohner, John A.; Dempsey, Brian P.; Herold, Leroy M.


    Space Station elements and advanced military spacecraft will require rejection of tens of kilowatts of waste heat. Large space radiators and two-phase heat transport loops will be required. To minimize radiator size and weight, it is critical to minimize the temperature drop between the heat source and sink. Under an Air Force contract, a unique, high-performance heat exchanger is developed for coupling the radiator to the transport loop. Since fluid flow through the heat exchanger is driven by capillary forces which are easily dominated by gravity forces in ground testing, it is necessary to perform microgravity thermal testing to verify the design. This contract consists of an experiment definition phase leading to a preliminary design and cost estimate for a shuttle-based flight experiment of this heat exchanger design. This program will utilize modified hardware from a ground test program for the heat exchanger.

  10. Asymmetric condensed dark matter

    Energy Technology Data Exchange (ETDEWEB)

    Aguirre, Anthony; Diez-Tejedor, Alberto, E-mail:, E-mail: [Santa Cruz Institute for Particle Physics and Department of Physics, University of California, Santa Cruz, CA, 95064 (United States)


    We explore the viability of a boson dark matter candidate with an asymmetry between the number densities of particles and antiparticles. A simple thermal field theory analysis confirms that, under certain general conditions, this component would develop a Bose-Einstein condensate in the early universe that, for appropriate model parameters, could survive the ensuing cosmological evolution until now. The condensation of a dark matter component in equilibrium with the thermal plasma is a relativistic process, hence the amount of matter dictated by the charge asymmetry is complemented by a hot relic density frozen out at the time of decoupling. Contrary to the case of ordinary WIMPs, dark matter particles in a condensate must be lighter than a few tens of eV so that the density from thermal relics is not too large. Big-Bang nucleosynthesis constrains the temperature of decoupling to the scale of the QCD phase transition or above. This requires large dark matter-to-photon ratios and very weak interactions with standard model particles.

  11. Decondensation in Nonequilibrium Photonic Condensates: When Less Is More (United States)

    Hesten, Henry J.; Nyman, Robert A.; Mintert, Florian


    We investigate the steady state of a system of photons in a pumped dye-filled microcavity. By varying pump and thermalization the system can be tuned between Bose-Einstein condensation, multimode condensation, and lasing. We present a rich nonequilibrium phase diagram which exhibits transitions between these phases, including decondensation of individual modes under conditions that would typically favor condensation.

  12. Experimental and computational investigation on the gas phase reaction of p-cymene with Cl atoms. (United States)

    Dash, Manas Ranjan; Srinivasulu, G; Rajakumar, B


    The rate coefficient for the gas-phase reaction of Cl atoms with p-cymene was determined as a function of temperature (288-350 K) and pressure (700-800 Torr) using the relative rate technique, with 1,3-butadiene and ethylene as reference compounds. Cl atoms were generated by UV photolysis of oxalyl chloride ((COCl)2) at 254 nm, and nitrogen was used as the diluent gas. The rate coefficient for the reaction of Cl atoms with p-cymene at 298 K was measured to be (2.58 ± 1.55) × 10(-10) cm(3) molecule(-1) s(-1). The kinetic data obtained over the temperature range 288-350 K were used to derive an Arrhenius expression: k(T) = (9.36 ± 2.90) × 10(-10) exp[-(488 ± 98)/T] cm(3) molecule(-1) s(-1). Theoretical kinetic calculations were also performed for the title reaction using canonical variational transition state theory (CVT) with small curvature tunneling (SCT) between 250 and 400 K. The calculated rate coefficients obtained over the temperature range 250-400 K were used to derive an Arrhenius expression: k(T) = 5.41 × 10(-13) exp[1837/T] cm(3) molecule(-1) s(-1). Theoretical study indicated that addition channels contribute maximum to the total reaction and H-abstraction channels can be neglected. The atmospheric lifetime (τ) of p-cymene due to its reactions with various tropospheric oxidants was estimated, and it was concluded that the reactions of p-cymene with Cl atoms may compete with OH radicals in the marine boundary layer and in coastal urban areas where the concentration of Cl atoms is high.

  13. Enantiomer-Selective Photo-Induced Reaction of Protonated Tryptophan with Disaccharides in the Gas Phase (United States)

    Doan, Thuc N.; Fujihara, Akimasa


    In order to investigate chemical evolution in interstellar molecular clouds, enantiomer-selective photo-induced chemical reactions between an amino acid and disaccharides in the gas phase were examined using a tandem mass spectrometer containing an electrospray ionization source and a cold ion trap. Ultraviolet photodissociation mass spectra of cold gas-phase noncovalent complexes of protonated tryptophan (Trp) enantiomers with disaccharides consisting of two uc(d)-glucose units, such as uc(d)-maltose or uc(d)-cellobiose, were obtained by photoexcitation of the indole ring of Trp. NH2CHCOOH loss via cleavage of the Cα-Cβ bond in Trp induced by hydrogen atom transfer from the NH3 + group of a protonated Trp was observed in a noncovalent heterochiral H+(uc(l)-Trp)(uc(d)-maltose) complex. In contrast, a photo-induced chemical reaction forming the product ion with m/z 282 occurs in homochiral H+(uc(d)-Trp)(uc(d)-maltose). For uc(d)-cellobiose, both NH2CHCOOH elimination and the m/z 282 product ion were observed, and no enantiomer-selective phenomena occurred. The m/z 282 product ion indicates that the photo-induced C-glycosylation, which links uc(d)-glucose residues to the indole moiety of Trp via a C-C bond, can occur in cold gas-phase noncovalent complexes, and its enantiomer-selectivity depends on the structure of the disaccharide.

  14. Direct Numerical Simulation of biomass pyrolysis and combustion with gas phase reactions (United States)

    Awasthi, A.; Kuerten, J. G. M.; Geurts, B. J.


    We present Direct Numerical Simulation of biomass pyrolysis and combustion in a turbulent channel flow. The model includes simplified models for biomass pyrolysis and char combustion along with a model for particle tracking. The gas phase is modelled as a mixture of reacting gas species. The gas-particle interactions for mass, momentum, and energy exchange are included by two-way coupling terms. The effect of two-way coupling on the conversion time of biomass particles is found noticeable for particle volume fractions > 10-5. We also observe that at constant volume fraction the effect of two-way coupling increases as the particle size is reduced, due to the higher total heat exchange area in case of smaller particles. The inclusion of gas phase homogeneous reactions in the DNS model decreases the biomass pyrolysis time due to higher gas temperatures. In contrast, including gas phase reactions increases the combustion time of biomass due to the lower concentration of oxygen at the particle surface.

  15. Gas-Phase Oxidation via Ion/Ion Reactions: Pathways and Applications (United States)

    Pilo, Alice L.; Zhao, Feifei; McLuckey, Scott A.


    Here, we provide an overview of pathways available upon the gas-phase oxidation of peptides and DNA via ion/ion reactions and explore potential applications of these chemistries. The oxidation of thioethers (i.e., methionine residues and S-alkyl cysteine residues), disulfide bonds, S-nitrosylated cysteine residues, and DNA to the [M+H+O]+ derivative via ion/ion reactions with periodate and peroxymono-sulfate anions is demonstrated. The oxidation of neutral basic sites to various oxidized structures, including the [M+H+O]+, [M-H]+, and [M-H-NH3]+ species, via ion/ion reactions is illustrated and the oxidation characteristics of two different oxidizing reagents, periodate and persulfate anions, are compared. Lastly, the highly efficient generation of molecular radical cations via ion/ion reactions with sulfate radical anion is summarized. Activation of the newly generated molecular radical peptide cations results in losses of various neutral side chains, several of which generate dehydroalanine residues that can be used to localize the amino acid from which the dehydroalanine was generated. The chemistries presented herein result in a diverse range of structures that can be used for a variety of applications, including the identification and localization of S-alkyl cysteine residues, the oxidative cleavage of disulfide bonds, and the generation of molecular radical cations from even-electron doubly protonated peptides. [Figure not available: see fulltext.

  16. Symmetry and the geometric phase in ultracold hydrogen-exchange reactions. (United States)

    Croft, J F E; Hazra, J; Balakrishnan, N; Kendrick, B K


    Quantum reactive scattering calculations are reported for the ultracold hydrogen-exchange reaction and its non-reactive atom-exchange isotopic counterparts, proceeding from excited rotational states. It is shown that while the geometric phase (GP) does not necessarily control the reaction to all final states, one can always find final states where it does. For the isotopic counterpart reactions, these states can be used to make a measurement of the GP effect by separately measuring the even and odd symmetry contributions, which experimentally requires nuclear-spin final-state resolution. This follows from symmetry considerations that make the even and odd identical-particle exchange symmetry wavefunctions which include the GP locally equivalent to the opposite symmetry wavefunctions which do not. It is shown how this equivalence can be used to define a constant which quantifies the GP effect and can be obtained solely from experimentally observable rates. This equivalence reflects the important role that discrete symmetries play in ultracold chemistry and highlights the key role that ultracold reactions can play in understanding fundamental aspects of chemical reactivity more generally.

  17. Two-Electron Reaction without Structural Phase Transition in Nanoporous Cathode Material

    Directory of Open Access Journals (Sweden)

    Tomoyuki Matsuda


    Full Text Available We investigated the charge/discharge properties, valence states, and structural properties of a nanoporous cathode material LixMn[Fe(CN6]0.83·3.5H2O. The film-type electrode of LixMn[Fe(CN6]0.83·3.5H2O exhibited a high charge capacity (=128 mAh g-1 and a good cyclability (87% of the initial value after 100 cycles and is one of the promising candidates for Li-ion battery cathode. X-ray absorption spectra near the Fe and Mn K-edges revealed that the charge/discharge process is a two-electron reaction; that is, MnII–NC–FeII, MnII–NC–FeIII, and MnIII–NC–FeIII. We further found that the crystal structure remains cubic throughout the charge/discharge process. The lattice constant slightly increased during the [FeII(CN6]4-/[FeIII(CN6]3- oxidization reaction while decreased during the MnII/MnIII oxidization reaction. The two-electron reaction without structural phase transition is responsible for the high charge capacity and the good cyclability.

  18. Universal Themes of Bose-Einstein Condensation (United States)

    Proukakis, Nick P.; Snoke, David W.; Littlewood, Peter B.


    Foreword; List of contributors; Preface; Part I. Introduction: 1. Universality and Bose-Einstein condensation: perspectives on recent work D. W. Snoke, N. P. Proukakis, T. Giamarchi and P. B. Littlewood; 2. A history of Bose-Einstein condensation of atomic hydrogen T. Greytak and D. Kleppner; 3. Twenty years of atomic quantum gases: 1995-2015 W. Ketterle; 4. Introduction to polariton condensation P. B. Littlewood and A. Edelman; Part II. General Topics: Editorial notes; 5. The question of spontaneous symmetry breaking in condensates D. W. Snoke and A. J. Daley; 6. Effects of interactions on Bose-Einstein condensation R. P. Smith; 7. Formation of Bose-Einstein condensates M. J. Davis, T. M. Wright, T. Gasenzer, S. A. Gardiner and N. P. Proukakis; 8. Quenches, relaxation and pre-thermalization in an isolated quantum system T. Langen and J. Schmiedmayer; 9. Ultracold gases with intrinsic scale invariance C. Chin; 10. Berezinskii-Kosterlitz-Thouless phase of a driven-dissipative condensate N. Y. Kim, W. H. Nitsche and Y. Yamamoto; 11. Superfluidity and phase correlations of driven dissipative condensates J. Keeling, L. M. Sieberer, E. Altman, L. Chen, S. Diehl and J. Toner; 12. BEC to BCS crossover from superconductors to polaritons A. Edelman and P. B. Littlewood; Part III. Condensates in Atomic Physics: Editorial notes; 13. Probing and controlling strongly correlated quantum many-body systems using ultracold quantum gases I. Bloch; 14. Preparing and probing chern bands with cold atoms N. Goldman, N. R. Cooper and J. Dalibard; 15. Bose-Einstein condensates in artificial gauge fields L. J. LeBlanc and I. B. Spielman; 16. Second sound in ultracold atomic gases L. Pitaevskii and S. Stringari; 17. Quantum turbulence in atomic Bose-Einstein condensates N. G. Parker, A. J. Allen, C. F. Barenghi and N. P. Proukakis; 18. Spinor-dipolar aspects of Bose-Einstein condensation M. Ueda; Part IV. Condensates in Condensed Matter Physics: Editorial notes; 19. Bose

  19. Soft Condensed Matter

    Energy Technology Data Exchange (ETDEWEB)

    Jones, Richard A L


    The author states in the preface of the book that the aim is ' give a unified overview of the various aspects of the physics of soft condensed matter'. The book succeeds in fulfilling this aim in many respects. The style is fluent and concise and gives the necessary explanations to make its content understandable to people with some knowledge of the basic principles of physics. The content of the book is complete enough to give a panoramic view of the landscape of soft condensed matter. The first two chapters give, respectively, a short introduction and a presentation of forces, energies and timescales, giving a general overview and pointing out the particular importance of different aspects such as timescales, which are much more important in soft condensed matter than in traditional or 'hard' condensed matter. The next chapter, devoted to phase transition, recalls that the equilibrium between two phases is controlled by free energy considerations. Spinodal decomposition is presented as a counterpart of nucleation and growth. Again, characteristic length scales are considered and applied to a phase separation mixture of polymers in a common solvent. The following three chapters are devoted respectively to specific topics: colloidal dispersion, polymers and gelation. The stability and phase behaviour of colloids are related to the interaction between colloidal particles. Properties of colloidal crystals as well as colloidal dispersion are depicted in terms of stabilization of crystalline colloids. The flow properties of colloidal dispersion are presented in terms of free energy minimization and the structure of the dispersion. After a brief introduction to polymer chemistry and architecture, the coil-globule transition is discussed. Viscoelasticity of polymers is described and discussed by introducing the notion of entanglement. This leads to the introduction of the tube model and the theory of reptation. The sol-gel transition is presented

  20. An improved stochastic algorithm for temperature-dependent homogeneous gas phase reactions

    CERN Document Server

    Kraft, M


    We propose an improved stochastic algorithm for temperature-dependent homogeneous gas phase reactions. By combining forward and reverse reaction rates, a significant gain in computational efficiency is achieved. Two modifications of modelling the temperature dependence (with and without conservation of enthalpy) are introduced and studied quantitatively. The algorithm is tested for the combustion of n-heptane, which is a reference fuel component for internal combustion engines. The convergence of the algorithm is studied by a series of numerical experiments and the computational cost of the stochastic algorithm is compared with the DAE code DASSL. If less accuracy is needed the stochastic algorithm is faster on short simulation time intervals. The new stochastic algorithm is significantly faster than the original direct simulation algorithm in all cases considered.

  1. Geometric phase and quantum interference in photosynthetic reaction center: Regulation of electron transfer

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Yuming, E-mail:; Su, Yuehua; Dai, Zhenhong; Wang, WeiTian


    Photosynthesis is driven by electron transfer in reaction centers in which the functional unit is composed of several simple molecules C{sub 2}-symmetrically arranged into two branches. In view of quantum mechanism, both branches are possible pathways traversed by the transferred electron. Due to different evolution of spin state along two pathways in transmembrane electric potential (TEP), quantum state of the transferred electron at the bridged site acquires a geometric phase difference dependent on TEP, the most efficient electron transport takes place in a specific range of TEP beyond which electron transfer is dramatically suppressed. What’s more, reaction center acts like elaborately designed quantum device preparing polarized spin dependent on TEP for the transferred electron to regulate the reduction potential at bridged site. In brief, electron transfer generates the TEP, reversely, TEP modulates the efficiency of electron transfer. This may be an important approach to maintaining an appreciable pH environment in photosynthesis.

  2. Geometric phase and quantum interference in photosynthetic reaction center: Regulation of electron transfer (United States)

    Sun, Yuming; Su, Yuehua; Dai, Zhenhong; Wang, WeiTian


    Photosynthesis is driven by electron transfer in reaction centers in which the functional unit is composed of several simple molecules C2-symmetrically arranged into two branches. In view of quantum mechanism, both branches are possible pathways traversed by the transferred electron. Due to different evolution of spin state along two pathways in transmembrane electric potential (TEP), quantum state of the transferred electron at the bridged site acquires a geometric phase difference dependent on TEP, the most efficient electron transport takes place in a specific range of TEP beyond which electron transfer is dramatically suppressed. What's more, reaction center acts like elaborately designed quantum device preparing polarized spin dependent on TEP for the transferred electron to regulate the reduction potential at bridged site. In brief, electron transfer generates the TEP, reversely, TEP modulates the efficiency of electron transfer. This may be an important approach to maintaining an appreciable pH environment in photosynthesis.

  3. Elementary steps and reaction pathways in the aqueous phase alkylation of phenol with ethanol

    Energy Technology Data Exchange (ETDEWEB)

    Eckstein, Sebastian; Hintermeier, Peter H.; Olarte, Mariefel V.; Liu, Yue; Baráth, Eszter; Lercher, Johannes A.


    The hydronium ion normalized reaction rate in aqueous phase alkylation of phenol with ethanol on H-MFI zeolites increases with decreasing concentration of acid sites. Higher rates are caused by higher concentrations of phenol in the zeolite pores, as the concentration of hydronium ions generated by zeolite Brønsted acid sites decreases. Considering the different concentrations of reacting species it is shown that the intrinsic rate constant for alkylation is independent of the concentration of hydronium ions in the zeolite pores. Alkylation at the aromatic ring of phenol and of toluene as well as O-alkylation of phenol have the same activation energy, 104 ± 5 kJ/mol. This is energetic barrier to form the ethyl carbenium ion from ethanol associated to the hydronium ion. Thus, in both the reaction pathways the catalyst involves a carbenium ion, which forms a bond to a nucleophilic oxygen (ether formation) or carbon (alkylation).

  4. Gas-phase thermolysis reaction of formaldehyde diperoxide. Kinetic study and theoretical mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Jorge, Nelly Lidia [Instituto Andaluz de Ciencias de la Tierra, CSIC-Universidad de Granada, Av. Las Palmeras 4, 18100 Armilla, Granada (Spain); Area de Quimica Fisica Facultad de Ciencias Exactas y Naturales y Agrimensura, UNNE, Avda. Libertad 5460, 3400 Corrientes (Argentina); Romero, Jorge Marcelo [Area de Quimica Fisica Facultad de Ciencias Exactas y Naturales y Agrimensura, UNNE, Avda. Libertad 5460, 3400 Corrientes (Argentina); Grand, Andre [INAC, SCIB, Laboratoire ' Lesions des Acides Nucleiques' , UMR CEA-UJF E3, CEA-Grenoble, 17 Rue des Martyrs, 38054 Grenoble cedex 9 (France); Hernandez-Laguna, Alfonso, E-mail: [Instituto Andaluz de Ciencias de la Tierra, CSIC-Universidad de Granada, Av. Las Palmeras 4, 18100 Armilla, Granada (Spain)


    Highlights: Black-Right-Pointing-Pointer Kinetic and mechanism of the gas-phase thermolysis of tetroxane were determined. Black-Right-Pointing-Pointer Gas chromatography and computational potential energy surfaces were performed. Black-Right-Pointing-Pointer A mechanism in steps looked like the most probable mechanism. Black-Right-Pointing-Pointer A spin-orbit coupling appeared at the singlet and triple diradical open structures. Black-Right-Pointing-Pointer A non-adiabatic crossing from the singlet to the triplet state occurred. - Abstract: Gas-phase thermolysis reaction of formaldehyde diperoxide (1,2,4,5-tetroxane) was performed in an injection chamber of a gas chromatograph at a range of 463-503 K. The average Arrhenius activation energy and pre-exponential factor were 29.3 {+-} 0.8 kcal/mol and 5.2 Multiplication-Sign 10{sup 13} s{sup -1}, respectively. Critical points and reaction paths of the ground singlet and first triplet potential energy surfaces (PES) were calculated, using DFT method at BHANDHLYP/6-311+G{sup Asterisk-Operator Asterisk-Operator} level of the theory. Also, G3 calculations were performed on the reactant and products. Reaction by the ground-singlet and first-triplet states turned out to be endothermic and exothermic, respectively. The mechanism in three steps seemed to be the most probable one. An electronically non-adiabatic process appeared, in which a crossing, at an open diradical structure, from the singlet to the triplet state PES occurred, due to a spin-orbit coupling, yielding an exothermic reaction. Theoretical kinetic constant coming from the non- adiabatic transition from the singlet to the triplet state agrees with the experimental values.

  5. Illustrating the Utility of X-Ray Crystallography for Structure Elucidation through a Tandem Aldol Condensation/Diels-Alder Reaction Sequence (United States)

    Hoang, Giang T.; Kubo, Tomohiro; Young, Victor G., Jr.; Kautzky, Jacob A.; Wissinger, Jane E.


    Two introductory organic chemistry laboratory experiments are described based on the Diels-Alder reaction of 2,3,4,5-tetraphenylcyclopentadienone, which is synthesized prior to or in a one-pot reaction, with styrene. Students are presented with three possible products, the "endo" and "exo" diastereomers and the decarbonylated…

  6. Phase-space geometry and reaction dynamics near index 2 saddles (United States)

    Ezra, Gregory S.; Wiggins, Stephen


    We study the phase-space geometry associated with index 2 saddles of a potential energy surface and its influence on reaction dynamics for n degree-of-freedom (DoF) Hamiltonian systems. In recent years, similar studies have been carried out for index 1 saddles of potential energy surfaces, and the phase-space geometry associated with classical transition state theory has been elucidated. In this case, the existence of a normally hyperbolic invariant manifold (NHIM) of saddle stability type has been shown, where the NHIM serves as the 'anchor' for the construction of dividing surfaces having the no-recrossing property and minimal flux. For the index 1 saddle case, the stable and unstable manifolds of the NHIM are co-dimension 1 in the energy surface and have the structure of spherical cylinders, and thus act as the conduits for reacting trajectories in phase space. The situation for index 2 saddles is quite different, and their relevance for reaction dynamics has not previously been fully recognized. We show that NHIMs with their stable and unstable manifolds still exist, but that these manifolds by themselves lack sufficient dimension to act as barriers in the energy surface in order to constrain reactions. Rather, in the index 2 case there are different types of invariant manifolds, containing the NHIM and its stable and unstable manifolds, that act as co-dimension 1 barriers in the energy surface. These barriers divide the energy surface in the vicinity of the index 2 saddle into regions of qualitatively different trajectories exhibiting a wider variety of dynamical behavior than for the case of index 1 saddles. In particular, we can identify a class of trajectories, which we refer to as 'roaming trajectories', which are not associated with reaction along the classical minimum energy path (MEP). We illustrate the significance of our analysis of the index 2 saddle for reaction dynamics with two examples. The first involves isomerization on a potential energy

  7. Linear free energy relationships between aqueous phase hydroxyl radical reaction rate constants and free energy of activation. (United States)

    Minakata, Daisuke; Crittenden, John


    The hydroxyl radical (HO(•)) is a strong oxidant that reacts with electron-rich sites on organic compounds and initiates complex radical chain reactions in aqueous phase advanced oxidation processes (AOPs). Computer based kinetic modeling requires a reaction pathway generator and predictions of associated reaction rate constants. Previously, we reported a reaction pathway generator that can enumerate the most important elementary reactions for aliphatic compounds. For the reaction rate constant predictor, we develop linear free energy relationships (LFERs) between aqueous phase literature-reported HO(•) reaction rate constants and theoretically calculated free energies of activation for H-atom abstraction from a C-H bond and HO(•) addition to alkenes. The theoretical method uses ab initio quantum mechanical calculations, Gaussian 1-3, for gas phase reactions and a solvation method, COSMO-RS theory, to estimate the impact of water. Theoretically calculated free energies of activation are found to be within approximately ±3 kcal/mol of experimental values. Considering errors that arise from quantum mechanical calculations and experiments, this should be within the acceptable errors. The established LFERs are used to predict the HO(•) reaction rate constants within a factor of 5 from the experimental values. This approach may be applied to other reaction mechanisms to establish a library of rate constant predictions for kinetic modeling of AOPs.

  8. Forces and stress in second order Møller-Plesset perturbation theory for condensed phase systems within the resolution-of-identity Gaussian and plane waves approach. (United States)

    Del Ben, Mauro; Hutter, Jürg; VandeVondele, Joost


    The forces acting on the atoms as well as the stress tensor are crucial ingredients for calculating the structural and dynamical properties of systems in the condensed phase. Here, these derivatives of the total energy are evaluated for the second-order Møller-Plesset perturbation energy (MP2) in the framework of the resolution of identity Gaussian and plane waves method, in a way that is fully consistent with how the total energy is computed. This consistency is non-trivial, given the different ways employed to compute Coulomb, exchange, and canonical four center integrals, and allows, for example, for energy conserving dynamics in various ensembles. Based on this formalism, a massively parallel algorithm has been developed for finite and extended system. The designed parallel algorithm displays, with respect to the system size, cubic, quartic, and quintic requirements, respectively, for the memory, communication, and computation. All these requirements are reduced with an increasing number of processes, and the measured performance shows excellent parallel scalability and efficiency up to thousands of nodes. Additionally, the computationally more demanding quintic scaling steps can be accelerated by employing graphics processing units (GPU's) showing, for large systems, a gain of almost a factor two compared to the standard central processing unit-only case. In this way, the evaluation of the derivatives of the RI-MP2 energy can be performed within a few minutes for systems containing hundreds of atoms and thousands of basis functions. With good time to solution, the implementation thus opens the possibility to perform molecular dynamics (MD) simulations in various ensembles (microcanonical ensemble and isobaric-isothermal ensemble) at the MP2 level of theory. Geometry optimization, full cell relaxation, and energy conserving MD simulations have been performed for a variety of molecular crystals including NH3, CO2, formic acid, and benzene.

  9. Phosphopeptidomimetic substance libraries from multicomponent reaction: enantioseparation on quinidine carbamate stationary phase. (United States)

    Gargano, Andrea F G; Lindner, Wolfgang; Lämmerhofer, Michael


    In the present contribution we report a HPLC enantioseparation method for a library of amido-aminophosphonate structures generated by a novel Ugi-multicomponent reaction. The enantioseparation of these novel potentially bioactive molecules was achieved by means of HPLC on cinchona-carbamate based chiral anion-exchangers under polar organic elution conditions. The compounds were synthesized with the aim of offering a wide degree of heterogeneity in terms of structural elements to evaluate the influence of various structural motifs on enantioselectivity. The resultant compound library allows to derive structure-enantioselectivity relationships useful for understanding the chiral recognition process. As part of the study mobile phase characteristics such as concentration and type of counterion, mobile phase composition, apparent pH and temperature were investigated with regards to their effect on the separation performances. Employing a single mass spectrometry-compatible mobile phase, 23 compounds out of a pool of 42 racemic amido-aminophosphonate structures reached full baseline separation (Rs>1.5) and 5 were almost baseline separated (1phases for this class of analytes. Copyright © 2013 Elsevier B.V. All rights reserved.

  10. Saccadic reaction times to audiovisual stimuli show effects of oscillatory phase reset.

    Directory of Open Access Journals (Sweden)

    Adele Diederich

    Full Text Available Initiating an eye movement towards a suddenly appearing visual target is faster when an accessory auditory stimulus occurs in close spatiotemporal vicinity. Such facilitation of saccadic reaction time (SRT is well-documented, but the exact neural mechanisms underlying the crossmodal effect remain to be elucidated. From EEG/MEG studies it has been hypothesized that coupled oscillatory activity in primary sensory cortices regulates multisensory processing. Specifically, it is assumed that the phase of an ongoing neural oscillation is shifted due to the occurrence of a sensory stimulus so that, across trials, phase values become highly consistent (phase reset. If one can identify the phase an oscillation is reset to, it is possible to predict when temporal windows of high and low excitability will occur. However, in behavioral experiments the pre-stimulus phase will be different on successive repetitions of the experimental trial, and average performance over many trials will show no signs of the modulation. Here we circumvent this problem by repeatedly presenting an auditory accessory stimulus followed by a visual target stimulus with a temporal delay varied in steps of 2 ms. Performing a discrete time series analysis on SRT as a function of the delay, we provide statistical evidence for the existence of distinct peak spectral components in the power spectrum. These frequencies, although varying across participants, fall within the beta and gamma range (20 to 40 Hz of neural oscillatory activity observed in neurophysiological studies of multisensory integration. Some evidence for high-theta/alpha activity was found as well. Our results are consistent with the phase reset hypothesis and demonstrate that it is amenable to testing by purely psychophysical methods. Thus, any theory of multisensory processes that connects specific brain states with patterns of saccadic responses should be able to account for traces of oscillatory activity in observable

  11. Collecting exhaled breath condensate (EBC) with two condensers in series: a promising technique for studying the mechanisms of EBC formation, and the volatility of selected biomarkers. (United States)

    Corradi, Massimo; Goldoni, Matteo; Caglieri, Andrea; Folesani, Giuseppina; Poli, Diana; Corti, Marina; Mutti, Antonio


    Exhaled breath condensate (EBC) consists mainly of water, but also contains semivolatile and nonvolatile compounds. The aim of this study was to develop a system in which two condensers are simultaneously used in series to clarify the mechanisms of EBC condensation. Two aliquots of EBC (EBC1 and EBC2) were collected from 20 asymptomatic smokers and 20 healthy young nonsmokers using a specifically designed device having two condensers in series in which total volume, hydrogen peroxide (H(2)O(2)), ammonium (NH(4)(+)), and conductivity before and after lyophilization were measured. Water, NH(4)(+) levels and conductivity before lyophilization were significantly lower in the EBC2 than in the EBC1 of smokers and nonsmokers; the contrary was true for H(2)O(2) levels. Almost all nonvolatile salts were collected in the first condenser, because more than 50% of postlyophilization conductivity was below the detection limit in EBC2. The recovery of volatile molecules and their derivatives (water and NH(4)(+)) was partial in the first condenser, but appreciable amounts of both were measured in the second; however, the condenser immediately in contact with exhaled air was more efficient in terms of water, NH(4)(+) and conductivity before lyophilization. On the contrary, nonvolatile ions (conductivity after lyophilization) were mainly collected in the first condenser. Finally, the behavior of H(2)O(2) cannot be explained on the basis of its chemical and physical properties, and the most probable explanation is that some was byproduced by a radical reaction in the gas phase or during the condensation process in water.

  12. Metastable carbon phases from CF/sub 4/ reactions. Part I. Reactions with SiC and Si

    Energy Technology Data Exchange (ETDEWEB)

    Holcombe, C.E. Jr.; Condon, J.B.; Johnson, D.H.


    Reactions of CF/sub 4/ with ..beta..-SiC and Si powders were studied by thermal analysis techniques. Products were examined by x-ray and electron diffraction and electron microscopy. Two exotherms occur with ..beta..-SiC: at 874/sup 0/C, possibly from preferential reaction of the (111) planes; at 982/sup 0/C, presumably from rapid reaction on arbitrary planes. The primary product is amorphous carbon; however, graphite, carbon VI, or lonsdaleite single crystals also form. With Si powder, an exothermic reaction at 990/sup 0/C results from the formation of textured ..beta..-SiC.

  13. Development of a group contribution method to predict aqueous phase hydroxyl radical (HO*) reaction rate constants. (United States)

    Minakata, Daisuke; Li, Ke; Westerhoff, Paul; Crittenden, John


    The hydroxyl radical (HO*) is a strong oxidant that reacts with electron-rich sites of organic compounds and initiates complex chain mechanisms. In order to help understand the reaction mechanisms, a rule-based model was previously developed to predict the reaction pathways. For a kinetic model, there is a need to develop a rate constant estimator that predicts the rate constants for a variety of organic compounds. In this study, a group contribution method (GCM) is developed to predict the aqueous phase HO* rate constants for the following reaction mechanisms: (1) H-atom abstraction, (2) HO* addition to alkenes, (3) HO* addition to aromatic compounds, and (4) HO* interaction with sulfur (S)-, nitrogen (N)-, or phosphorus (P)-atom-containing compounds. The GCM hypothesizes that an observed experimental rate constant for a given organic compound is the combined rate of all elementary reactions involving HO*, which can be estimated using the Arrhenius activation energy, E(a), and temperature. Each E(a) for those elementary reactions can be comprised of two parts: (1) a base part that includes a reactive bond in each reaction mechanism and (2) contributions from its neighboring functional groups. The GCM includes 66 group rate constants and 80 group contribution factors, which characterize each HO* reaction mechanism with steric effects of the chemical structure groups and impacts of the neighboring functional groups, respectively. Literature-reported experimental HO* rate constants for 310 and 124 compounds were used for calibration and prediction, respectively. The genetic algorithms were used to determine the group rate constants and group contribution factors. The group contribution factors for H-atom abstraction and HO* addition to the aromatic compounds were found to linearly correlate with the Taft constants, sigma*, and electrophilic substituent parameters, sigma+, respectively. The best calibrations for 83% (257 rate constants) and predictions for 62% (77

  14. Sequential patterns of inflammatory events during developing and expressed skin late-phase reactions. (United States)

    Zweiman, B; Haralabatos, I C; Pham, N C; David, M; von Allmen, C


    Although there has been much study of the histologic features of the late-phase reactions (LPR) seen 6 to 24 hours after intradermal injection of allergens, much less is known about the events occurring during development of such LPR. Our purpose was to compare sequential gross and histologic inflammatory responses during developing skin LPR within 6 hours after challenge. Gross reactions were measured and biopsy specimens obtained at 20 minutes and 1, 2, and 6 hours after intradermal allergen (Ag) and buffer diluent control (B) injections in 7 atopic subjects with known immediate and LPR. Inflammatory cell responses were compared, as detected by immunohistochemistry in Ag and B sites. These findings were then compared with those at 24 hours. Gross LPR evolved without a hiatus from the immediate wheal responses over the next 6 hours (P =.04 vs that in B sites) and then decreased by 24 hours. Prominent PMN accumulation started by 20 minutes, peaking at 1 hour (P Skin LPR is characterized by evolution of a gross indurated reaction from the immediate whealing response over the first 6 hours after intradermal Ag challenge, with an early accumulation of PMN and eosinophils, not directly attributable to lymphocyte entry or vascular cell adhesion molecule expression. Likely, multiple other factors may also play roles in the complex pathogenesis of LPR.

  15. Elementary Reactions and Their Role in Gas-Phase Prebiotic Chemistry

    Directory of Open Access Journals (Sweden)

    Nadia Balucani


    Full Text Available The formation of complex organic molecules in a reactor filled with gaseous mixtures possibly reproducing the primitive terrestrial atmosphere and ocean demonstrated more than 50 years ago that inorganic synthesis of prebiotic molecules is possible, provided that some form of energy is provided to the system. After that groundbreaking experiment, gas-phase prebiotic molecules have been observed in a wide variety of extraterrestrial objects (including interstellar clouds, comets and planetary atmospheres where the physical conditions vary widely. A thorough characterization of the chemical evolution of those objects relies on a multi-disciplinary approach: 1 observations allow us to identify the molecules and their number densities as they are nowadays; 2 the chemistry which lies behind their formation starting from atoms and simple molecules is accounted for by complex reaction networks; 3 for a realistic modeling of such networks, a number of experimental parameters are needed and, therefore, the relevant molecular processes should be fully characterized in laboratory experiments. A survey of the available literature reveals, however, that much information is still lacking if it is true that only a small percentage of the elementary reactions considered in the models have been characterized in laboratory experiments. New experimental approaches to characterize the relevant elementary reactions in laboratory are presented and the implications of the results are discussed.

  16. Steam condenser developments (United States)

    Lang, H. V.

    Factors determining condenser size and tube arrangement are reviewed, including steam side pressure drop; incondensible blanketing; effect of incondensibles on heat transfer; vent requirements; deaeration; condensate depression; cooling water velocity; tube material and diameter selection; fouling; and enhanced heat transfer tubes. Tube nest shapes and condenser concepts are described. Thermal design, and condenser acceptance testing are treated; field test results on "Church Window'' condensers are reported.

  17. Fermion masses through four-fermion condensates

    CERN Document Server

    Ayyar, Venkitesh


    Fermion masses can be generated through four-fermion condensates when symmetries prevent fermion bilinear condensates from forming. This less explored mechanism of fermion mass generation is responsible for making four reduced staggered lattice fermions massive at strong couplings in a lattice model with a local four-fermion coupling. The model has a massless fermion phase at weak couplings and a massive fermion phase at strong couplings. In particular there is no spontaneous symmetry breaking of any lattice symmetries in both these phases. Recently it was discovered that in three space-time dimensions there is a direct second order phase transition between the two phases. Here we study the same model in four space-time dimensions and find results consistent with the existence of a narrow intermediate phase with fermion bilinear condensates, that separates the two asymptotic phases by continuous phase transitions.

  18. Reactions of important OVOCs with hydrogen peroxide and ozone in the tropospheric aqueous phase (United States)

    Schöne, Luisa; Weller, Christian; Herrmann, Hartmut


    Besides research on the microphysics of cloud droplets and similar aqueous systems in the troposphere, the chemistry of volatile organic compounds (VOCs) from anthropogenic and biogenic sources cannot be neglected for the understanding of tropospheric processes such as the organic particle mass formation. Emissions of biogenic volatile organic compounds (BVOCs) can exceed those of VOCs from anthropogenic sources by a factor of 10[1]. Oxidation products of BVOCs like glyoxal, methylglyoxal, glycolate, glyoxylate and pyruvate, glycolaldehyde, and the unsaturated compounds methacrolein and methyl vinyl ketone are known precursors for less volatile organic substances found in secondary organic aerosols[2,3]. Yet, the main decomposition of these substances is believed to occur via radical reactions. However, Tilgner and Herrmann[2] showed evidence that the turnovers by non-radical reactions with H2O2 or ozone and some non-oxidative organic accretion reactions may even exceed those from the most reactive species in the lower troposphere, the hydroxyl radical OH. This work investigated the reactivities of the atmospheric relevant oxidation products including pyruvic acid and glyoxylic acid towards O3 and H2O2 in the aqueous phase. Furthermore, pH effects were studied by measuring the kinetics of both the protonated and deprotonated forms. The measurements were performed using a UV/VIS-spectrometer (conventional and in addition a Stopped Flow technique) and capillary electrophoresis. In some cases the results indicate higher turnovers of H2O2 and ozone reactions compared to interactions with atmospheric radicals. The experimental data obtained will be presented and their implications for atmospheric multiphase chemistry are discussed. [1] Guenther et al., 1995, Journal of Geophysical Research - Atmosphere, 100(D5), 8873-8892. [2] Tilgner and Herrmann, 2010, Atmospheric Environment, 44, 5415-5422. [3] van Pinxteren et al., 2005, Atmospheric Environment, 39, 4305-4320.

  19. Comparison of TiO2 photocatalysis, electrochemically assisted Fenton reaction and direct electrochemistry for simulation of phase I metabolism reactions of drugs. (United States)

    Ruokolainen, Miina; Gul, Turan; Permentier, Hjalmar; Sikanen, Tiina; Kostiainen, Risto; Kotiaho, Tapio


    The feasibility of titanium dioxide (TiO2) photocatalysis, electrochemically assisted Fenton reaction (EC-Fenton) and direct electrochemical oxidation (EC) for simulation of phase I metabolism of drugs was studied by comparing the reaction products of buspirone, promazine, testosterone and 7-ethoxycoumarin with phase I metabolites of the same compounds produced in vitro by human liver microsomes (HLM). Reaction products were analysed by UHPLC-MS. TiO2 photocatalysis simulated the in vitro phase I metabolism in HLM more comprehensively than did EC-Fenton or EC. Even though TiO2 photocatalysis, EC-Fenton and EC do not allow comprehensive prediction of phase I metabolism, all three methods produce several important metabolites without the need for demanding purification steps to remove the biological matrix. Importantly, TiO2 photocatalysis produces aliphatic and aromatic hydroxylation products where direct EC fails. Furthermore, TiO2 photocatalysis is an extremely rapid, simple and inexpensive way to generate oxidation products in a clean matrix and the reaction can be simply initiated and quenched by switching the UV lamp on/off. Copyright © 2015 Elsevier B.V. All rights reserved.

  20. Kinetics and products of gas-phase reactions of ozone with methyl methacrylate, methyl acrylate, and ethyl acrylate. (United States)

    Bernard, F; Eyglunent, G; Daële, V; Mellouki, A


    The kinetics and products of the gas-phase reactions of ozone with methyl methacrylate, methyl acrylate, and ethyl acrylate have been investigated at 760 Torr total pressure of air and 294 +/- 2 K. The rate coefficients obtained (in cm(3) molecule(-1) s(-1) units) were as follows: k(methyl methacrylate) = (6.7 +/- 0.9) x 10(-18), k(methyl acrylate) = (0.95 +/- 0.07) x 10(-18), and k(ethyl acrylate) = (1.3 +/- 0.1) x 10(-18). In addition to formaldehyde being observed as a product of the three reactions, the other major reaction products were methyl pyruvate from reaction of ozone with methyl methacrylate, methyl glyoxylate from reaction of ozone with methyl acrylate, and ethyl glyoxylate from reaction of ozone with ethyl acrylate. Possible reaction mechanisms leading to the observed products are presented and discussed.

  1. Prebiotic molecules formation through the gas-phase reaction between HNO and CH2CHOH2+ (United States)

    Redondo, Pilar; Martínez, Henar; Largo, Antonio; Barrientos, Carmen


    Context. Knowing how the molecules that are present in the ISM can evolve to more complex ones is an interesting topic in interstellar chemistry. The study of possible reactions between detected species can help to understand the evolution in complexity of the interstellar matter and also allows knowing the formation of new molecules which could be candidates to be detected. We focus our attention on two molecules detected in space, vinyl alcohol (CH2CHOH) and azanone (HNO). Aims: We aim to carry out a theoretical study of the ion-molecule reaction between protonated vinyl alcohol and azanone. The viability of formation of complex organic molecules (COMs) from these reactants is expected to provide some insight into the formation of prebiotic species through gas phase reactions. Methods: The reaction of protonated vinyl alcohol with azanone has been theoretically studied by using ab initio methods. Stationary points on the potential energy surface (PES) were characterized at the second-order Moller-Plesset level in conjunction with the aug-cc-pVTZ (correlation-consistent polarized valence triple-zeta) basis set. In addition, the electronic energies were refined by means of single-point calculations at the CCSD(T) level (coupled cluster single and double excitation model augmented with a non-iterative treatment of triple excitations) with the same basis set. Results: From a thermodynamic point of view, twelve products, composed of carbon, oxygen, nitrogen, and hydrogen which could be precursors in the formation of more complex biological molecules, can be obtained from this reaction. Among these, we focus especially on ionized glycine and two of its isomers. The analysis of the PES shows that only formation of cis- and trans-O-protonated imine acetaldehyde, CH2NHCOH+ and, CHNHCHOH+, are viable under interstellar conditions. Conclusions: The reaction of protonated vinyl alcohol with azanone can evolve in the interstellar medium to more complex organic molecules of

  2. Kinetics and mechanistic study of the gas-phase reaction of ozone with methylbutenol (United States)

    Klawatsch-Carrasco, N.; Doussin, J. F.; Rea, G.; Wenger, J.; Carlier, P.


    Biogenic volatile organic compounds (BVOCs) account for around 90% of hydrocarbon emissions into the Earth's atmosphere ([1], [2]). Several thousand different BVOCs have been identified, the most well known being unsaturated hydrocarbons. However, over the last ten years an increasing number of oxygenated BVOCs, such as methylbutenol (MBO), have also been detected in field measurement campaigns and plant emission studies ([3], [4]). In order to determine the environmental impact of BVOCs, a thorough knowledge of the rates and mechanisms for their atmospheric degradation is required. The major atmospheric degradation processes for BVOCs are gas-phase reaction with hydroxyl radicals (OH), nitrate radicals (NO_3) and ozone (O_3). These reactions produce oxidised hydrocarbons, ozone and secondary organic aerosol and, as a result, exert a strong influence on the chemical composition of the atmosphere. Very few studies are available concerning the reactivity of MBO. To extend the available database on the atmospheric chemistry of biogenic compounds, the reaction of O_3 with MBO at 296(±2) K has been investigated in atmospheric simulation chambers at LISA in Créteil (France) and CRAC in Cork (Ireland), using complementary techniques such as FTIR spectroscopy, PFBHA derivatization with GC-MS detection and a particle sizer and counter. The rate constant for the reaction was determined using an absolute rate technique, yielding a value of (8.3±0.9)× 10-18 cm^3 molecule-1s-1. Mechanistic studies of the reaction lead to the following observations: a primary formation of only three carbonyl compounds, formaldehyde (yield=0.40±0.03), acetone (yield=0.27±0.02) and 2-methyl-2-hydroxy-propanal. In addition, there is a noticeable formation of aerosols at the very beginning of the reaction that seemed to depend on the relative humidity. References: [1] Wayne, R. P. (2000). 3rd edition. Oxford university press inc. Edition. [2] Finlayson-Pitts, B. and Pitts Jr, J. N. ( 2000

  3. The physics of exciton-polariton condensates

    CERN Document Server

    Lagoudakis, Konstantinos


    In 2006 researchers created the first polariton Bose-Einstein condensate at 19K in the solid state. Being inherently open quantum systems, polariton condensates open a window into the unpredictable world of physics beyond the “fifth state of matter”: the limited lifetime of polaritons renders polariton condensates out-of-equilibrium and provides a fertile test-bed for non-equilibrium physics. This book presents an experimental investigation into exciting features arising from this non-equilibrium behavior. Through careful experimentation, the author demonstrates the ability of polaritons to synchronize and create a single energy delocalized condensate. Under certain disorder and excitation conditions the complete opposite case of coexisting spatially overlapping condensates may be observed. The author provides the first demonstration of quantized vortices in polariton condensates and the first observation of fractional vortices with full phase and amplitude characterization. Finally, this book investigate...

  4. Performance of a passive emergency heat removal system of advanced reactors in two-phase flow and with high concentration of non-condensable; Atuacao de um sistema passivo de remocao de calor de emergencia de reatores avancados em escoamento bifasico e com alta concentracao de nao-condensaveis

    Energy Technology Data Exchange (ETDEWEB)

    Macedo, Luiz Alberto


    The research and the development of passive emergency cooling systems are necessary for the new generation of thermo-nuclear systems. Some basic information on the operation of these systems require the research of some relative processes to the natural circulation, mainly in conditions of two-phase flow involving processes of condensation in the presence of non-condensable gases, because many found situations are new. The experimental facility called Bancada de Circulacao Natural (BCN) was used for the realization of tests with diverse concentrations of non-condensable and power levels. The non-condensable gas present in the circuit decreases the rate of heat transfer for the secondary of the heat exchanger, determining low efficiency of the heat exchanger. High concentration of non-condensable in the vapor condensation, determines negative pressure, and cause the inversion of the flow in the circuit. The initial concentration of non-condensable and the geometry of the circuit, in the inlet of the heat exchanger, determines the establishment of transitory with two-phase flow. The BCN was performed with the computational code of Analysis of Accidents and Thermal-Hydraulics RELAP5/MOD 3.3 and, the calculated values had been compared with the experimental data, presenting good agreement for small non-condensable concentrations. The values calculated for high concentrations of non-condensable had been satisfactory after the circuit to have reached the temperature of saturation in the electric heater. (author)

  5. Fluid phase equilibria of the reaction mixture during the selective hydrogenation of 2-butenal in dense carbon dioxide

    DEFF Research Database (Denmark)

    Musko, Nikolai; Jensen, Anker Degn; Baiker, Alfons


    Knowledge of the phase behaviour and composition is of paramount importance for understanding multiphase reactions. We have investigated the effect of the phase behaviour in the palladium-catalysed selective hydrogenation of 2-butenal to saturated butanal in dense carbon dioxide. The reactions were...... cell. The results of the catalytic experiments showed that small amounts of carbon dioxide added to the system significantly decrease the conversion, whereas at higher loadings of CO2 the reaction rate gradually increases reaching a maximum. The CPA calculations revealed that this maximum is achieved...... in the so-called “expanded liquid” region, which is located near the critical point of the reacting mixture. It was also found that in this point the hydrogen concentration achieved its maximum in the CO2-expanded phase. Furthermore, the pressure – temperature regions where the multicomponent reaction...

  6. Differential reaction cross sections from rotationally resolved quantum scattering calculations: application to gas-phase S(N)2 reactions. (United States)

    Hennig, Carsten; Schmatz, Stefan


    Differential reaction cross sections have been computed based on previous rotationally resolved time-independent quantum-mechanical scattering calculations for the complex-forming S(N)2 reaction Cl(-) + CH(3)Br → ClCH(3) + Br(-). The results show almost isotropic cross sections for reactant molecules with high rotational quantum numbers. Backward scattering is disfavoured for reaction out of states with small rotational excitation, in particular the rovibrational ground state. This is a quantum-mechanical effect (interference of partial waves) that can partly be rationalized by simple classical arguments. In particular for higher vibrational excitations, an umbrella effect can be observed that favours the backward direction. It can be explained by the strong enhancement of the reactivity by opening a direct mechanism. The ion-dipole interaction exerts a torque onto the molecule which carries out a rotation by about 90° and then completes the reaction.

  7. Phase equilibria basic principles, applications, experimental techniques

    CERN Document Server

    Reisman, Arnold


    Phase Equilibria: Basic Principles, Applications, Experimental Techniques presents an analytical treatment in the study of the theories and principles of phase equilibria. The book is organized to afford a deep and thorough understanding of such subjects as the method of species model systems; condensed phase-vapor phase equilibria and vapor transport reactions; zone refining techniques; and nonstoichiometry. Physicists, physical chemists, engineers, and materials scientists will find the book a good reference material.

  8. Born-Kothari Condensation for Fermions

    Directory of Open Access Journals (Sweden)

    Arnab Ghosh


    Full Text Available In the spirit of Bose–Einstein condensation, we present a detailed account of the statistical description of the condensation phenomena for a Fermi–Dirac gas following the works of Born and Kothari. For bosons, while the condensed phase below a certain critical temperature, permits macroscopic occupation at the lowest energy single particle state, for fermions, due to Pauli exclusion principle, the condensed phase occurs only in the form of a single occupancy dense modes at the highest energy state. In spite of these rudimentary differences, our recent findings [Ghosh and Ray, 2017] identify the foregoing phenomenon as condensation-like coherence among fermions in an analogous way to Bose–Einstein condensate which is collectively described by a coherent matter wave. To reach the above conclusion, we employ the close relationship between the statistical methods of bosonic and fermionic fields pioneered by Cahill and Glauber. In addition to our previous results, we described in this mini-review that the highest momentum (energy for individual fermions, prerequisite for the condensation process, can be specified in terms of the natural length and energy scales of the problem. The existence of such condensed phases, which are of obvious significance in the context of elementary particles, have also been scrutinized.

  9. Synthesis of pyrazole containing α-amino acids via a highly regioselective condensation/aza-Michael reaction of β-aryl α,β-unsaturated ketones

    NARCIS (Netherlands)

    Gilfillan, Lynne; Artschwager, Raik; Harkiss, Alexander H.; Liskamp, Rob M J; Sutherland, Andrew


    A synthetic approach for the preparation of a new class of highly conjugated unnatural α-amino acids bearing a 5-arylpyrazole side-chain has been developed. Horner-Wadsworth-Emmons reaction of an aspartic acid derived β-keto phosphonate ester with a range of aromatic aldehydes gave β-aryl

  10. Low-temperature Condensation of Carbon (United States)

    Krasnokutski, S. A.; Goulart, M.; Gordon, E. B.; Ritsch, A.; Jäger, C.; Rastogi, M.; Salvenmoser, W.; Henning, Th.; Scheier, P.


    Two different types of experiments were performed. In the first experiment, we studied the low-temperature condensation of vaporized graphite inside bulk liquid helium, while in the second experiment, we studied the condensation of single carbon atoms together with H2, H2O, and CO molecules inside helium nanodroplets. The condensation of vaporized graphite leads to the formation of partially graphitized carbon, which indicates high temperatures, supposedly higher than 1000°C, during condensation. Possible underlying processes responsible for the instant rise in temperature during condensation are discussed. This suggests that such processes cause the presence of partially graphitized carbon dust formed by low-temperature condensation in the diffuse interstellar medium. Alternatively, in the denser regions of the ISM, the condensation of carbon atoms together with the most abundant interstellar molecules (H2, H2O, and CO), leads to the formation of complex organic molecules (COMs) and finally organic polymers. Water molecules were found not to be involved directly in the reaction network leading to the formation of COMs. It was proposed that COMs are formed via the addition of carbon atoms to H2 and CO molecules ({{C}}+{{{H}}}2\\to {HCH},{HCH}+{CO}\\to {{OCCH}}2). Due to the involvement of molecular hydrogen, the formation of COMs by carbon addition reactions should be more efficient at high extinctions compared with the previously proposed reaction scheme with atomic hydrogen.

  11. Low Energy Nuclear Reaction Aircraft- 2013 ARMD Seedling Fund Phase I Project (United States)

    Wells, Douglas P.; McDonald, Robert; Campbell, Robbie; Chase, Adam; Daniel, Jason; Darling, Michael; Green, Clayton; MacGregor, Collin; Sudak, Peter; Sykes, Harrison; hide


    This report serves as the final written documentation for the Aeronautic Research Mission Directorate (ARMD) Seedling Fund's Low Energy Nuclear Reaction (LENR) Aircraft Phase I project. The findings presented include propulsion system concepts, synergistic missions, and aircraft concepts. LENR is a form of nuclear energy that potentially has over 4,000 times the energy density of chemical energy sources. It is not expected to have any harmful emissions or radiation which makes it extremely appealing. There is a lot of interest in LENR, but there are no proven theories. This report does not explore the feasibility of LENR. Instead, it assumes that a working system is available. A design space exploration shows that LENR can enable long range and high speed missions. Six propulsion concepts, six missions, and four aircraft concepts are presented. This report also includes discussion of several issues and concerns that were uncovered during the study and potential research areas to infuse LENR aircraft into NASA's aeronautics research.

  12. Reaction-Controlled Phase-Transfer Catalysis for Propylene Epoxidation to Propylene Oxide (United States)

    Zuwei, Xi; Ning, Zhou; Yu, Sun; Kunlan, Li


    The epoxidation of olefins with H2O2 was performed with a tungsten-containing catalyst. This insoluble catalyst forms soluble active species by the action of H2O2, and when the H2O2 is used up, the catalyst precipitates for easy recycling. Thus, the advantages of both homogeneous and heterogeneous catalysts are combined in one system through reaction-controlled phase transfer of the catalyst. When coupled with the 2-ethylanthraquinone/2-ethylanthrahydroquinone redox process for H2O2 production, O2 can be used for the epoxidation of propylene to propylene oxide with 85% yield based on 2-ethylanthrahydroquinone without any co-products. This approach avoids the problematic co-products normally associated with the industrial production of propylene oxide.

  13. Energy condensed packaged systems. Composition, production, properties


    Igor L. Kovalenko; Vitaliy P. Kuprin; Dmytro V. Kiyaschenko


    In this paper it is presented the substantiation of choice of fuel phase composition and optimal technology of emulsion production on the basis of binary solution of ammonium and calcium nitrates, which provide the obtaining of energy condensed packaged systems with specified properties. The thermal decomposition of energy condensed systems on the basis of ammonium nitrate is investigated. It is shown that the fuel phase of emulsion systems should be based on esters of polyunsaturated acids o...

  14. Highly active Pd-on-magnetite nanocatalysts for aqueous phase hydrodechlorination reactions. (United States)

    Hildebrand, Heike; Mackenzie, Katrin; Kopinke, Frank-Dieter


    Nanoscale catalyst particles are already in focus as excellent tools in catalytic processes and intensive research is currently optimizing their performance. As known from nanosized metal particles, nanocatalysts have the potential of very high reaction rates due to their high specific surface areas and low mass transfer restrictions. In this study, we generated extremely active palladium catalysts on the basis of colloidal magnetic carriers. The most active catalyst contains only traces of Pd (0.15 wt %) on nanomagnetite as carrier. Pd-on-magnetite was successfully tested in batch experiments for the hydrodechlorination (HDC) of the chlorohydrocarbons trichloroethene (TCE) and chlorobenzene. For the HDC of TCE, second-order rate coefficients of approximately 1.6 x 10(4) L g(-1) min(-1) were measured. Such high activities have never been described before for Pd-containing catalysts in aqueous phase HDC reactions. The ferrimagnetism of the carrier enables a separation of the nanocatalyst from the treated water by means of magnetic separation. This allows the catalyst to be reused several times, which is an important advantage compared to other nanoscale catalytic systems such as pure Pd or Pd-on-Au colloids.

  15. Phase Evolution in Boride-Based Cermets and Reaction Bonding onto Plain Low Carbon Steel Substrate (United States)

    Palanisamy, B.; Upadhyaya, A.


    Reaction sinter bonding is a process that aims to bond two materials for improvement in properties through reactive sintering technique. The process has been effectively used to sinter hard materials like borides in situ which not only possess excellent oxidation resistance, good corrosion resistance but also resistant to abrasive wear. Sinter bonding is a unique surface modification process achieved through powder metallurgy and is competent with other techniques like boronizing sintering and sinter-brazing since it eliminates the additional operations of heat treatment and assembly and removes the inherent setbacks with these processes. This study focuses on identifying the phase evolution mechanism using characterization tools like x-ray diffractometry and energy dispersive spectroscopy and study of sinter bonding of the boron containing precursors (Mo-Cr-Fe-Ni-FeB-MoB) onto plain carbon steel. A microstructure containing Fe-based matrix dispersed with complex borides develops with temperature in the tape cast sheets. A fivefold increase in hardness between plain carbon steel in wrought condition and sinter bonded steel was observed. The multilayer consisted of a reaction zone adjacent to the interface and was investigated with the composition profile and hardness measurements. A model of sinter bonding between the cermet and the steel has also been proposed.

  16. Gas-Phase Photolysis of Pyruvic Acid: The Effect of Pressure on Reaction Rates and Products. (United States)

    Reed Harris, Allison E; Doussin, Jean-Francois; Carpenter, Barry K; Vaida, Veronica


    In this work, we investigate the impact of pressure and oxygen on the kinetics of and products from the gas-phase photolysis of pyruvic acid. The results reveal a decrease in the photolysis quantum yield as pressure of air or nitrogen is increased, a trend not yet documented in the literature. A Stern-Volmer analysis demonstrates this effect is due to deactivation of the singlet state of pyruvic acid when the photolysis is performed in nitrogen, and from quenching of both the singlet and triplet state in air. Consistent with previous studies, acetaldehyde and CO 2 are observed as the major products; however, other products, most notably acetic acid, are also identified in this work. The yield of acetic acid increases with increasing pressure of buffer gas, an effect that is amplified by the presence of oxygen. At least two mechanisms are necessary to explain the acetic acid, including one that requires reaction of photolysis intermediates with O 2 . These findings extend the fundamental understanding of the gas-phase photochemistry of pyruvic acid, highlighting the importance of pressure on the photolysis quantum yields and products.

  17. The coupling effect of gas-phase chemistry and surface reactions on oxygen permeation and fuel conversion in ITM reactors

    KAUST Repository

    Hong, Jongsup


    © 2015 Elsevier B.V. The effect of the coupling between heterogeneous catalytic reactions supported by an ion transport membrane (ITM) and gas-phase chemistry on fuel conversion and oxygen permeation in ITM reactors is examined. In ITM reactors, thermochemical reactions take place in the gas-phase and on the membrane surface, both of which interact with oxygen permeation. However, this coupling between gas-phase and surface chemistry has not been examined in detail. In this study, a parametric analysis using numerical simulations is conducted to investigate this coupling and its impact on fuel conversion and oxygen permeation rates. A thermochemical model that incorporates heterogeneous chemistry on the membrane surface and detailed chemical kinetics in the gas-phase is used. Results show that fuel conversion and oxygen permeation are strongly influenced by the simultaneous action of both chemistries. It is shown that the coupling somewhat suppresses the gas-phase kinetics and reduces fuel conversion, both attributed to extensive thermal energy transfer towards the membrane which conducts it to the air side and radiates to the reactor walls. The reaction pathway and products, in the form of syngas and C2 hydrocarbons, are also affected. In addition, the operating regimes of ITM reactors in which heterogeneous- or/and homogeneous-phase reactions predominantly contribute to fuel conversion and oxygen permeation are elucidated.

  18. The phase transport and reactions of γ-irradiated aqueous-ionic liquids

    Energy Technology Data Exchange (ETDEWEB)

    Howett, S.; Joseph, J.; Noel, J.J.; Wren, J.C., E-mail: [Univ. of Western Ontario, Dept. of Chemistry, London, Ontario (Canada)


    A novel technology based on the transfer of chemical species across water/ionic liquid interfaces via specific complexation reactions is currently being considered for the separation and sequestration of metal ion contaminants from radioactive waste effluents in the nuclear fuel cycle. An ideal solvent for these applications should have a high intrinsic selectivity for a targeted metal or group of metals (e.g., trans-Pu actinides, lanthanides, or other fission products), an efficient switching mechanism (between complexation and decomplexation), and a high immiscibility with aqueous solutions. These characteristics must be maintained in the chemical, radiation, and mass transport environments present during the separation process. Ionic liquids (ILs) have an almost negligible vapour pressure and high thermal stability. Their ability to dissolve a wide range of substrate molecules and potential to be highly resilient in radiation fields make ILs particularly promising media. The separation efficiency of the biphasic system will depend on many parameters, including the aqueous oxidation state of the targeted metal ion, and the thermodynamics and kinetics of interfacial transport and metal-ligand complex formation at the water/IL interface or in the IL phase. The most uncertain and unstudied area for these applications is the effect of ionizing radiation on the stability and separation efficiency of the biphasic system. The present study investigates the effect of γ-radiation on gas/IL and water/IL interfacial stability and mass transfer with trihexyltetradecylphosphonium bis(trifluoromethyl-sulfonyl)imide, a phosphonium-based IL. The IL, in contact with either gas or water, was irradiated at a dose rate of 6.4 kGy·h{sup -1}. Gas-phase samples were analyzed by gas chromatography-mass spectrometry (GC-MS) and the changes in the IL and aqueous phases were monitored by conductivity measurements and Raman spectroscopy. In this paper we discuss these observations and

  19. Ozonolysis of α/β-farnesene mixture: Analysis of gas-phase and particulate reaction products (United States)

    Jaoui, Mohammed; Lewandowski, Michael; Offenberg, John H.; Docherty, Kenneth S.; Kleindienst, Tadeusz E.


    Atmospheric oxidation of sesquiterpenes has been of considerable interest recently because of their likely contribution to ambient organic aerosol, but farnesene oxidation has been reported in only a few studies and with limited data. In the present study, a detailed chemical analysis of the organic fraction of gas and particle phases originating from the ozonolysis of a mixture of α-farnesene and β-farnesene was carried out in a 14.5 m3 smog chamber. More than 80 organic compounds bearing OH functionality were detected for the first time in this system in the gas and particle phases. The major secondary organic aerosol (SOA) components included conjugated α-farnesene trienols, hydroxyl carboxylic acid and its corresponding lactones, C3-C7 linear dicarboxylic acids, and hydroxy/carbonyl/carboxylic compounds. Of particular importance was 5,6-dihydroxy-6-methylheptan-2-one (DHMHO), which was detected at high concentration. In the gas phase, the main species identified were trienols and their corresponding epoxides and diepoxides. Proposed reaction schemes are provided for selected compounds. A similar analysis was performed for ambient PM2.5 samples collected during summer 2013 as part of the SOAS to determine farnesene contributions to PM2.5. Gas chromatography-mass spectrometry analysis were consistent with the occurrence of several farnesene SOA compounds, indicating the potential impact of farnesene on the regional aerosol burden. The high abundance of DHMHO in chamber SOA and its presence in ambient PM2.5 is particularly important because to our knowledge it is specific to farnesene and therefore could serve as an indicator for farnesene emitted into ambient aerosol. In the absence of authentic standards, however, it is difficult to accurately quantify the contribution of SOA originating from farnesene to ambient PM2.5.

  20. Organobase-catalyzed three-component reactions for the synthesis of 4H-2-aminopyrans, condensed pyrans and polysubstituted benzenes


    Moustafa Sherief Moustafa; Saleh Mohammed Al-Mousawi; Maghraby Ali Selim; Ahmed Mohamed Mosallam; Mohamed Hilmy Elnagdi


    Novel routes for the preparation of 2-amino-4H-pyran-3-carbonitrile 9, amino-arylbenzoic acid ester derivatives 13a,b, 2-aminotetrahydro-4H-chromene-3-carbonitrile 18, 3-amino-4-cyanotetrahydronaphthalene-2-carboxylic acid ester 26 and 4-amino-3,5-dicyanophthalic acid ester derivatives 37a–c were developed. The synthetic methods utilize one-pot reactions of acetylene carboxylic acid esters, α,β-unsaturated nitriles and/or active methylenenitriles in the presence of L-proline or DABCO. Plausib...

  1. Bimodal condensation silicone elastomers as dielectric elastomers

    DEFF Research Database (Denmark)

    Yu, Liyun; Madsen, Frederikke Bahrt; Skov, Anne Ladegaard

    unimodal refers to that there is one polymer only in the system. As an alternative to unimodal networks there are the bimodal networks where two polymers with significantly different molecular weights are mixed with one crosslinker. [2]Silicone rubber can be divided into condensation type and addition type...... according to the curing reaction. The advantages of condensation silicones compared to addition are the relatively low cost, the curing rate largely being independent of temperature, the excellent adhesion, and the catalyst being nontoxic. [3]In this work, a series of bimodal condensation silicone...

  2. Mast cell and eosinophil activation during early phase of grass pollen-induced ocular allergic reaction. (United States)

    Jedrzejczak-Czechowicz, Monika; Lewandowska-Polak, Anna; Jarzebska, Marzanna; Kowalski, Marek L


    Both mast cells and eosinophils were implicated in the pathophysiology of allergic conjunctivitis; however, the potential role of eosinophils in an early phase of allergic reaction has not been elucidated. The aim of this study was to assess the relation between clinical symptoms and sequence of mast cells and eosinophils specific mediators release into tear fluid during conjunctival allergen provocation. Patients with grass pollen rhinoconjunctivitis (n = 38) and healthy volunteers (n = 10) were challenged with increasing doses of allergen applied on the conjunctiva. The clinical symptoms were assessed by clinical score. Tear fluid was collected from 12 patients before provocation, at 20 and 40 minutes after positive response. Tryptase and eosinophil cationic protein (ECP) were measured using UniCap and 15-hydroxyeicosanoid acid (15-HETE) with a specific immunoassay. All allergic patients (but no control subjects) had a positive clinical response to the challenge. In 1 patient symptoms appeared after 50 BU/mL of grass allergen administration, in 3 patients symptoms appeared after 500 BU/mL (7.9% of patients), in 14 patients symptoms appeared after 1600 BU/mL (36.8%), and in 20 patients symptoms appeared after 5000 BU/mL (52.6%). The allergen dose was not correlated with the skin-prick test diameter. The mean tryptase concentration increased at 20 minutes from "nondetectable" to 5.89 ± 1.97 micrograms/L and then decreased to 1.77 ± 1.07 micrograms/L (n = 12; p allergic reaction in conjunctiva and activation of eosinophils is preceded by activation of mast cells.

  3. Condensation in insulated homes

    Energy Technology Data Exchange (ETDEWEB)

    Wiley, R A


    A research proposal on condensation in insulated homes is presented. Information is provided on: justification for condensation control; previous work and present outlook (good vapor barrier, condensation and retrofit insulation, vapor barrier decreases condensation, brick-veneer walls, condensation in stress-skin panels, air-conditioned buildings, retrofitting for conservation, study on mobile homes, high indoor relative humidity, report on various homes); and procedure (after funding has been secured). Measures are briefly described on opening walls, testing measures, and retrofitting procedures. An extensive bibliography and additional informative citations are included. (MCW)

  4. Analysis of the multistage phase separation reaction in Fe-25 at%Co-9 at%Mo

    Energy Technology Data Exchange (ETDEWEB)

    Eidenberger, Elisabeth; Schober, Michael; Schmoelzer, Thomas; Stergar, Erich; Clemens, Helmut [Department of Physical Metallurgy, Montanuniversitaet Leoben, Roseggerstrasse 12, 8700 Leoben (Austria); Staron, Peter [Institute of Materials Research, GKSS Research Centre Geesthacht, Max-Planck Strasse 1, 21502 Geesthacht (Germany); Leitner, Harald [Christian Doppler Laboratory for Early Stages of Precipitation, Montanuniversitaet Leoben, Roseggerstrasse 12, 8700 Leoben (Austria)


    Differential scanning calorimetry (DSC) has been used to characterize the phase reactions during age hardening of a Fe-25 at%Co-9 at%Mo alloy. The heat of reaction which can be accounted for the development of the hardening phase was further analyzed on the basis of the Kissinger method and a fit based on the JMA model. Additionally, the precipitation sequence was studied by in situ small-angle neutron scattering (SANS) as well as in situ X-ray diffraction (XRD) to gain knowledge on the chemistry and crystallography of the prevailing phases. As direct imaging techniques 3D atom probe (3DAP) and high-resolution transmission electron microscopy (HRTEM) were used. The combination of these methods revealed that hardening in the investigated alloy starts with spinodally formed Mo-rich clusters followed by precipitation of the intermetallic {mu}-phase (Fe,Co){sub 7}Mo{sub 6}. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

  5. Condensation phenomenon detection through surface plasmon resonance. (United States)

    Ibrahim, Joyce; Al Masri, Mostafa; Veillas, Colette; Celle, Frédéric; Cioulachtjian, Serge; Verrier, Isabelle; Lefèvre, Frédéric; Parriaux, Olivier; Jourlin, Yves


    The aim of this work is to optically detect the condensation of acetone vapor on an aluminum plate cooled down in a two-phase environment (liquid/vapor). Sub-micron period aluminum based diffraction gratings with appropriate properties, exhibiting a highly sensitive plasmonic response, were successfully used for condensation experiments. A shift in the plasmonic wavelength resonance has been measured when acetone condensation on the aluminum surface takes place due to a change of the surrounding medium close to the surface, demonstrating that the surface modification occurs at the very beginning of the condensation phenomenon. This paper presents important steps in comprehending the incipience of condensate droplet and frost nucleation (since both mechanisms are similar) and thus to control the phenomenon by using an optimized engineered surface.

  6. Polariton condensation in a disordered potential

    DEFF Research Database (Denmark)

    Antón, C.; Tosi, G.; Lingg, C. A.


    We study polariton condensation under OPO (Optical Parametric Oscillator) out-of-equilibrium conditions [1] in the presence of linear and point defects. Because of the simultaneous presence of pump, signal and idler emitting at different wave vectors, as well as of photonic disorder, the system....... Furthermore, a detailed study of the condensate phase demonstrates that the map of the supercurrents is unambiguously determined by the different defect geometries. We have studied two similar λ/2 GaAs-based microcavities, differing mainly by the thickness of the cavity and of the quantum well placed...... of a surrounding 2D OPO condensate. A spectral analysis of the real space emission (Fig. 1 (b)) resolves the 2D emission (1.5505 eV) and that of the 1D condensate (1.5500 eV). The linear defect separates the 2D condensate in two parts, each one of them having a different finite momentum pointing towards the low...

  7. Sulphide phases in Y zeolite for hydro-treatment reactions; Phase sulfures dans une zeolithe Y pour l'hydrotraitement

    Energy Technology Data Exchange (ETDEWEB)

    Leyrit, P.


    Several types of single (Mo, Co, Pd, Pt) or binary (MoCo, PdCo, PtCo) sulphides phases supported on a HY zeolite were studied. The catalysts were first prepared and characterised in the oxide form. Their reactivity was then evaluated in toluene hydrogenation and 4.6-dimethyl-dibenzo-thiophene hydro-desulfurization reactions. Characterisation of sulphide phases supported on HY zeolite was carried out by elemental analysis, X-Ray Diffraction (XRD), Transmission Electron Microscopy and Scanning Transmission Electron Microscopy (STEM), Extended X-Ray Absorption Fine Structure (EXAFS) and Temperature Programmed Reduction coupled with HS analysis. The results show that. compared with alumina supported catalysts, zeolite used as a support enables extremely active catalysts to be obtained. It appears in particular that molybdenum sulphide phases inside the zeolite have a very high intrinsic activity at low molybdenum content. This activity is attributed to highly dispersed molybdenum sulphide phases differing from MoS{sub 2} slabs and probably present as clusters. The influence of cobalt depends of its concentration. Thus at low loadings cobalt has a strong negative effect. It has been shown, in the molybdenum case, that cobalt interaction leads to an increase in the sulphur content of the molybdenum phases. At higher cobalt loading, the formation of a mixed phase is possible but the degree of promotion remains limited. This work emphasises the advantages of using zeolite supported sulphide phases, and especially Mo and Pd phases, in the hydro-treatment reactions. It seems however that single phases present a greater interest than binary phases. (author)

  8. (1)H NMR: A Novel Approach To Determining the Thermodynamic Properties of Acetaldehyde Condensation Reactions with Glycerol, (+)-Catechin, and Glutathione in Model Wine. (United States)

    Peterson, Ana L; Waterhouse, Andrew L


    As wine oxidizes, ethanol is converted to acetaldehyde, but its accumulation is not predictable, due to poorly characterized reactions with alcohols, SO2, thiols, flavanols, and others. Measurement of these components has been thwarted by equilibria into the other forms during sample preparation. NMR spectra can be taken on intact samples and is thus ideal for this situation. Equilibria of acetaldehyde with glycerol, (+)-catechin, and glutathione were studied separately in model wine solutions at pH 3-4 by (1)H NMR and 2D ((1)H-(1)H) COSY spectra. Glycerol acetals had equilibrium constants between 1.14 ± 0.056 and 2.53 ± 0.043 M(-1), whereas ethylidene-bridged (+)-catechin dimers and glutathione thiohemiacetals had more favorable equilibria: from (3.92 ± 0.13) × 10(3) to (6.13 ± 0.32) × 10(3) M(-2) and from 10.18 ± 0.22 to 11.17 ± 0.47 M(-1), respectively. These data can be used to create accurate measures of acetaldehyde in its various forms and, consequently, offer insight into wine oxidation.

  9. Advanced aqueous-phase phosphoramidation reactions for effectively synthesizing peptide-oligonucleotide conjugates trafficked into a human cell line. (United States)

    Wang, Tzu-Pin; Ko, Ni Chien; Su, Yu-Chih; Wang, Eng-Chi; Severance, Scott; Hwang, Chi-Ching; Shih, Ying Ting; Wu, Min Hui; Chen, Yen-Hsu


    Peptide-oligonucleotide conjugates (POCs) have held promise as effective therapeutic agents in treating microbial infections and human genetic diseases including cancers. In clinical applications, POCs are especially useful to circumvent cellular delivery and specificity problems of oligonucleotides. We previously reported that nucleic acid phosphoramidation reactions performed in aqueous solutions have the potential for facile POC synthesis. Here, we carried out further studies to significantly improve aqueous-phase two-step phosphoramidation reaction yield. Optimized reactions were employed to effectively synthesize POCs for delivery into human A549 cells. We achieved optimization of aqueous-phase two-step phosphoramidation reaction and improved reaction yield by (1) determining appropriate co-solutes and co-solute concentrations to acquire higher reaction yields, (2) exploring a different nucleophilicity of imidazole and its derivatives to stabilize essential nucleic acid phosphorimidazolide intermediates prior to POC formation, and (3) enhancing POC synthesis by increasing reactant nucleophilicity. The advanced two-step phosphoramidation reaction was exploited to effectively conjugate a well-studied cell penetrating peptide, the Tat(48-57) peptide, with oligonucleotides, bridged by either no linkers or a disulfide-containing linker, to have the corresponding POC yields of 47-75%. Phosphoramidation-synthesized POCs showed no cytotoxicity to human A549 cells at studied POC concentrations after 24 h inoculation and were successfully trafficked into the human A549 cell line as demonstrated by flow cytometry, fluorescent microscopy, and confocal laser scanning microscopy study. The current report provides insight into aqueous-phase phosphoramidation reactions, the knowledge of which was used to develop effective strategies for synthesizing POCs with crucial applications including therapeutic agents for medicine.

  10. Pure and stable metallic phase molybdenum disulfide nanosheets for hydrogen evolution reaction. (United States)

    Geng, Xiumei; Sun, Weiwei; Wu, Wei; Chen, Benjamin; Al-Hilo, Alaa; Benamara, Mourad; Zhu, Hongli; Watanabe, Fumiya; Cui, Jingbiao; Chen, Tar-Pin


    Metallic-phase MoS2 (M-MoS2) is metastable and does not exist in nature. Pure and stable M-MoS2 has not been previously prepared by chemical synthesis, to the best of our knowledge. Here we report a hydrothermal process for synthesizing stable two-dimensional M-MoS2 nanosheets in water. The metal-metal Raman stretching mode at 146 cm(-1) in the M-MoS2 structure, as predicted by theoretical calculations, is experimentally observed. The stability of the M-MoS2 is associated with the adsorption of a monolayer of water molecules on both sides of the nanosheets, which reduce restacking and prevent aggregation in water. The obtained M-MoS2 exhibits excellent stability in water and superior activity for the hydrogen evolution reaction, with a current density of 10 mA cm(-2) at a low potential of -175 mV and a Tafel slope of 41 mV per decade.

  11. Femtosecond phase of charge separation in reaction centers of Chloroflexus aurantiacus. (United States)

    Yakovlev, A G; Shkuropatova, T A; Vasilieva, L G; Shkuropatov, A Ya; Shuvalov, V A


    Difference absorption spectroscopy with temporal resolution of approximately 20 fsec was used to study the primary phase of charge separation in isolated reaction centers (RCs) of Chloroflexus aurantiacus at 90 K. An ensemble of difference (light-minus-dark) absorption spectra in the 730-795 nm region measured at -0.1 to 4 psec delays relative to the excitation pulse was analyzed. Comparison with analogous data for RCs of HM182L mutant of Rhodobacter sphaeroides having the same pigment composition identified the 785 nm absorption band as the band of bacteriopheophytin Phi(B) in the B-branch. By study the bleaching of this absorption band due to formation of Phi(B)(-), it was found that a coherent electron transfer from P* to the B-branch occurs with a very small delay of 10-20 fsec after excitation of dimer bacteriochlorophyll P. Only at 120 fsec delay electron transfer from P* to the A-branch occurs with the formation of bacteriochlorophyll anion B(A)(-) absorption band at 1028 nm and the appearance of P* stimulated emission at 940 nm, as also occurs in native RCs of Rb. sphaeroides. It is concluded that a nuclear wave packet motion on the potential energy surface of P* after a 20-fsec light pulse excitation leads to the coherent formation of the P(+)Phi(B)(-) and P(+)B(A)(-) states.

  12. Deep-release of Epon 828 epoxy from the shock-driven reaction product phase (United States)

    Lang, John; Fredenburg, Anthony; Coe, Joshua; Dattelbaum, Dana


    A challenge in improving equations-of-state (EOS) for polymers and their product phase is the lack of off-Hugoniot data. Here, we describe a novel experimental approach for obtaining release pathways along isentropes from the shocked products. A series of gas-gun experiments was conducted to obtain release isentropes of the products for 70/30 wt% Epon 828 epoxy resin/Jeffamine T-403 curing agent. Thin epoxy flyers backed by a low-density syntactic foam were impacted into LiF windows at up to 6.3 mm/ μs, creating stresses in excess of those required for reaction ( 25 GPa). Following a sustained shock input, a rarefaction fan from the back of the thin flyer reduced the pressure in the epoxy products along a release isentrope. Optical velocimetry (PDV) was used to measure the particle velocity at the epoxy/LiF interface. Numerical simulations using several different EOS describing the reactant-to-product transformation were conducted, and the results were compared with measured wave profiles. The best agreement with experiment was obtained using separate tabular EOS for the polymer ``reactant'' (e.g. epoxy) and product mixture, suggesting the transition to the products is irreversible.

  13. Bose-Einstein condensates form in heuristics learned by ciliates deciding to signal 'social' commitments. (United States)

    Clark, Kevin B


    Fringe quantum biology theories often adopt the concept of Bose-Einstein condensation when explaining how consciousness, emotion, perception, learning, and reasoning emerge from operations of intact animal nervous systems and other computational media. However, controversial empirical evidence and mathematical formalism concerning decoherence rates of bioprocesses keep these frameworks from satisfactorily accounting for the physical nature of cognitive-like events. This study, inspired by the discovery that preferential attachment rules computed by complex technological networks obey Bose-Einstein statistics, is the first rigorous attempt to examine whether analogues of Bose-Einstein condensation precipitate learned decision making in live biological systems as bioenergetics optimization predicts. By exploiting the ciliate Spirostomum ambiguum's capacity to learn and store behavioral strategies advertising mating availability into heuristics of topologically invariant computational networks, three distinct phases of strategy use were found to map onto statistical distributions described by Bose-Einstein, Fermi-Dirac, and classical Maxwell-Boltzmann behavior. Ciliates that sensitized or habituated signaling patterns to emit brief periods of either deceptive 'harder-to-get' or altruistic 'easier-to-get' serial escape reactions began testing condensed on initially perceived fittest 'courting' solutions. When these ciliates switched from their first strategy choices, Bose-Einstein condensation of strategy use abruptly dissipated into a Maxwell-Boltzmann computational phase no longer dominated by a single fittest strategy. Recursive trial-and-error strategy searches annealed strategy use back into a condensed phase consistent with performance optimization. 'Social' decisions performed by ciliates showing no nonassociative learning were largely governed by Fermi-Dirac statistics, resulting in degenerate distributions of strategy choices. These findings corroborate

  14. Photoinduced intramolecular charge-transfer reactions in 4-amino-3 ...

    Indian Academy of Sciences (India)

    Photoinduced intramolecular charge-transfer reactions in 4-amino-3-methyl benzoic acid methyl ester (AMBME) have been investigated spectroscopically. AMBME, with its weak charge donor primary amino group, shows dual emission in polar solvents. Absorption and emission measurements in the condensed phase ...

  15. Interleukin-6 release and the acute-phase reaction in patients with acute myocardial infarction: a pilot study

    NARCIS (Netherlands)

    Sturk, A.; Hack, C. E.; Aarden, L. A.; Brouwer, M.; Koster, R. R.; Sanders, G. T.


    We investigated the potential role of interleukin-6 as a mediator of the acute-phase reaction (APR) in patients with acute myocardial infarction. Of the six patients studied, five demonstrated increased plasma interleukin-6 levels. Interleukin-6 levels began to increase at 14 hours (mean; range = 8

  16. Structured catalysts and reactors for three phase catalytic reactions: manipulating activity and selectivity in nitrite hydrogenation

    NARCIS (Netherlands)

    Brunet Espinosa, Roger


    This work aimed at fabricating structured catalytic reactors for fast multiphase reactions, namely, nitrite hydrogenation and H2O2 decomposition. These reactors allowed a better understanding of these reactions and an improvement in terms of catalytic activity and selectivity.

  17. Solid-state reaction synthesis for mixed-phase Eu3+-doped bismuth molybdate and its luminescence properties (United States)

    Liang, Danyang; Ding, Yu; Wang, Nan; Cai, Xiaomeng; Li, Jia; Han, Linyu; Wang, Shiqi; Han, Yuanyuan; Jia, Guang; Wang, Liyong


    A method for mixed-phase bismuth molybdate doped with Eu3+ ions was developed by solid-state reaction assisting with polyvinyl alcohol (PVA). The results of powder X-ray diffraction showed a mixed-phase structure and the microscopical characterization technology revealed the formation process with the addition of PVA. As a structure inducer, the PVA molecules played a vital role in the formation of phase structure. The as-obtained Eu3+-doped bismuth molybdates were also characterized by using different spectroscopic techniques including FTIR and photoluminescence (PL). The results show that doping concentration, PVA addition and calcination temperature affect photoluminescence properties remarkably.

  18. Enhancing gas-phase reaction in a plasma using high intensity and high power ultrasonic acoustic waves

    DEFF Research Database (Denmark)


    substantially 100 W. In this way, a high sound intensity and power are obtained that efficiently enhances a gas-phase reaction in the plasma, which enhances the plasma process, e.g. enabling more efficient ozone or hydrogen generation using plasma in relation to reaction speed and/or obtained concentration......This invention relates to enhancing a gas-phase reaction in a plasma comprising: creating plasma (104) by at least one plasma source (106), and wherein that the method further comprises: generating ultrasonic high intensity and high power acoustic waves (102) having a predetermined amount...... of acoustic energy by at least one ultrasonic high intensity and high power gas-jet acoustic wave generator (101), where said ultrasonic high intensity and high power acoustic waves are directed to propagate towards said plasma (104) so that at least a part of said predetermined amount of acoustic energy...

  19. DFT study of the reactions of Mo and Mo with CO2 in gas phase

    Indian Academy of Sciences (India)

    row metal reacting with CO2. The minimum energy reaction path is found to involve the spin inversion in the different reaction steps. This potential energy curve-crossing dramati- cally affects reaction exothermic. The present results show that ...

  20. Modeling mass transfer and reaction of dilute solutes in a ternary phase system by the lattice Boltzmann method (United States)

    Fu, Yu-Hang; Bai, Lin; Luo, Kai-Hong; Jin, Yong; Cheng, Yi


    In this work, we propose a general approach for modeling mass transfer and reaction of dilute solute(s) in incompressible three-phase flows by introducing a collision operator in lattice Boltzmann (LB) method. An LB equation was used to simulate the solute dynamics among three different fluids, in which the newly expanded collision operator was used to depict the interface behavior of dilute solute(s). The multiscale analysis showed that the presented model can recover the macroscopic transport equations derived from the Maxwell-Stefan equation for dilute solutes in three-phase systems. Compared with the analytical equation of state of solute and dynamic behavior, these results are proven to constitute a generalized framework to simulate solute distributions in three-phase flows, including compound soluble in one phase, compound adsorbed on single-interface, compound in two phases, and solute soluble in three phases. Moreover, numerical simulations of benchmark cases, such as phase decomposition, multilayered planar interfaces, and liquid lens, were performed to test the stability and efficiency of the model. Finally, the multiphase mass transfer and reaction in Janus droplet transport in a straight microchannel were well reproduced.

  1. Capillary condensation between disks in two dimensions

    DEFF Research Database (Denmark)

    Gil, Tamir; Ipsen, John Hjorth


    Capillary condensation between two two-dimensional wetted circular substrates (disks) is studied by an effective free energy description of the wetting interface. The interfacial free-energy potential is developed on the basis of the theory for the wetting of a single disk, where interfacial...... capillary fluctuations play a dominant role. A simple approximative analytical expression of the interfacial free energy is developed and is validated numerically. The capillary condensation is characterized by the analysis of the coverage of the condensed phase, its stability, and asymptotic behaviors...

  2. Study of gas-phase reactions of NO2+ with aromatic compounds using proton transfer reaction time-of-flight mass spectrometry. (United States)

    Li, Jianquan; Du, Xubing; Guo, Teng; Peng, Zhen; Xu, Li; Dong, Junguo; Cheng, Ping; Zhou, Zhen


    The study of ion chemistry involving the NO2+ is currently the focus of considerable fundamental interest and is relevant in diverse fields ranging from mechanistic organic chemistry to atmospheric chemistry. A very intense source of NO2+ was generated by injecting the products from the dielectric barrier discharge of a nitrogen and oxygen mixture upstream into the drift tube of a proton transfer reaction time-of-flight mass spectrometry (PTR-TOF-MS) apparatus with H3 O+ as the reagent ion. The NO2+ intensity is controllable and related to the dielectric barrier discharge operation conditions and ratio of oxygen to nitrogen. The purity of NO2+ can reach more than 99% after optimization. Using NO2+ as the chemical reagent ion, the gas-phase reactions of NO2+ with 11 aromatic compounds were studied by PTR-TOF-MS. The reaction rate coefficients for these reactions were measured, and the product ions and their formation mechanisms were analyzed. All the samples reacted with NO2+ rapidly with reaction rate coefficients being close to the corresponding capture ones. In addition to electron transfer producing [M]+ , oxygen ion transfer forming [MO]+ , and 3-body association forming [M·NO2 ]+ , a new product ion [M-C]+ was also formed owing to the loss of C═O from [MO]+ .This work not only developed a new chemical reagent ion NO2+ based on PTR-MS but also provided significant interesting fundamental data on reactions involving aromatic compounds, which will probably broaden the applications of PTR-MS to measure these compounds in the atmosphere in real time. Copyright © 2017 John Wiley & Sons, Ltd.

  3. Turbulence and heat transfer in condensate in drying cylinders at high g-forces. Phase 2; Turbulens och vaermeoeverfoering i kondensat i torkcylindrar vid hoega g-krafter. Fas 2

    Energy Technology Data Exchange (ETDEWEB)

    Stenstroem, Stig; Ingvarsson, David [Lund Inst. of Tech. (Sweden). Dept. of Chemical Engineering


    During paper drying a condensate layer is formed on the inside surface of the rotating cylinder which acts as resistance for heat transfer through the cylinder. The heat transfer resistance in the condensate layer is mainly dependant on the layer thickness and the turbulence in the layer. Consequently the resistance increases with higher cylinder speeds due to increased centrifugal forces and thus reduced turbulence in the layer. In order to minimize the influence of condensate on the heat transfer process the cylinder used in Phase 1 has been equipped with axial grooves. The aim of the project has been to study the water movement in the cylinder and to investigate how the drying capacity is influenced by condensate accumulating in the grooves rather than moving along the smooth surface of a paper dryer cylinder. This knowledge should be considered preferably before construction of cylinders for new machines. For existing machines with smooth cylinders the importance of axial vertical flanges for improved heat transfer has been investigated. In addition the capacity of stationary siphons has been evaluated. The results are of importance for the manufacturers of paper machines as well as the producing newsprint and printing paper companies. According to the results from the experiments the water flows mainly in the grooves, assuming that the number of grooves and that the dimensions of the grooves are adjusted to the water load. Then the surfaces between the grooves can be considered as completely dry unlike in a smooth cylinder where the surfaces more or less are covered with a thin layer of condensate. Furthermore the centrifugal force helps the water to flow down into the grooves. Consequently a high water flow will rely on a high cylinder speed in order to keep the water flowing into the axial grooves. The computer simulations show that the drying capacity increases with up to 46 % in dryer cylinders provided with axial grooves compared to smooth cylinders

  4. Communication: Charge transfer dominates over proton transfer in the reaction of nitric acid with gas-phase hydrated electrons (United States)

    Lengyel, Jozef; Med, Jakub; Slavíček, Petr; Beyer, Martin K.


    The reaction of HNO3 with hydrated electrons (H2O)n- (n = 35-65) in the gas phase was studied using Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry and ab initio molecular dynamics simulations. Kinetic analysis of the experimental data shows that OH-(H2O)m is formed primarily via a reaction of the hydrated electron with HNO3 inside the cluster, while proton transfer is not observed and NO3-(H2O)m is just a secondary product. The reaction enthalpy was determined using nanocalorimetry, revealing a quite exothermic charge transfer with -241 ± 69 kJ mol-1. Ab initio molecular dynamics simulations indicate that proton transfer is an allowed reaction pathway, but the overall thermochemistry favors charge transfer.

  5. Single-molecule chemical reaction reveals molecular reaction kinetics and dynamics. (United States)

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


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

  6. Stress reduction in phase-separated, cross-linked networks: influence of phase structure and kinetics of reaction. (United States)

    Szczepanski, Caroline R; Stansbury, Jeffrey W


    A mechanism for polymerization shrinkage and stress reduction was developed for heterogeneous networks formed via ambient, photo-initiated polymerization-induced phase separation (PIPS). The material system used consists of a bulk homopolymer matrix of triethylene glycol dimethacrylate (TEGDMA) modified with one of three non-reactive, linear prepolymers (poly-methyl, ethyl and butyl methacrylate). At higher prepolymer loading levels (10-20 wt%) an enhanced reduction in both shrinkage and polymerization stress is observed. The onset of gelation in these materials is delayed to a higher degree of methacrylate conversion (~15-25%), providing more time for phase structure evolution by thermodynamically driven monomer diffusion between immiscible phases prior to network macro-gelation. The resulting phase structure was probed by introducing a fluorescently tagged prepolymer into the matrix. The phase structure evolves from a dispersion of prepolymer at low loading levels to a fully co-continuous heterogeneous network at higher loadings. The bulk modulus in phase separated networks is equivalent or greater than that of poly(TEGDMA), despite a reduced polymerization rate and cross-link density in the prepolymer-rich domains.

  7. Bose-Einstein condensation in quantum glasses. (United States)

    Carleo, Giuseppe; Tarzia, Marco; Zamponi, Francesco


    The role of geometrical frustration in strongly interacting bosonic systems is studied with a combined numerical and analytical approach. We demonstrate the existence of a novel quantum phase featuring both Bose-Einstein condensation and spin-glass behavior. The differences between such a phase and the otherwise insulating "Bose glasses" are elucidated.

  8. Evaluated kinetic and photochemical data for atmospheric chemistry: Volume IV – gas phase reactions of organic halogen species

    Directory of Open Access Journals (Sweden)

    R. Atkinson


    Full Text Available This article, the fourth in the series, presents kinetic and photochemical data sheets evaluated by the IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry. It covers the gas phase and photochemical reactions of organic halogen species, which were last published in 1997, and were updated on the IUPAC website in 2006/07. The article consists of a summary sheet, containing the recommended kinetic parameters for the evaluated reactions, and four appendices containing the data sheets, which provide information upon which the recommendations are made.

  9. Evaluated kinetic and photochemical data for atmospheric chemistry: Volume I - gas phase reactions of Ox, HOx, NOx and SOx species

    Directory of Open Access Journals (Sweden)

    R. Atkinson


    Full Text Available This article, the first in the series, presents kinetic and photochemical data evaluated by the IUPAC Subcommittee on GasKinetic Data Evaluation for Atmospheric Chemistry. It covers the gas phase and photochemical reactions of Ox, HOx, NOx and SOx species, which were last published in 1997, and were updated on the IUPAC website in late 2001. The article consists of a summary sheet, containing the recommended kinetic parameters for the evaluated reactions, and five appendices containing the data sheets, which provide information upon which the recommendations are made.

  10. Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II – gas phase reactions of organic species

    Directory of Open Access Journals (Sweden)

    R. Atkinson


    Full Text Available This article, the second in the series, presents kinetic and photochemical data evaluated by the IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry. It covers the gas phase and photochemical reactions of Organic species, which were last published in 1999, and were updated on the IUPAC website in late 2002, and subsequently during the preparation of this article. The article consists of a summary table of the recommended rate coefficients, containing the recommended kinetic parameters for the evaluated reactions, and eight appendices containing the data sheets, which provide information upon which the recommendations are made.

  11. Decomposition reaction rate of BCl3-C3H6(propene)-H2 in the gas phase. (United States)

    Xiao, Jun; Su, Kehe; Liu, Yan; Ren, Hongjiang; Zeng, Qingfeng; Cheng, Laifei; Zhang, Litong


    The decomposition reaction rate in the BCl(3)-C(3)H(6)-H(2) gas phase reaction system in preparing boron carbides was investigated based on the most favorable reaction pathways proposed by Jiang et al. [Theor. Chem. Accs. 2010, 127, 519] and Yang et al. [J. Theor. Comput. Chem. 2012, 11, 53]. The rate constants of all the elementary reactions were evaluated with the variational transition state theory. The vibrational frequencies for the stationary points as well as the selected points along the minimum energy paths (MEPs) were calculated with density functional theory at the B3PW91/6-311G(d,p) level and the energies were refined with the accurate model chemistry method G3(MP2). For the elementary reaction associated with a transition state, the MEP was obtained with the intrinsic reaction coordinates, while for the elementary reaction without transition state, the relaxed potential energy surface scan was employed to obtain the MEP. The rate constants were calculated for temperatures within 200-2000 K and fitted into three-parameter Arrhenius expressions. The reaction rates were investigated by using the COMSOL software to solve numerically the coupled differential rate equations. The results show that the reactions are, consistent with the experiments, appropriate at 1100-1500 K with the reaction time of 30 s for 1100 K, 1.5 s for 1200 K, 0.12 s for 1300 K, 0.011 s for 1400 K, or 0.001 s for 1500 K, for propene being almost completely consumed. The completely dissociated species, boron carbides C(3)B, C(2)B, and CB, have very low concentrations, and C(3)B is the main product at higher temperatures, while C(2)B is the main product at lower temperatures. For the reaction time 1 s, all these concentrations approach into a nearly constant. The maximum value (in mol/m(3)) is for the highest temperature 1500 K with the orders of -13, -17, and -23 for C(3)B, C(2)B, and CB, respectively. It was also found that the logarithm of the overall reaction rate and reciprocal

  12. Solid-phase Synthesis of Combinatorial 2,4-Disubstituted-1,3,5-Triazine via Amine Nucleophilic Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Moon, Sung Won [KIST Gangneung Institute, Gangneung (Korea, Republic of); Ham, Jungyeob [Gangneung-Wonju National University, Gangneung (Korea, Republic of); Chang, Young-Tae [National University of Singapore, Singapore (Singapore); Lee, Jae Wook [University of Science and Technology, Daejon (Korea, Republic of)


    In combinatorial chemistry, solid-phase synthesis is a popular approach formass production of small molecules. Compared to solution-phase synthesis, it is easy to prepare and purify a large number of heterocyclic small molecules via solid-phase chemistry; the overall reaction time is decreased as well. 1,3,5-Triazine is a nitrogen-containing heterocyclic aromatic scaffold that was shown to be a druggable scaffold in recent studies. These structures have been reported as anticancer, antimicrobial, and antiretroviral compounds, as CDKs and p38 MAP kinase inhibitors, as estrogen receptor modulators, and as inosine monophosphate dehydrogenase inhibitors. we designed and synthesized disubstituted triazine compounds as an analog of disubstituted pyrimidine compounds. These disubstituted triazine compounds possess a linear structure which may have biological activity similar to that of disubstituted pyrimidine. Here we report the solid-phase synthesis of disubstituted triazine compounds.

  13. Rate of reaction of dimethylmercury with oxygen atoms in the gas phase

    DEFF Research Database (Denmark)

    Egsgaard, Helge


    The rate constant for the reaction of atomic oxygen (O(3P)) with dimethylmercury has been measured at room temperature at a pressure of about 1 Torr using a fast flow system with electron paramagnetic resonance and mass spectrometric detection. Some reaction products were identified. The rate...

  14. Systematic text condensation

    DEFF Research Database (Denmark)

    Malterud, Kirsti


    To present background, principles, and procedures for a strategy for qualitative analysis called systematic text condensation and discuss this approach compared with related strategies.......To present background, principles, and procedures for a strategy for qualitative analysis called systematic text condensation and discuss this approach compared with related strategies....

  15. Measure Guideline: Evaporative Condensers

    Energy Technology Data Exchange (ETDEWEB)

    German, A [Alliance for Residential Building Innovation (ARBI), Davis, CA (United States); Dakin, B. [Alliance for Residential Building Innovation (ARBI), Davis, CA (United States); Hoeschele, M. [Alliance for Residential Building Innovation (ARBI), Davis, CA (United States)


    This measure guideline on evaporative condensers provides information on properly designing, installing, and maintaining evaporative condenser systems as well as understanding the benefits, costs, and tradeoffs. This is a prescriptive approach that outlines selection criteria, design and installation procedures, and operation and maintenance best practices.

  16. Condenser-free contrast methods for transmitted-light microscopy


    Webb, Kevin F.


    Phase contrast microscopy allows the study of highly transparent yet detail-rich specimens by producing intensity contrast from phase objects within the sample. Presented here is a generalized phase contrast illumination schema in which condenser optics are entirely abrogated, yielding a condenser- free yet highly effective method of obtaining phase contrast in transmitted-light microscopy. A ring of light emitting diodes (LEDs) is positioned within the light-path such that observation of the...

  17. Two-phase model of hydrogen transport to optimize nanoparticle catalyst loading for hydrogen evolution reaction

    DEFF Research Database (Denmark)

    Kemppainen, Erno; Halme, Janne; Hansen, Ole


    With electrocatalysts it is important to be able to distinguish between the effects of mass transport and reaction kinetics on the performance of the catalyst. When the hydrogen evolution reaction (HER) is considered, an additional and often neglected detail of mass transport in liquid is the evo......With electrocatalysts it is important to be able to distinguish between the effects of mass transport and reaction kinetics on the performance of the catalyst. When the hydrogen evolution reaction (HER) is considered, an additional and often neglected detail of mass transport in liquid...... current densities the increase in the gas volume fraction makes the H2 surface concentration nonlinear with respect to the current density. Compared to the typical diffusion layer model, our model is an extension that allows more detailed studies of reaction kinetics and mass transport in the electrolyte...

  18. Chocolate HILIC phases: development and characterization of novel saccharide-based stationary phases by applying non-enzymatic browning (Maillard reaction) on amino-modified silica surfaces. (United States)

    Schuster, Georg; Lindner, Wolfgang


    Novel saccharide-based stationary phases were developed by applying non-enzymatic browning (Maillard Reaction) on aminopropyl silica material. During this process, the reducing sugars glucose, lactose, maltose, and cellobiose served as "ligand primers". The reaction cascade using cellobiose resulted in an efficient chromatographic material which further served as our model Chocolate HILIC column. (Chocolate refers to the fact that these phases are brownish.) In this way, an amine backbone was introduced to facilitate convenient manipulation of selectivity by additional attractive or repulsive ionic solute-ligand interactions in addition to the typical HILIC retention mechanism. In total, six different test sets and five different mobile phase compositions were investigated, allowing a comprehensive evaluation of the new polar column. It became evident that, besides the so-called HILIC retention mechanism based on partition phenomena, additional adsorption mechanisms, including ionic interactions, take place. Thus, the new column is another example of a HILIC-type column characterized by mixed-modal retention increments. The glucose-modified materials exhibited the relative highest overall hydrophobicity of all grafted Chocolate HILIC columns which enabled retention of lipophilic analytes with high water content mobile phases.

  19. A New Method for Determining the Nanocrystallite Size Distribution in Systems Where Chemical Reaction between Solid and a Gas Phase Occurs

    Directory of Open Access Journals (Sweden)

    Rafał Pelka


    Full Text Available The proposed method, based on measuring the chemical reaction rate in solid phase, is, therefore, limited to such systems where reaction between nanocrystalline materials and a gas phase occurs. Additionally, assumptions of the model of reaction between nanocrystalline materials and a gas phase, where the surface chemical reaction rate is the rate limiting step, are used. As an example of such a reaction, nitriding (with ammonia of the prereduced industrial iron catalysts for ammonia synthesis of different average crystallite sizes was used. To measure the reaction rate, the differential reactor equipped with systems for thermogravimetric measurements and analysis of the chemical composition of the gas phase was used. The crystallites mass and size distributions for the analyzed samples of catalyst were determined.

  20. Significance of vapor phase chemical reactions on CVD rates predicted by chemically frozen and local thermochemical equilibrium boundary layer theories (United States)

    Gokoglu, Suleyman A.


    This paper investigates the role played by vapor-phase chemical reactions on CVD rates by comparing the results of two extreme theories developed to predict CVD mass transport rates in the absence of interfacial kinetic barrier: one based on chemically frozen boundary layer and the other based on local thermochemical equilibrium. Both theories consider laminar convective-diffusion boundary layers at high Reynolds numbers and include thermal (Soret) diffusion and variable property effects. As an example, Na2SO4 deposition was studied. It was found that gas phase reactions have no important role on Na2SO4 deposition rates and on the predictions of the theories. The implications of the predictions of the two theories to other CVD systems are discussed.

  1. Periodic reciprocating motion of a polymer gel on an aqueous phase synchronized with the Belousov-Zhabotinsky reaction. (United States)

    Nakata, Satoshi; Yoshii, Miyu; Suzuki, Seiichi; Yoshida, Ryo


    A self-oscillating gel induced by the Belousov-Zhabotinsky (BZ) reaction was investigated on an aqueous phase. When the Ru-catalyst in the gel was rapidly oxidized, the gel was accelerated in a direction opposite to the side of oxidation. The gel then returned to its original position while the Ru-catalyst in the gel was slowly reduced. To clarify the mechanism of this periodic reciprocation of the gel, the contact angle between a sessile bubble and the gel and the time-variation of the adhesive force of the gel on the aqueous phase were measured. The experimental results suggest that the periodic reciprocation of the gel is driven by the periodic change in the contact angle of the gel induced by the BZ reaction.

  2. Synthesis of Optically Active Poly(diphenylacetylenes Using Polymer Reactions and an Evaluation of Their Chiral Recognition Abilities as Chiral Stationary Phases for HPLC

    Directory of Open Access Journals (Sweden)

    Katsuhiro Maeda


    Full Text Available A series of optically active poly(diphenylacetylene derivatives bearing a chiral substituent (poly-2S or chiral and achiral substituents (poly-(2Sx-co-31−x on all of their pendant phenyl rings were synthesized by the reaction of poly(bis(4-carboxyphenylacetylene with (S-1-phenylethylamine ((S-2 or benzylamine (3 in the presence of a condensing reagent. Their chiroptical properties and chiral recognition abilities as chiral stationary phases (CSPs for high-performance liquid chromatography (HPLC were investigated. Poly-2S and poly-(2Sx-co-31−x (0.06 < x < 0.71 formed a preferred-handed helical conformation with opposite helical senses after thermal annealing despite possessing the same chiral pendant (h-poly-2S and h-poly-(2Sx-co-31−x. Furthermore, h-poly-2S and h-poly-(2S0.36-co-30.64 emitted circularly polarized luminescence with opposite signs. h-Poly-2S showed higher chiral recognition abilities toward a larger number of racemates than poly-2S without a preferred-handed helicity and the previously reported preferred-handed poly(diphenylacetylene derivative bearing the same chiral substituent on half of its pendant phenyl rings. h-Poly-(2S0.36-co-30.64 also exhibited good chiral recognition abilities toward several racemates, though the elution order of some enantiomers was reversed compared with h-poly-2S.

  3. Vulcanization reaction of squalene and S8 powder studied by Sulfur K-edge NEXAFS under liquid phase (United States)

    Yagi, S.; Menjo, Y.; Tsukada, C.; Ogawa, S.; Kutluk, G.; Namatame, H.; Taniguchi, M.


    Vulcanized rubber materials are useful in our surroundings. However, detail structure and reaction are not revealed even in present. Since squalene molecule possesses some same properties compared with natural rubber, we have prepared the samples of vulcanized squalene at 140 °C for several hours. To understand the vulcanization reaction,sulfur K-edge NEXAFS measurements have been carried out for the vulcanized squalene under liquid phase with He-path system and fluorescence detection mode. Moreover, we have tried curve fitting analysis of NEXAFS spectra. The results indicate that the squalene has been vulcanized by the S8 molecule at 140 °C and the S8 molecule length is shortened from 8 to 5-6 after the vulcanization reaction.

  4. Phosphoramidate-peptide synthesis by solution- and solid-phase Staudinger-phosphite reactions. (United States)

    Serwa, Remigiusz A; Swiecicki, Jean-Marie; Homann, Denise; Hackenberger, Christian P R


    The chemoselective incorporation of phosphoramidate moieties into peptides by a Staudinger-phosphite reaction of azides can be performed in many solvents, including water. In this report, we present two strategies for an efficient synthesis of phosphoramidate-containing peptides, in which the Staudinger-phosphite reaction is performed either on the solid support or in solution with aryl azido-containing peptides. The corresponding Staudinger reactions proceed in high conversion rates and deliver phosphoramidate peptides, in which the modification site is located in the middle of the peptide sequence. © 2010 European Peptide Society and John Wiley & Sons, Ltd.

  5. Aldimine Formation Reaction, the First Step of the Maillard Early-phase Reaction, Might be Enhanced in Variant Hemoglobin, Hb Himeji. (United States)

    Koga, Masafumi; Inada, Shinya; Shimizu, Sayoko; Hatazaki, Masahiro; Umayahara, Yutaka; Nishihara, Eijun


    Hb Himeji (β140Ala→Asp) is known as a variant hemoglobin in which glycation is enhanced and HbA1c measured by immunoassay shows a high value. The phenomenon of enhanced glycation in Hb Himeji is based on the fact that the glycation product of variant hemoglobin (HbX1c) shows a higher value than HbA1c. In this study, we investigated whether aldimine formation reaction, the first step of the Maillard early-phase reaction, is enhanced in Hb Himeji in vitro. Three non-diabetic subjects with Hb Himeji and four non-diabetic subjects without variant hemoglobin were enrolled. In order to examine aldimine formation reaction, whole blood cells were incubated with 500 mg/dl of glucose at 37°C for 1 hour and were analyzed by high-performance liquid chromatography. Both HbA1c and HbX1c were not increased in this condition. After incubation with glucose, labile HbA1c (LA1c) fraction increased in the controls (1.1±0.3%). In subjects with Hb Himeji increases in the labile HbX1c (LX1c) fraction as well as the LA1c fraction were observed, and the degree of increase in the LX1c fraction was significantly higher than that of the LA1c fraction (1.8±0.1% vs. 0.5±0.2%, PHb Himeji in vitro. The 140th amino acid in β chain of hemoglobin is suggested to be involved in aldimine formation reaction. © 2015 by the Association of Clinical Scientists, Inc.

  6. Phase formation sequence in the Ti/InP system during thin film solid-state reactions (United States)

    Ghegin, E.; Rodriguez, Ph.; Lábár, J. L.; Menyhárd, M.; Favier, S.; Sagnes, I.; Nemouchi, F.


    The metallurgical properties of the Ti/InP system meet a great interest for its use as a contact in the scope of various applications such as the Si Photonics. The investigations conducted on this system highlight the initiation of a reaction between the Ti and the InP substrate during the deposition process conducted at 100 °C. The simultaneous formation of two binary phases, namely, Ti2In5 and TiP, is attributed to the compositional gradient induced in the InP by the wet surface preparation and enhanced by the subsequent in situ Ar+ preclean. Once formed, the TiP layer acts as a diffusion barrier inhibiting further reaction up to 450 °C in spite of the presence of an important Ti reservoir. At higher temperature, however, i.e., from 550 °C, the reaction is enabled either by the enhancement of the species diffusion through the TiP layer or by its agglomeration. This reaction gives rise to the total consumption of the Ti2In5 and Ti while the TiP and In phases are promoted.

  7. The formation of urea in space. I. Ion-molecule, neutral-neutral, and radical gas-phase reactions (United States)

    Brigiano, Flavio Siro; Jeanvoine, Yannick; Largo, Antonio; Spezia, Riccardo


    Context. Many organic molecules have been observed in the interstellar medium thanks to advances in radioastronomy, and very recently the presence of urea was also suggested. While those molecules were observed, it is not clear what the mechanisms responsible to their formation are. In fact, if gas-phase reactions are responsible, they should occur through barrierless mechanisms (or with very low barriers). In the past, mechanisms for the formation of different organic molecules were studied, providing only in a few cases energetic conditions favorable to a synthesis at very low temperature. A particularly intriguing class of such molecules are those containing one N-C-O peptide bond, which could be a building block for the formation of biological molecules. Urea is a particular case because two nitrogen atoms are linked to the C-O moiety. Thus, motivated also by the recent tentative observation of urea, we have considered the synthetic pathways responsible to its formation. Aims: We have studied the possibility of forming urea in the gas phase via different kinds of bi-molecular reactions: ion-molecule, neutral, and radical. In particular we have focused on the activation energy of these reactions in order to find possible reactants that could be responsible for to barrierless (or very low energy) pathways. Methods: We have used very accurate, highly correlated quantum chemistry calculations to locate and characterize the reaction pathways in terms of minima and transition states connecting reactants to products. Results: Most of the reactions considered have an activation energy that is too high; but the ion-molecule reaction between NH2OHNH2OH2+ and formamide is not too high. These reactants could be responsible not only for the formation of urea but also of isocyanic acid, which is an organic molecule also observed in the interstellar medium.

  8. Acidic ionic liquids for n-alkane isomerization in a liquid-liquid or slurry-phase reaction mode

    Energy Technology Data Exchange (ETDEWEB)

    Meyer, C.; Hager, V.; Geburtig, D.; Kohr, C.; Wasserscheid, P. [Erlangen-Nuernberg Univ. (Germany). Lehrstuhl fuer Chemische Reaktionstechnik; Haumann, M. [Chemical Reaction Engineering, FAU Busan Campus, Korea (Korea, Republic of)


    Highly acidic ionic liquid (IL) catalysts offer the opportunity to convert n-alkanes at very low reaction temperatures. The results of IL catalyzed isomerization and cracking reactions of pure n-octane are presented. Influence of IL composition, [C{sub 4}C{sub 1}Im]Cl / AlCl{sub 3} / H{sub 2}SO{sub 4} and [C{sub 4}C{sub 1}Im]Cl / AlCl{sub 3} / 1-chlorooctane, on catalyst activity and selectivities to branched alkanes was investigated. Acidic chloroaluminate IL catalysts form liquid-liquid biphasic systems with unpolar organic product mixtures. Thus, recycling of the acidic IL is enabled by simple phase separation in the liquid-liquid biphasic reaction mode or the IL can be immobilized on an inorganic support with a large specific surface area. These supported ionic liquid phase (SILP) catalysts offer the advantage to get a macroscopically heterogeneous system while still preserving all benefits of the homogeneous catalyst which can be used for the slurry-phase n-alkane isomerization. The interaction of the solid support and acidic IL influences strongly the catalytic activity. (orig.)

  9. Reaction of chlorine radical with tetrahydrofuran: a theoretical investigation on mechanism and reactivity in gas phase. (United States)

    Begum, Samiyara; Subramanian, Ranga


    Reaction of chlorine (Cl) radical with heterocyclic saturated ether, tetrahydrofuran has been studied. The detailed reactivity and mechanism of this reaction is analyzed using hybrid density functional theory (DFT), B3LYP and BB1K methods, and aug-cc-pVTZ basis set. To explore the mechanism of the reaction of tetrahydrofuran with Cl radical, four possible sites of hydrogen atom (H) abstraction pathways in tetrahydrofuran were analyzed. The barrier height and rate constants are calculated for the four H-abstraction channels. The BB1K calculated rate constant for α-axial H-abstraction is comparable with the experimentally determined rate constant. It reflects that α-axial H-abstraction is the main degradation pathway of tetrahydrofuran with Cl radical. DFT-based reactivity descriptors are also calculated and these values describe α-axial H-abstraction as the main reaction channel.



    Kuruvilla, A.; Kuruvilla, K.


    Five hundred and ninety two patients attending a psychiatric department as outpatients or as inpatient were included in this study. Details regarding age, sex, diagnosis and drugs prescribed were entered in a proforma. The information regarding drugs prescribed, dosage and the types of reactions were noted. All patients were followed up for a period of 3 to 4 weeks. Incidence of adverse reactions was calculated as percentage of the total number of prescriptions of the same group of drugs. The...

  11. Kinetics and mechanism of the gas phase reaction of Cl atoms with iodobenzene

    DEFF Research Database (Denmark)

    Andersen, Mads Peter Sulbæk; Ponomarev, DA; Nielsen, OJ


    Smog chamber/FTIR techniques were used to study the kinetics and mechanism of the reaction of Cl atoms with iodobenzene (C6H5I) in 20-700 Torr of N-2, air, or O-2 diluent at 296 K. The reaction proceeds with a rate constant k(Cl + QH(5)I) = (3.3 +/- 0.7) x 10(-11) cm(3) molecule(-1) s(-1) to give...

  12. Theoretical Studies of Gas Phase Elementary and Carbon Nanostructure Growth Reactions (United States)


    photodissociation reactions of ketene, methylamine, formic acid , methyl ethyl ketone, acetone and NO3. For instance, for NO3, a totally photodissociation reactions of ketene, methylamine, formic acid , methyl ethyl ketone, acetone and NO3. For instance, for NO3, a totally unknown...K. R. S. Chandrakumar, A. J. Page, S. Irle and K. Morokuma, Carbon Coating Precedes SWCNT Nucleation on Silicon Nanoparticles : Insights from QM/MD


    Energy Technology Data Exchange (ETDEWEB)

    Clayton, Donald D., E-mail: [Department of Physics and Astronomy, Clemson University, Clemson, SC (United States)


    I present analytic approximations for some issues related to condensation of graphite, TiC, and silicon carbide in oxygen-rich cores of supernovae of Type II. Increased understanding, which mathematical analysis can support, renders researchers more receptive to condensation in O-rich supernova gases. Taking SN 1987A as typical, my first analysis shows why the abundance of CO molecules reaches an early maximum in which free carbon remains more abundant than CO. This analysis clarifies why O-rich gas cannot oxidize C if {sup 56}Co radioactivity is as strong as in SN 1987A. My next analysis shows that the CO abundance could be regarded as being in chemical equilibrium if the CO molecule is given an effective binding energy rather than its laboratory dissociation energy. The effective binding energy makes the thermal dissociation rate of CO equal to its radioactive dissociation rate. This preserves possible relevance for the concept of chemical equilibrium. My next analysis shows that the observed abundances of CO and SiO molecules in SN 1987A rule out frequent suggestions that equilibrium condensation of SUNOCONs has occurred following atomic mixing of the He-burning shell with more central zones in such a way as to reproduce roughly the observed spectrum of isotopes in SUNOCONs while preserving C/O > 1. He atoms admixed along with the excess carbon would destroy CO and SiO molecules, leaving their observed abundances unexplained. The final analysis argues that a chemical quasiequilibrium among grains (but not gas) may exist approximately during condensation, so that its computational use is partially justified as a guide to which mineral phases would be stable against reactions with gas. I illustrate this point with quasiequilibrium calculations by Ebel and Grossman that have shown that graphite is stable even when O/C >1 if prominent molecules are justifiably excluded from the calculation of chemical equilibrium.

  14. Prediction of the distribution of alkali and trace elements between the condensed and gaseous phases in a municipal solid waste incinerator

    Energy Technology Data Exchange (ETDEWEB)

    D. Poole; B.B. Argent; V.N. Sharifi; J. Swithenbank [University of Sheffield, Sheffield (United Kingdom). Department of Chemical and Process Engineering


    The FactSage thermodynamic calculation package and databases have been used to predict the equilibrium composition of the solid, liquid and gaseous products from municipal solid waste incineration. One series of calculations has considered the equilibrium for municipal waste combustion over a range of temperatures (850-1350{sup o}C) that includes the typical combustion temperature of 950{sup o}C and covers excursions to both lower and higher temperatures. A second set covers cooling of the combustion gas to 300{sup o}C and the formation of condensates. However, it is recognised that the lower the temperature the greater the importance of kinetics and no attempt is made to deal with such topics as nucleation by pre-existing airborne particulates. Consideration is given to the effect of oxygen potential together with alkali, chlorine, and water content on the equilibrium products. Further calculations conceptualising 'local equilibrium' around specific metal-containing items in the waste stream, for example a CRT tube, have illustrated how lack of global equilibrium, arising from non-uniformity in the burning bed could lead to atypical local metal distributions. Combined, these calculations provide a greater understanding of the behaviour of metals in municipal waste incineration than previous studies, accounting to some extent for the great variation in waste composition and local combustion conditions in a complex and variable industrial system. 19 refs., 13 figs., 10 tabs.

  15. Gas-Phase Reaction Pathways and Rate Coefficients for the Dichlorosilane-Hydrogen and Trichlorosilane-Hydrogen Systems (United States)

    Dateo, Christopher E.; Walch, Stephen P.


    As part of NASA Ames Research Center's Integrated Process Team on Device/Process Modeling and Nanotechnology our goal is to create/contribute to a gas-phase chemical database for use in modeling microelectronics devices. In particular, we use ab initio methods to determine chemical reaction pathways and to evaluate reaction rate coefficients. Our initial studies concern reactions involved in the dichlorosilane-hydrogen (SiCl2H2--H2) and trichlorosilane-hydrogen (SiCl2H-H2) systems. Reactant, saddle point (transition state), and product geometries and their vibrational harmonic frequencies are determined using the complete-active-space self-consistent-field (CASSCF) electronic structure method with the correlation consistent polarized valence double-zeta basis set (cc-pVDZ). Reaction pathways are constructed by following the imaginary frequency mode of the saddle point to both the reactant and product. Accurate energetics are determined using the singles and doubles coupled-cluster method that includes a perturbational estimate of the effects of connected triple excitations (CCSD(T)) extrapolated to the complete basis set limit. Using the data from the electronic structure calculations, reaction rate coefficients are obtained using conventional and variational transition state and RRKM theories.

  16. Sensitivity analysis and economic optimization studies of inverted five-spot gas cycling in gas condensate reservoir

    Directory of Open Access Journals (Sweden)

    Shams Bilal


    Full Text Available Gas condensate reservoirs usually exhibit complex flow behaviors because of propagation response of pressure drop from the wellbore into the reservoir. When reservoir pressure drops below the dew point in two phase flow of gas and condensate, the accumulation of large condensate amount occurs in the gas condensate reservoirs. Usually, the saturation of condensate accumulation in volumetric gas condensate reservoirs is lower than the critical condensate saturation that causes trapping of large amount of condensate in reservoir pores. Trapped condensate often is lost due to condensate accumulation-condensate blockage courtesy of high molecular weight, heavy condensate residue. Recovering lost condensate most economically and optimally has always been a challenging goal. Thus, gas cycling is applied to alleviate such a drastic loss in resources.

  17. Physics of condensed matter

    CERN Document Server

    Misra, Prasanta K


    Physics of Condensed Matter is designed for a two-semester graduate course on condensed matter physics for students in physics and materials science. While the book offers fundamental ideas and topic areas of condensed matter physics, it also includes many recent topics of interest on which graduate students may choose to do further research. The text can also be used as a one-semester course for advanced undergraduate majors in physics, materials science, solid state chemistry, and electrical engineering, because it offers a breadth of topics applicable to these majors. The book be

  18. The premenstrual phase and reactions to aversive events: a study of hormonal influences on emotionality.

    NARCIS (Netherlands)

    Goozen, van St.H.M.; Frijda, N.H.; Wiegant, V.M.; Endert, E.; Poll, van de N.E.


    Fifty-eight normal cycle, healthy women were confronted with an aversive, anger-provoking situation in the laboratory. Eighteen women were tested in their follicular phase. A further 40 women were tested in the premenstrual phase, half of whom reported suffering from complaints of premenstrual

  19. Effect of an organoclay on the reaction-induced phase-separation in a dynamically asymmetric epoxy/PCL system

    Directory of Open Access Journals (Sweden)

    J. Rotrekl


    Full Text Available The addition of layered silicates can significantly affect the phase behaviour of both immiscible thermoplastic blends and partially miscible thermoset systems that undergo reaction-induced phase separation (RIPS during curing. This study focuses on the phase behaviour of polycaprolactone (PCL/epoxy in the presence of organically modified montmorillonite (oMMT. Due to the high dynamic asymmetry caused by the differences in the molecular weights and viscosities of the PCL and the uncured epoxy, the critical point is localised at low PCL concentrations, as indicated by the pseudophase diagram. The addition of oMMT to the system led to the marked shift of the critical point towards higher concentrations of PCL, with an increase in the oMMT content occurring as a consequence of the preferential localisation of the clay in the epoxy phase, making this phase more dynamically slow. Significant changes in morphology, including phase inversion of the PCL/epoxy systems caused by the presence of oMMT, were recorded for PCL concentrations ranging from 10 to 30%.

  20. Reaction paths and host phases of uranium isotopes (235U; 238U), Saanich Inlet (United States)

    Amini, M.; Holmden, C. E.; Francois, R. H.


    In recent times, Uranium has become increasingly the focus of stable isotope fractionation studies. Variations in 238U/235U have been reported as a result of redox reactions [1,2] from the nuclear field shift effect [3], and a mass-dependent, microbially-mediated, kinetic isotope effect [4]. The 238U/235U variability caused by changes in environmental redox conditions leads to an increase in the 238U/235U ratios of the reduced U species sequestered into marine sediments. This points to U isotope variability as a new tool to study ancient ocean redox changes. However, the process by which reduced sediments become enriched in the heavy isotopes of U is not yet known, and hence the utility of 238U/235U as a redox tracer remains to be demonstrated. In order to further constrain sedimentary U enrichment and related isotope effect, we are investigating U isotopic compositions of water samples and fresh surface sediment grab samples over a range of redox conditions in the seasonally anoxic Saanich Inlet, on the east coast of Vancouver Island. U was sequentially extracted from sediments in order to characterize specific fractions for their isotopic composition. The measurements were carried out by MC-ICPMS using 233U/236U-double spike technique. The data are reported as δ238U relative to NBL 112a with a 238U/235U ratio of 137.88 (2sd). External precision is better than 0.10‰ (2sd). Fifteeen analyses of seawater yielded δ238U of -0.42±0.08‰ (2sd). The results for the water samples indicate a homogenous δ238U value throughout the Saanich Inlet water column that matches the global seawater signature. All of the water samples from above and below average -0.42±0.05‰ (2sd). In contrast, a plankton net sample yielded a distinctly different, (about 0.5‰ lighter) isotope value. Bacterial reduction experiments [4] have also shown isotope enrichment factors of about -0.3‰. In addition, metal isotope fractionation occurs during adsorption with the light isotope being

  1. Chelate-Modified Fenton Reaction for the Degradation of Trichloroethylene in Aqueous and Two-Phase Systems

    Energy Technology Data Exchange (ETDEWEB)

    Lewis, Scott [Univ of KY, dept of chemical and materials engineering; lynch, Andrew [Univ of KY, dept of chemical and materials engineering; Bachas, Leonidas [Univ of KY, Dept of Chemistry; hampson, Steve [Univ of KY Center for Applied Energy Research - KY Research Consortium of Energy and Environment; Ormsbee, Lindelle [Univ of KY Center for Applied Energy Research - KY Research Consortium of Energy and Environment; Bhattacharyya, Dibakar [Univ of KY, dept of chemical and materials engineering


    The Standard Fenton reaction has been used for In-Situ Chemical Oxidation (ISCO) of toxic organics in groundwater. However, it requires low pH operating conditions, and thus has limitations for in situ applications. In addition, hydroxyl radicals are rapidly consumed by hydroxyl scavengers found in the subsurface. These problems are alleviated through the chelate-modified Fenton (hydroxyl radical) reaction, which includes the addition of nontoxic chelate (L) such as citrate or gluconic acid. This chelate allows the reaction to take place at bear neutral pH and control hydrogen peroxide consumption by binding to Fe(II), forming an FeL complex. The chelate also binds to Fe(III), preventing its precipitation as ferric hydroxide and thus prevents problems associated with injection well plugging. The rate of TCE dechlorination in chelate-modified Fenton systems is a function of pH, H2O2 concentration, and FE:L ratio. The primary objective of this research is to model and apply this process to the destruction of trichloroethylene (TCE) present in both the aqueous and organic (in the form of droplets) phases. Experimentation proved the chelate-modified Fenton reaction effectively dechlorinates TCE in both the aqueous and organic phases at near-neutral pH. Other focuses of this work include determining the effect of [L]:[Fe] ratios on H2O2 and TCE degradation as well as reusability of the FE citrate solution under repeated H2O2 injections. Generalized models were developed to predict the concentration of TCE in the aqueous phase and TCE droplet radius as a function of time using established hydroxyl radial kinetics and mass transfer relationships.

  2. The late phase of the immediate wheal and flare skin reaction. Its dependence upon IgE antibodies. (United States)

    Solley, G O; Gleich, G J; Jordon, R E; Schroeter, A L


    IgE antibodies are usually thought to induce only immediate skin reactions. We have shown that the intradermal injection of a number of different allergens can produce a prolonged inflammatory reaction after the immediate wheal and flare in most sensitive subjects. This late inflammatory response occurs 6-12 h after challenge and is characterized by diffuse edema, erythema, pruritus, and heat. Both immediate and late responses can also be seen after passive sensitization of skin sites in nonatopic subjects. That IgE is involved in inducing the reaction was shown by the abolition of both immediate and late responses by passive transfer tests in the following experiments: (a) heating atopic serum at 56degreesC for 4 h, (b) removing IgE from the atopic serum by a solid phase anti-IgE immunoabsorbent, and (c) competitively inhibiting the binding of IgE antibodies to cells by an IgE myeloma protein. In addition, both responses were induced by affinity chromatography-purified IgE antibody, followed by antigenic challenge. Very similar lesions could also be induced by intradermal injection of Compound 48/80, thus suggesting a central role in the reaction for the mast cell or basophil. Histologically, the late phase is characterized by edema and a mixed cellular infiltration, predominantly lymphocytic but also containing eosinophils, neutrophils and basophils. Direct immunofluorescent staining did not show deposition of immunoglobulins or complement components, except IgM in 2 of 15 and C3 in 1 of 15 patients. This finding indicates that the late phase does not depend on the deposition of immune complexes. The results of the study suggest that IgE-allergen interaction on the surfaces of mast cells or on infiltrating basophils causes both immediate and late cutaneous responses. Images PMID:783199

  3. Synthesis of lipidated eNOS peptides by combining enzymatic, noble metal- and acid-mediated protecting group techniques with solid phase peptide synthesis and fragment condensation in solution. (United States)

    Machauer, R; Waldmann, H


    Lipid-modified proteins play decisive roles in important biological processes such as signal transduction, organization of the cytoskeleton, and vesicular transport. Lipidated peptides embodying the characteristic partial structures of their parent lipidated proteins and semisynthetic proteins synthesized from such peptides are valuable tools for the study of these biological phenomena. We have developed an efficient synthesis strategy that allows for the synthesis of long multiply lipidated peptides embodying various side chain functional groups. The strategy was successfully applied in the synthesis of the N-terminal undetrigintapeptide of endothelial NO-synthase and related lipopeptides. Key elements of the synthesis strategy are the combined use of the enzyme-labile para-phenylacetoxybenzyloxycarbonyl (PhAcOZ) urethane as N-terminal blocking group, the Pd0-sensitive allyl ester as C-terminal protecting function and acid-labile side chain protecting groups for solution-phase synthesis of labile S-palmitoylated building blocks under the mildest conditions with solid-phase techniques and solution-phase fragment condensations. The successful synthesis of the triply lipidated 29-mer eNOS peptide convincingly demonstrates the full capacity of the protecting group methods.


    The use of solid-liquid phase transfer catalysis has an advantage of carrying out reaction between two immiscible substrates, one in solid phase and the other in liquid phase, with high selectivity and at relatively low temperatures. In this study we investigated the synthesis ci...

  5. Isomeric Differentiation of Green Tea Catechins using Gas-Phase Hydrogen/Deuterium Exchange Reactions (United States)

    Niemeyer, Emily D.; Brodbelt, Jennifer S.


    Hydrogen/deuterium exchange reactions in a quadrupole ion trap mass spectrometer are used to differentiate galloylated catechin stereoisomers (catechin gallate and epicatechin gallate; gallocatechin gallate and epigallocatechin gallate) and the non-galloylated analogs (catechin and epicatechin, gallocatechin and epigallocatechin). Significant differences in the hydrogen/deuterium exchange behavior of the four pairs of deprotonated catechin stereoisomers are observed upon reaction with D2O. Interestingly, the non-galloylated catechins undergo H/D exchange to a much greater extent than the galloylated species, incorporating deuterium at both aromatic/allylic and active phenolic sites. Non-galloylated catechin isomers are virtually indistinguishable by their H/D exchange kinetics over a wide range of reaction times (0.05 to 10 s). Our experimental results are explained using high-level ab initio calculations to elucidate the subtle structural variations in the catechin stereoisomers that lead to their differing H/D exchange kinetics. PMID:17702600

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  7. Two-phase model of hydrogen transport to optimize nanoparticle catalyst loading for hydrogen evolution reaction

    DEFF Research Database (Denmark)

    Kemppainen, Erno; Halme, Janne; Hansen, Ole


    With electrocatalysts it is important to be able to distinguish between the effects of mass transport and reaction kinetics on the performance of the catalyst. When the hydrogen evolution reaction (HER) is considered, an additional and often neglected detail of mass transport in liquid...... the gas volume fraction is sufficiently high to facilitate H2 transfer to bubbles within a distance shorter than the diffusion layer thickness. At current densities below about 40 mA/cm2 the model reduces to an analytical approximation that has characteristics similar to the diffusion of H2. At higher...... current densities the increase in the gas volume fraction makes the H2 surface concentration nonlinear with respect to the current density. Compared to the typical diffusion layer model, our model is an extension that allows more detailed studies of reaction kinetics and mass transport in the electrolyte...

  8. Measure Guideline: Evaporative Condensers

    Energy Technology Data Exchange (ETDEWEB)

    German, A.; Dakin, B.; Hoeschele, M.


    The purpose of this measure guideline on evaporative condensers is to provide information on a cost-effective solution for energy and demand savings in homes with cooling loads. This is a prescriptive approach that outlines selection criteria, design and installation procedures, and operation and maintenance best practices. This document has been prepared to provide a process for properly designing, installing, and maintaining evaporative condenser systems as well as understanding the benefits, costs, and tradeoffs.

  9. Influence of Solvent on Liquid Phase Hydrodeoxygenation of Furfural-Acetone Condensation Adduct using Ni/Al2O3-ZrO2 Catalysts (United States)

    Ulfa, S. M.; Mahfud, A.; Nabilah, S.; Rahman, M. F.


    Influence of water and acidic protic solvent on hydrodeoxygenation (HDO) of the furfural-acetone adduct (FAA) over Ni/Al2O3-ZrO2 (NiAZ) catalysts were investigated. The HDO of FAA was carried out in a batch reactor at 150°C for 8 hours. The NiAZ catalysts were home-made catalysts which were prepared by wet impregnation method with 10 and 20% nickel loading. The HDO reaction of FAA using 10NiAZ in water at 150°C gave alkane and oxygenated hydrocarbons at 31.41% with selectivity over tridecane (C13) in 6.67%. On the other hand, a reaction using acetic acid:water (1:19 v/v) in similar reaction condition gave only oxygenated compounds and hydrocracking product (C8-C10). The formation of tridecane (C13) was proposed by hydrogenation of C=O and C=C followed by decarboxylation without hydrocracking process. The presence of water facilitated decarboxylation mechanism by stabilized dehydrogenated derivatives of FAA.

  10. PdCu Nanoalloy Electrocatalysts in Oxygen Reduction Reaction: Role of Composition and Phase State in Catalytic Synergy. (United States)

    Wu, Jinfang; Shan, Shiyao; Luo, Jin; Joseph, Pharrah; Petkov, Valeri; Zhong, Chuan-Jian


    The catalytic synergy of nanoalloy catalysts depends on the nanoscale size, composition, phase state, and surface properties. This report describes findings of an investigation of their roles in the enhancement of electrocatalytic activity of PdCu alloy nanoparticle catalysts for oxygen reduction reaction (ORR). Pd(n)Cu(100-n) nanoalloys with controlled composition and subtle differences in size and phase state were synthesized by two different wet chemical methods. Detailed electrochemical characterization was performed to determine the surface properties and the catalytic activities. The atomic-scale structures of these catalysts were also characterized by high-energy synchrotron X-ray diffraction coupled with atomic pair distribution function analysis. The electrocatalytic activity and stability were shown to depend on the size, composition, and phase structure. With Pd(n)Cu(100-n) catalysts from both methods, a maximum ORR activity was revealed at Pd/Cu ratio close to 50:50. Structurally, Pd50Cu50 nanoalloys feature a mixed phase consisting of chemically ordered (body-centered cubic type) and disordered (face-centered cubic type) domains. The phase-segregated structure is shown to change to a single phase upon electrochemical potential cycling in ORR condition. While the surface Cu dissolution occurred in PdCu catalysts from the two different synthesis methods, the PdCu with a single-phase character is found to exhibit a tendency of a much greater dissolution than that with the phase segregation. Analysis of the results, along theoretical modeling based on density functional theory calculation, has provided new insights for the correlation between the electrocatalytic activity and the catalyst structures.

  11. Field theories of condensed matter physics

    CERN Document Server

    Fradkin, Eduardo


    Presenting the physics of the most challenging problems in condensed matter using the conceptual framework of quantum field theory, this book is of great interest to physicists in condensed matter and high energy and string theorists, as well as mathematicians. Revised and updated, this second edition features new chapters on the renormalization group, the Luttinger liquid, gauge theory, topological fluids, topological insulators and quantum entanglement. The book begins with the basic concepts and tools, developing them gradually to bring readers to the issues currently faced at the frontiers of research, such as topological phases of matter, quantum and classical critical phenomena, quantum Hall effects and superconductors. Other topics covered include one-dimensional strongly correlated systems, quantum ordered and disordered phases, topological structures in condensed matter and in field theory and fractional statistics.

  12. The synthesis and properties of the phases obtained by solid-solid reactions


    Blonska-Tabero A.; Bosacka M.; Dabrowska G.; Filipek E.; Piz M.; Rychlowska-Himmel I.; Tabero P.; Tomaszewicz E.


    The presented work encompasses the subject of the studies and the results obtained over the last years by the research workers of the Department of Inorganic Chemistry. They include mainly the studies on the reactivity of metal oxides, searching for new phases in binary and ternary systems of metal oxides as well as describing phase relations establishing in such systems. They also encompass works on the extensive characteristics of physico-chemical properties of the newly obtained compounds.

  13. The synthesis and properties of the phases obtained by solid-solid reactions

    Directory of Open Access Journals (Sweden)

    Blonska-Tabero A.


    Full Text Available The presented work encompasses the subject of the studies and the results obtained over the last years by the research workers of the Department of Inorganic Chemistry. They include mainly the studies on the reactivity of metal oxides, searching for new phases in binary and ternary systems of metal oxides as well as describing phase relations establishing in such systems. They also encompass works on the extensive characteristics of physico-chemical properties of the newly obtained compounds.

  14. Pronounced Size Dependence in Structure and Morphology of Gas-Phase Produced, Partially Oxidized Cobalt Nanoparticles under Catalytic Reaction Conditions

    Energy Technology Data Exchange (ETDEWEB)

    Bartling, Stephan; Yin, Chunrong; Barke, Ingo; Oldenburg, Kevin; Hartmann, Hannes; von Oeynhausen, Viola; Pohl, Marga-Martina; Houben, Kelly; Tyo, Eric C.; Seifert, Sönke; Lievens, Peter; Meiwes-Broer, Karl-Heinz; Vajda, Stefan


    It is generally accepted that optimal particle sizes are key for efficient nanocatalysis. Much less attention is paid to the role of morphology and atomic arrangement during catalytic reactions. Here we unravel the structural, stoichiometric, and morphological evolution of gas-phase produced cobalt nanoparticles in a broad size range. Particles with diameters between 1.4 nm and 22nm generated in cluster sources are size selected and deposited on amorphous alumina (Al2O3) and ultrananocrystalline diamond (UNCD) films. A combination of different techniques is employed to monitor particle properties at the stages of production, exposure to ambient conditions, and catalytic reaction, in this case the oxidative dehydrogenation of cyclohexane at elevated temperatures. A pronounced size dependence is found, naturally classifying the particles into three size regimes. While small and intermediate clusters essentially retain their compact morphology, large particles transform into hollow spheres due to the nanoscale Kirkendall effect. Depending on the substrate an isotropic (Al2O3) or anisotropic (UNCD) Kirkendall effect is observed. The latter results in dramatic lateral size changes. Our results shed light on the interplay between chemical reactions and the catalyst's structure and provide an approach to tailor the cobalt oxide phase composition required for specific catalytic schemes.

  15. Geometric Phase Effects in the Ultracold D + HD $\\to$ D + HD and D + HD $\\leftrightarrow$ H + D$_2$ Reactions

    CERN Document Server

    Kendrick, Brian K; Balakrishnan, N


    The results of accurate quantum reactive scattering calculations for the D + HD($v=4$, $j=0$) $\\to$ D + HD($v'$, $j'$), D + HD($v=4$, $j=0$) $\\to$ H + D$_2$($v'$, $j'$) and H + D$_2$($v=4$, $j=0$) $\\to$ D + HD($v'$,$j'$) reactions are presented for collision energies between $1\\,\\mu{\\rm K}$ and $100\\,{\\rm K}$. The ${\\it ab\\ initio}$ BKMP2 PES for the ground electronic state of H$_3$ is used and all values of total angular momentum between $J=0-4$ are included. The general vector potential approach is used to include the geometric phase. The rotationally resolved, vibrationally resolved, and total reaction rate coefficients are reported as a function of collision energy. Rotationally resolved differential cross sections are also reported as a function of collision energy and scattering angle. Large geometric phase effects appear in the ultracold reaction rate coefficients which result in a significant enhancement or suppression of the rate coefficient (up to $3$ orders of magnitude) relative to calculations wh...

  16. Aqueous-phase Suzuki-Miyaura cross-coupling reactions of free halopurine bases

    Czech Academy of Sciences Publication Activity Database

    Čapek, Petr; Vrábel, Milan; Hasník, Zbyněk; Pohl, Radek; Hocek, Michal

    -, č. 20 (2006), s. 3515-3526 ISSN 0039-7881 R&D Projects: GA ČR(CZ) GA203/05/0043 Institutional research plan: CEZ:AV0Z40550506 Keywords : purines * cross-coupling * reactions Subject RIV: CC - Organic Chemistry Impact factor: 2.333, year: 2006

  17. Phosphopeptidomimetic substance libraries from multicomponent reaction: Enantioseparation on quinidine carbamate stationary phase

    NARCIS (Netherlands)

    Gargano, Andrea F.G.; Lindner, Wolfgang; Lämmerhofer, Michael


    In the present contribution we report a HPLC enantioseparation method for a library of amido-aminophosphonate structures generated by a novel Ugi-multicomponent reaction. The enantioseparation of these novel potentially bioactive molecules was achieved by means of HPLC on cinchona-carbamate based

  18. The reaction of nitromethane with hydrogen and deuterium atoms in the gas phase. A mechanistic study

    DEFF Research Database (Denmark)

    Lund Thomsen, E.; Nielsen, O.J.; Egsgaard, H.


    The mechanism of the reaction between H and CH3NO2, has been studied in a discharge flow system using electron paramagnetic resonance and modulated molecular beam mass spectrometry for the detection of reactants and products. Deuterium atoms have, in addition to CD3NO2, been used to support...

  19. Gas-Phase Reactions of Bare and Ligated Uranium Ions with Sulfer Hexafluoride

    Energy Technology Data Exchange (ETDEWEB)

    Jackson, Glen P. [Ohio University, Athens; Gibson, John K [ORNL; Duckworth, Douglas {Doug} C [ORNL


    Reactions of bare and ligated uranium ions with sulfur hexafluoride were studied in a quadrupole ion trap mass spectrometer. Bare U{sup +} was found to react rather efficiently with SF{sub 6} (k/k{sub ADO} {approx} 0.4) to produce both UF{sub n}{sup +} (n = 1, 2, 3, 4) and SF{sub n}{sup +} (n = 1, 2, 3). Whereas the UF{sup +}/SF{sub 6} reaction rate was essentially the same as that for U{sup +}/SF{sub 6}, both UF{sub 2}{sup +} and UF{sub 3}{sup +} were inert; this is attributed to a repulsive interaction between UF{sub n}{sup +} and SF{sub 6} when n exceeds 1. Reactions of UF{sup +} (k/k{sub ADO} {approx} 0.2) and UF{sub 2}{sup +} (k/k{sub ADO} {approx} 0.05) with H{sub 2}O resulted in both F {yields} OH exchange and oxidation. In contrast, UF{sub 3}{sup +} reacted very efficiently with H{sub 2}O (k/k{sub ADO} {approx} 1), exhibiting only F {yields} OH exchange. The primary ion products of the UO{sup +}/SF{sub 6} reaction (k/k{sub ADO} {approx} 0.2) were SF{sub 3}{sup +} and UOF{sub 2}{sup +}; those of the UOH{sup +}/SF{sub 6} reaction (k/k{sub ADO} {approx} 0.3) were SF{sub 3}{sup +} and UOF{sup +}. The reaction results are discussed in the context of a previously proposed reaction model, the distinctive chemistry of uranium, and thermodynamic considerations. The results illuminate the nature of uranium as well as general aspects of the interaction of bare and ligated transition-metal ions with SF{sub 6}. Results for collision-induced dissociation (CID) of selected uranium molecular ions support the concept of CID being a quasithermal process under these experimental conditions, with rearrangements prior to fragmentation possible for certain ions.

  20. Gas phase kinetics and equilibrium of allyl radical reactions with NO and NO2. (United States)

    Rissanen, Matti P; Amedro, Damien; Krasnoperov, Lev; Marshall, Paul; Timonen, Raimo S


    Allyl radical reactions with NO and NO(2) were studied in direct, time-resolved experiments in a temperature controlled tubular flow reactor connected to a laser photolysis/photoionization mass spectrometer (LP-PIMS). In the C(3)H(5) + NO reaction 1 , a dependence on the bath gas density was observed in the determined rate coefficients and pressure falloff parametrizations were performed. The obtained rate coefficients vary between 0.30-14.2 × 10(-12) cm(3) s(-1) (T = 188-363 K, p = 0.39-23.78 Torr He) and possess a negative temperature dependence. The rate coefficients of the C(3)H(5) + NO(2) reaction 2 did not show a dependence on the bath gas density in the range used (p = 0.47-3.38 Torr, T = 201-363 K), and they can be expressed as a function of temperature with k(C(3)H(5) + NO(2)) = (3.97 ± 0.84) × 10(-11) × (T/300 K) (-1.55±0.05) cm(3) s(-1). In the C(3)H(5) + NO reaction, above 410 K the observed C(3)H(5) radical signal did not decay to the signal background, indicating equilibrium between C(3)H(5) + NO and C(3)H(5)NO. This allowed the C(3)H(5) + NO ⇄ C(3)H(5)NO equilibrium to be studied and the equilibrium constants of the reaction between 414 and 500 K to be determined. With the standard second- and third-law analysis, the enthalpy and entropy of the C(3)H(5) + NO ⇄ C(3)H(5)NO reaction were obtained. Combined with the calculated standard entropy of reaction (ΔS°(298) = 137.2 J mol(-1)K(-1)), the third-law analysis resulted in ΔH°(298) = 102.4 ± 3.2 kJ mol(-1) for the C(3)H(5)-NO bond dissociation enthalpy.

  1. Solution phase and membrane immobilized iron-based free radical reactions: Fundamentals and applications for water treatment (United States)

    Lewis, Scott Romak

    Membrane-based separation processes have been used extensively for drinking water purification, wastewater treatment, and numerous other applications. Reactive membranes synthesized through functionalization of the membrane pores offer enhanced reactivity due to increased surface area at the polymer-solution interface and low diffusion limitations. Oxidative techniques utilizing free radicals have proven effective for both the destruction of toxic organics and non-environmental applications. Most previous work focuses on reactions in the homogeneous phase; however, the immobilization of reactants in membrane pores offers several advantages. The use of polyanions immobilized in a membrane or chelates in solution prevents ferric hydroxide precipitation at near-neutral pH, a common limitation of iron(Fe(II/III))-catalyzed hydrogen peroxide (H 2O2) decomposition. The objectives of this research are to develop a membrane-based platform for the generation of free radicals, degrade toxic organic compounds using this and similar solution-based reactions, degrade toxic organic compounds in droplet form, quantify hydroxyl radical production in these reactions, and develop kinetic models for both processes. In this study, a functionalized membrane containing poly(acrylic acid) (PAA) was used to immobilize iron ions and conduct free radical reactions by permeating H2O2 through the membrane. The membrane's responsive behavior to pH and divalent cations was investigated and modeled. The conversion of Fe(II) to Fe(III) in the membrane and its effect on the decomposition of hydrogen peroxide were monitored and used to develop kinetic models for predicting H2O2 decomposition in these systems. The rate of hydroxyl radical production, and hence contaminant degradation can be varied by changing the residence time, H2O2 concentration, and/or iron loading. Using these membrane-immobilized systems, successful removal of toxic organic compounds, such as pentachlorophenol (PCP), from water

  2. Numerical simulation of condensation on structured surfaces. (United States)

    Fu, Xiaowu; Yao, Zhaohui; Hao, Pengfei


    Condensation of liquid droplets on solid surfaces happens widely in nature and industrial processes. This phase-change phenomenon has great effect on the performance of some microfluidic devices. On the basis of micro- and nanotechnology, superhydrophobic structured surfaces can be well-fabricated. In this work, the nucleating and growth of droplets on different structured surfaces are investigated numerically. The dynamic behavior of droplets during the condensation is simulated by the multiphase lattice Boltzmann method (LBM), which has the ability to incorporate the microscopic interactions, including fluid-fluid interaction and fluid-surface interaction. The results by the LBM show that, besides the chemical properties of surfaces, the topography of structures on solid surfaces influences the condensation process. For superhydrophobic surfaces, the spacing and height of microridges have significant influence on the nucleation sites. This mechanism provides an effective way for prevention of wetting on surfaces in engineering applications. Moreover, it suggests a way to prevent ice formation on surfaces caused by the condensation of subcooled water. For hydrophilic surfaces, however, microstructures may be submerged by the liquid films adhering to the surfaces. In this case, microstructures will fail to control the condensation process. Our research provides an optimized way for designing surfaces for condensation in engineering systems.

  3. Theoretical investigations of the gas phase reaction of limonene (C10H16) with OH radical (United States)

    Ranjan Dash, Manas; Rajakumar, B.


    The rate coefficients of hydroxyl radical (OH) reaction with limonene were computed using canonical variational transition state theory with small-curvature tunnelling between 275 and 400 K. The geometries and frequencies of all the stationary points are calculated using hybrid density functional theory methods M06-2X and MPWB1K with 6-31+G(d,p), 6-311++G(d,p), and 6-311+G(2df,2p) basis sets. Both addition and abstraction channels of the title reaction were explored. The rate coefficients obtained over the temperature range of 275-400 K were used to derive the Arrhenius expressions: k(T) = 4.06×10-34 T7.07 exp[4515/T] and k(T) = 7.37×10-25 T3.9 exp[3169/T] cm3 molecule-1 s-1 at M06-2X/6-311+G(2df,2p) and MPWB1K/6-311+G(2df,2p) levels of theory, respectively. Kinetic study indicated that addition reactions are major contributors to the total reaction in the studied temperature range. The atmospheric lifetime (τ) of limonene due to its reactions with various tropospheric oxidants was calculated and concluded that limonene is lost in the atmosphere within a few hours after it is released. The ozone production potential of limonene was computed to be (14-18) ppm, which indicated that degradation of limonene would lead to a significant amount of ozone production in the troposphere.

  4. Sub/supercritical carbon dioxide induced phase switching for the reaction and separation in ILs/methanol

    Directory of Open Access Journals (Sweden)

    Jiayu Xin


    Full Text Available Separation of products from ionic liquid (IL solvents is one of the main challenges that hinder their utilizations. In this study, the production of γ-valerolactone (GVL by selective hydrogenation of α-angelica lactone (AL and separation of the products from the IL solvent were carried out by using subcritical CO2 as a “switch” at room temperature. After the mixture was separated into two phases by subcritical CO2, AL and nano Pd/C catalyst were only found in the lower IL-rich phase, GVL was produced with quantitative yield and enriched in the upper methanol-rich phase. Pure GVL can be obtained by depressurizing to release CO2 and evaporation to remove methanol of the upper phase, the lower phase containing IL, catalyst and methanol can be recycled for the next reaction. The strategy may provide a new approach to produce and separate products from IL solvents at mild conditions. Keywords: Separation, Ionic liquids, Selective hydrogenation, Mild condition, Subcritical CO2

  5. Effect of Attapulgite Nanorods and Calcium Sulfate Microwhiskers on the Reaction-Induced Phase Separation of Epoxy/PES Blends

    Directory of Open Access Journals (Sweden)

    Xiaolin Tang


    Full Text Available The influence of two kinds of mesoscale inorganic rod fillers, nanoscale attapulgite and micron-sized CaSO4 whisker, on the reaction-induced phase separation of epoxy/aromatic amine/poly- (ether sulfone (PES blends has been investigated by optical microscopy (OM, scanning electron microscopy (SEM, and time resolved light scattering (TRLS. By varying the PES concentration and curing temperature, we found that the incorporation of attapulgite and CaSO4 had dramatic impact on the phase separation process and the final phase morphology of blends. In blends at higher content than critical concentration, the process of phase separation was retarded by the incorporation of nanoscale fillers but accelerated by that of the micron-sized fillers, mainly due to the enhanced viscoelastic effect and the preferential wettable effect, respectively. Meanwhile both mesoscale fillers could change the cocontinuous phase structure of blends with lower PES content than critical concentration into PES-rich dispersed structure due to the surface affinity of fillers to epoxy matrix.

  6. On the solid–liquid phase diagrams of binary mixtures of even saturated fatty alcohols: Systems exhibiting peritectic reaction

    Energy Technology Data Exchange (ETDEWEB)

    Carareto, Natália D.D. [EXTRAE, Department of Food Engineering, Food Engineering Faculty, University of Campinas, UNICAMP, CEP 13083-862 Campinas, SP (Brazil); Santos, Adenílson O. dos [Social Sciences, Health and Technology Center, University of Maranhão, UFMA, CEP 65900-410 Imperatriz, MA (Brazil); Rolemberg, Marlus P. [Institute of Science and Technology, University of Alfenas, UNIFAL, Rodovia José AurélioVilela, CEP 37715400 Poços de Caldas, MG (Brazil); Cardoso, Lisandro P. [Institute of Physics GlebWataghin, University of Campinas, UNICAMP, C.P. 6165, CEP 13083-970 Campinas, SP (Brazil); Costa, Mariana C. [School of Applied Science, University of Campinas, UNICAMP, CEP 13484-350 Limeira, SP (Brazil); Meirelles, Antonio J.A., E-mail: [EXTRAE, Department of Food Engineering, Food Engineering Faculty, University of Campinas, UNICAMP, CEP 13083-862 Campinas, SP (Brazil)


    Highlights: • SLE of binary mixtures of saturated fatty alcohols was studied. • Experimental data were obtained using DSC and stepscan DSC. • Microscopy and X-ray diffraction used as complementary techniques. • Systems presented eutectic, peritectic and metatectic points. - Abstract: The solid–liquid phase diagrams of the following binary mixtures of even saturated fatty alcohols are reported in the literature for the first time: 1-octanol (C8OH) + 1-decanol (C10OH), 1-decanol + 1-dodecanol (C12OH), 1-dodecanol + 1-hexadecanol (C16OH) and 1-tetradecanol (C14OH) + 1-octadecanol (C18OH). The phase diagrams were obtained by differential scanning calorimetry (DSC) using a linear heating rate of 1 K min{sup −1} and further investigated by using a stepscan DSC method. X-ray diffraction (XRD) and polarized light microscopy were also used to complement the characterization of the phase diagrams which have shown a complex global behavior, presenting not only peritectic and eutectic reactions, but also the metatectic reaction and partial immiscibility on solid state.

  7. Hydration Leads to Efficient Reactions of the Carbonate Radical Anion with Hydrogen Chloride in the Gas Phase. (United States)

    Tang, Wai Kit; van der Linde, Christian; Siu, Chi-Kit; Beyer, Martin K


    The carbonate radical anion CO3•- is a key intermediate in tropospheric anion chemistry. Despite its radical character, only a small number of reactions have been reported in the literature. Here we investigate the gas-phase reactions of CO3•- and CO3•-(H2O) with HCl under ultrahigh vacuum conditions. Bare CO3•- forms OHCl•- with a rate constant of 4.2 × 10-12 cm3 s-1, which corresponds to an efficiency of only 0.4%. Hydration accelerates the reaction, and ligand exchange of H2O against HCl proceeds with a rate of 2.7 × 10-10 cm3 s-1. Quantum chemical calculations reveal that OHCl•- is best described as an OH• hydrogen bonded to Cl-, while the ligand exchange product is Cl-(HCO3•). Under tropospheric conditions, where CO3•-(H2O) is the dominant species, Cl-(HCO3•) is efficiently formed. These reactions must be included in models of tropospheric anion chemistry.

  8. LSENS: A General Chemical Kinetics and Sensitivity Analysis Code for homogeneous gas-phase reactions. Part 3: Illustrative test problems (United States)

    Bittker, David A.; Radhakrishnan, Krishnan


    LSENS, the Lewis General Chemical Kinetics and Sensitivity Analysis Code, has been developed for solving complex, homogeneous, gas-phase chemical kinetics problems and contains sensitivity analysis for a variety of problems, including nonisothermal situations. This report is part 3 of a series of three reference publications that describe LSENS, provide a detailed guide to its usage, and present many example problems. Part 3 explains the kinetics and kinetics-plus-sensitivity analysis problems supplied with LSENS and presents sample results. These problems illustrate the various capabilities of, and reaction models that can be solved by, the code and may provide a convenient starting point for the user to construct the problem data file required to execute LSENS. LSENS is a flexible, convenient, accurate, and efficient solver for chemical reaction problems such as static system; steady, one-dimensional, inviscid flow; reaction behind incident shock wave, including boundary layer correction; and perfectly stirred (highly backmixed) reactor. In addition, the chemical equilibrium state can be computed for the following assigned states: temperature and pressure, enthalpy and pressure, temperature and volume, and internal energy and volume. For static problems the code computes the sensitivity coefficients of the dependent variables and their temporal derivatives with respect to the initial values of the dependent variables and/or the three rate coefficient parameters of the chemical reactions.

  9. In Situ and in Operando Characterization of Mixing Dynamics in Liquid-Phase Reactions by129Xe NMR Spectroscopy. (United States)

    Zaheer, Muhammad A; Zill, Jeremias C; Matysik, Jörg; Gläser, Roger; Dvoyashkin, Muslim


    129 Xe NMR spectroscopy is applied under in situ and in operando conditions to study the mixing process in a multicomponent liquid mixture with partially miscible components. The process of mixing of an oil-methanol mixture was triggered by an industrially relevant catalytic transesterification reaction to form fatty acid methyl esters and glycerol. Up to date, kinetic limitations in liquid-phase reactions originating from the poor miscibility of the reacting species have been addressed solely under ex situ conditions, typically by chromatography. In the approach presented here, xenon gas, solvated in the reacting species, acts as a sensor, providing information on the progress of mixing and on the composition during the course of the catalytic reaction. We believe that this study offers a new tool to the set of established techniques for addressing mixing and/or separation processes in liquids, including but not limited to the ones resulting from catalytic reactions. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Gait Phases Recognition from Accelerations and Ground Reaction Forces: Application of Neural Networks

    Directory of Open Access Journals (Sweden)

    S. Rafajlović


    Full Text Available The goal of this study was to test the applicability of accelerometer as the sensor for assessment of the walking. We present here the comparison of gait phases detected from the data recorded by force sensing resistors mounted in the shoe insoles, non-processed acceleration and processed acceleration perpendicular to the direction of the foot. The gait phases in all three cases were detected by means of a neural network. The output from the neural network was the gait phase, while the inputs were data from the sensors. The results show that the errors were in the ranges: 30 ms (2.7% – force sensors; 150 ms (13.6% – nonprocessed acceleration, and 120 ms (11% – processed acceleration data. This result suggests that it is possible to use the accelerometer as the gait phase detector, however, with the knowledge that the gait phases are time shifted for about 100 ms with respect the neural network predicted times.

  11. Photochemistry and kinetics of gas phase reactions involving HO and Cl radicals

    Energy Technology Data Exchange (ETDEWEB)

    Nelson, H.H.


    The kinetics of the reaction of the HO radical with HNO/sub 3/ and H/sub 2/O/sub 2/, the kinetics of Cl atom reactions with ClNO and ClNO/sub 2/, and the photochemistry of ClNO/sub 2/ and ClONO/sub 2/ were examined. The ultraviolet absorption cross sections of HNO/sub 3/ and ClNO/sub 2/ were also determined as part of the kinetics work. The rate constant for the reaction of HO with HNO/sub 3/ at room temperature was measured to be (8.2 +- 1.8) x 10/sup -14/ cm/sup 3/ molecule/sup -1/ s/sup -1/, where the uncertainty reported here and in all cases reflects twice the experimental standard deviation plus an estimate of systematic errors. The rate constant for the reaction HO + H/sub 2/O/sub 2/ was measured as (1.57 +- 0.23) x 10/sup -12/ cm/sup 3/ molecule/sup -1/ s/sup -1/. This agrees well with the two latest determinations and serves as a calibration of the experimental apparatus used. The Cl + ClNO reaction rate constant was determined to be (1.65 +- 0.32) x 10/sup -11/ cm/sup 3/ molecule/sup -1/ s/sup -1/. The rate constant for the reaction of Cl + ClNO/sub 2/ was found to be (5.05 +- 0.75) x 10/sup -12/ cm/sup 3/ molecule/sup -1/ s/sup -1/. This is the first direct measurement of this rate constant. The photodissociation of ClNO/sub 2/ was studied in great detail. The absorption cross sections were measured in the ultraviolet and found to be substantially lower than the literature values in the Cl/sub 2/ absorption region (300 to 360 nm). Two product channels were investigated; products representative of the two channels were Cl and O atoms. Absolute calibration for the product detection systems was provided by Cl/sub 2/ and NO/sub 2/ photolysis respectively. The quantum uields measured for photolysis at 350 nm, calcualted using the absorption spectrum measured in this work, are: 0.93 +- 0.1 for Cl and less than or equal to 0.025 for O. An upper limit of 0.1 was measured for the O atom channel in ClOHO/sub 2/ photolysis.

  12. Bright soliton trains of trapped Bose-Einstein condensates


    Al Khawaja, U.; Stoof, H.T C; Hulet, R. G.; Strecker, K. E.; Patridge, G.B.


    We variationally determine the dynamics of bright soliton trains composed of harmonically trapped Bose-Einstein condensates with attractive interatomic interactions. In particular, we obtain the interaction potential between two solitons. We also discuss the formation of soliton trains due to the quantum mechanical phase fluctuations of a one-dimensional condensate.

  13. Ionic transformations in extremely nonpolar fluorous media: easily recoverable phase-transfer catalysts for halide-substitution reactions. (United States)

    Mandal, Debaprasad; Jurisch, Markus; Consorti, Crestina S; Gladysz, John A


    Solutions of the fluorous alkyl halides R(f8)(CH(2))(m)X (R(fn)=(CF(2))(n-1)CF(3); m=2, 3; X=Cl, Br, I) in perfluoromethylcyclohexane or perfluoromethyldecalin are inert towards solid or aqueous NaCl, NaBr, KI, KCN, and NaOAc. However, halide substitution occurs in the presence of fluorous phosphonium salts (R(f8)(CH(2))(2))(R(f6)(CH(2))(2))(3)P(+)X(-) (X=I (1), Br (3)) and (R(f8)(CH(2))(2))(4)P(+)I(-) (10 mol %), which are soluble in the fluorous solvents under the reaction conditions (76-100 degrees C). Stoichiometric reactions of a) 1 with R(f8)(CH(2))(2)Br and b) 3 with R(f8)(CH(2))(2)I were conducted under homogenous conditions in perfluoromethyldecalin at 100 degrees C and yielded the same R(f8)(CH(2))(2)I/R(f8)(CH(2))(2)Br equilibrium ratio ( approximately 60:40). This shows that ionic displacements can take place in extremely nonpolar fluorous phases and suggests a classical phase-transfer mechanism for the catalyzed reactions. Interestingly, the nonfluorous salt (CH(3)(CH(2))(11))(CH(3)(CH(2))(7))(3)P(+)I(-) (4) also catalyzes halide substitutions, but under triphasic conditions with 4 suspended between the lower fluorous and upper aqueous layers. NMR experiments established very low solubilities in both phases, which suggests interfacial catalysis. Catalyst 1 is easily recycled, optimally by simple precipitation onto teflon tape.

  14. Modeling-gas phase reactions in indoor environments using computational fluid dynamics

    DEFF Research Database (Denmark)

    Sørensen, Dan Nørtoft; Weschler, Charles J.


    This CFD modeling study examines the concentrations of two gaseous compounds that react in an indoor setting to produce a hypothetical product. The reactants are ozone and either d-limonene or alpha-terpinene (which reacts with ozone about 40 times faster than d-limonene). In addition to two...... surfaces while the terpenes do not. The results show that for all four scenarios, under steady-state conditions, there are large concentration gradients within the room for both reactants and product. To some extent this is due to imperfect mixing. However. it also reflects that reactions occur...... at different rates across the room (because of varying reactant concentrations) and that the time available for reactions to occur varies with the room location (because the "age of the air" varies from point to point). Locally, within the room, the concentrations calculated by the CFID method differ...

  15. Energy condensed packaged systems. Composition, production, properties

    Directory of Open Access Journals (Sweden)

    Igor L. Kovalenko


    Full Text Available In this paper it is presented the substantiation of choice of fuel phase composition and optimal technology of emulsion production on the basis of binary solution of ammonium and calcium nitrates, which provide the obtaining of energy condensed packaged systems with specified properties. The thermal decomposition of energy condensed systems on the basis of ammonium nitrate is investigated. It is shown that the fuel phase of emulsion systems should be based on esters of polyunsaturated acids or on combinations thereof with petroleum products. And ceresin or petroleum wax can be used as the structuring additive. The influence of the technology of energy condensed systems production on the physicochemical and detonation parameters of emulsion explosives is considered. It is shown the possibility of obtaining of emulsion systems with dispersion of 1.3...1.8 microns and viscosity higher than 103 Pa∙s in the apparatus of original design. The sensitizing effect of chlorinated paraffin CP-470 on the thermolysis of energy condensed emulsion system is shown. The composition and production technology of energy condensed packaged emulsion systems of mark Ukrainit-P for underground mining in mines not dangerous on gas and dust are developed.

  16. Condensate formation in a Bose gas

    NARCIS (Netherlands)

    Stoof, H.T.C.


    Using magnetically trapped atomic hydrogen as an example, we investigate the prospects of achieving Bose-Einstein condensation in a dilute Bose gas. We show that, if gas is quenched sufficiently far into the critical region of the phase transition, the typical time scale for the nucleation of the

  17. Composite Si/C/N powder production by laser induced gas phase reactions

    Energy Technology Data Exchange (ETDEWEB)

    Borsella, E.; Botti, S.; Fantoni, R.; Alexandrescu, R.; Morjan, I.; Popescu, C.; Dikonimos-Makris, T.; Giorgi, R.; Enzo, S.


    Ultrafine amorphous Si/C/N ternary powders were prepared in a CO/sub 2/ laser assisted process. This paper demonstrates the possibility of driving the C/N ratio the powder by properly choosing the experimental conditions and the gaseous reactant ratio in the initial mixture containing silane, dimethylamine and ammonia. A kinetic model which accounts for reaching the equilibrium between the gaseous reaction intermediates and the solid products is proposed.

  18. Metal-Organic Frameworks as Basic Catalysts for Liquid Phase Reactions


    Fischer, Marcus


    To overcome the drawbacks of homogeneous catalysis, which is state of the art for many base catalyzed reactions on industrial scale, the development of new basic solids for the use as heterogeneous basic catalysts is of high scientific interest. In the last decades, several types of basic solids were investigated for this purpose, including metal oxides, ion-exchanged zeolites, amino-functionalized mesoporous silica and nitridated aluminosilicate and aluminophosphate materials. In recent year...

  19. A New Paradigm to Identify Reaction Pathways in Gas-phase (United States)


    13 3.1 Monoatomic particle in 2D potential 13 3.2 Ethane decomposition 18 3.2.1 FE calculations...13 3.1 Monoatomic particle in 2D potential 3.2 Ethane decomposition 3.3 t-decalin + methyl radical 4 Conclusions...bimolecular reactions are presented. 3.1 Monoatomic particle in 2D potential The behavior of a single particle in a customizable analytic potential is

  20. Reaction of the BCG Scar in the Acute Phase of Kawasaki Disease in Mexican Children. (United States)

    Garrido-García, Luis Martín; Castillo-Moguel, Ariel; Vázquez-Rivera, Mirella; Cravioto, Patricia; Fernando, Galván


    Kawasaki disease (KD) is an acute self-limited systemic vasculitis that primarily affects children BCG) inoculation site has been reported as a common finding in patients with KD where BCG vaccination is mandatory. The purpose of this study was to evaluate the frequency of reactivation of the BCG in Mexican children diagnosed with KD. A retrospective study of all patients diagnosed with KD from August 1, 1995, to August 31, 2015, at our Institution was performed. The clinical profile, laboratory results, treatment used and coronary artery abnormalities in the BCG reactive and the BCG nonreactive groups were analyzed and compared. We included 399 patients with KD. Ninety-seven (24.3%) had BCG reaction at the inoculation site. The BCG(+) group was younger than the BCG(-) group (P BCG(+) group compared with 65 (21.52%) in the BCG(-) group without statistical significance. The BCG+ group developed coronary artery aneurysms in 37 cases and the BCG(-) group developed coronary artery aneurysms in 111 cases without statistical significance. Multivariate analysis showed that younger age at diagnosis was the only variable associated with a reaction at the BCG inoculation site in patients with KD. In Mexico, a country with a National BCG Vaccination Program and a low incidence of KD, reaction at the BCG inoculation site could be a useful diagnostic sign of KD.

  1. Theoretical study on the gas phase reaction of acrylonitrile with a hydroxyl radical. (United States)

    Sun, Jingyu; Wang, Rongshun; Wang, Baoshan


    The mechanism and kinetics of the reaction of acrylonitrile (CH(2)=CHCN) with hydroxyl (OH) has been investigated theoretically. This reaction is revealed to be one of the most significant loss processes of acrylonitrile. BHandHLYP and M05-2X methods are employed to obtain initial geometries. The reaction mechanism conforms that OH addition to C[double bond, length as m-dash]C double bond or C atom of -CN group to form the chemically activated adducts, 1-IM1(HOCH(2)=CHCN), 2-IM1(CH(2)=HOCHCN), and 3-IM1(CH(2)=CHCOHN) via low barriers, and direct hydrogen abstraction paths may also occur. Temperature- and pressure-dependent rate constants have been evaluated using the Rice-Ramsperger-Kassel-Marcus theory. The calculated rate constants are in good agreement with the experimental data. At atmospheric pressure with N(2) as bath gas, 1-IM1(OHCH(2)=CHCN) formed by collisional stabilization is the major product in the temperature range of 200-1200 K. The production of CH(2)CCN and CHCHCN via hydrogen abstractions becomes dominant at high temperatures (1200-3000 K).

  2. Ab initio molecular dynamics simulations of the gas-phase reaction of hydroxyl radical with nitrogen dioxide radical (United States)

    Doclo, Karel; Röthlisberger, Ursula


    The reaction between the hydroxyl radical and the nitrogen dioxide radical in the gas phase has been studied with ab initio molecular dynamics simulations based on density functional theory. Nitric acid HONO 2 and cis- cis peroxynitrous acid ONOOH are formed spontaneously, whereas for the formation of the corresponding trans- perp conformer of peroxynitrous acid, a barrier is observed. The relative energetics of the different conformers of ONOOH are in good agreement with MP2 results. The same holds for the structural properties, except for the N-O single bond which turns out to be highly sensitive to the exchange-correlation functional and is generally overestimated.

  3. A Lattice Boltzmann Approach to Multi-Phase Surface Reactions with Heat Effects

    NARCIS (Netherlands)

    Kamali, M.R.


    The aim of the present research was to explore the promises and shift the limits of the numerical framework of lattice Boltzmann (LB) for studying the physics behind multi-component two-phase heterogeneous non-isothermal reactive flows under industrial conditions. An example of such an industrially

  4. Condensed Matter Field Theory (United States)

    Altland, Alexander; Simons, Ben


    Over the past few decades, in concert with ground-breaking experimental advances, condensed matter theory has drawn increasingly from the language of low-energy quantum field theory. This primer is aimed at elevating graduate students of condensed matter theory to a level where they can engage in independent research. It emphasizes the development of modern methods of classical and quantum field theory with applications oriented around condensed matter physics. Topics covered include second quantization, path and functional field integration, mean-field theory and collective phenomena, the renormalization group, and topology. Conceptual aspects and formal methodology are emphasized, but the discussion is rooted firmly in practical experimental application. As well as routine exercises, the text includes extended and challenging problems, with fully worked solutions, designed to provide a bridge between formal manipulations and research-oriented thinking. This book will complement graduate level courses on theoretical quantum condensed matter physics. Spans the field of modern condensed matter theory focusing on field theory techniques Written to facilitate learning, with numerous challenging exercises, with fully worked solutions, aimed at physicists starting graduate-level courses The theoretical methods are firmly set in concrete experimental applications

  5. Kinetics, mechanism, and thermochemistry of the gas-phase reaction of atomic chlorine with pyridine. (United States)

    Zhao, Z; Huskey, D T; Olsen, K J; Nicovich, J M; McKee, M L; Wine, P H


    A laser flash photolysis-resonance fluorescence technique has been employed to study the kinetics of the reaction of atomic chlorine with pyridine (C(5)H(5)N) as a function of temperature (215-435 K) and pressure (25-250 Torr) in nitrogen bath gas. At T> or = 299 K, measured rate coefficients are pressure independent and a significant H/D kinetic isotope effect is observed, suggesting that hydrogen abstraction is the dominant reaction pathway. The following Arrhenius expression adequately describes all kinetic data at 299-435 K for C(5)H(5)N: k(1a) = (2.08 +/- 0.47) x 10(-11) exp[-(1410 +/- 80)/T] cm(3) molecule(-1) s(-1) (uncertainties are 2sigma, precision only). At 216 K rate coefficients are pressure dependent and are much faster than computed from the above Arrhenius expression for the H-abstraction pathway, suggesting that the dominant reaction pathway at low temperature is formation of a stable adduct. Over the ranges of temperature, pressure, and pyridine concentration investigated, the adduct undergoes dissociation on the time scale of our experiments (10(-5)-10(-2) s) and establishes an equilibrium with Cl and pyridine. Equilibrium constants for adduct formation and dissociation are determined from the forward and reverse rate coefficients. Second- and third-law analyses of the equilibrium data lead to the following thermochemical parameters for the addition reaction: Delta(r)H = -47.2 +/- 2.8 kJ mol(-1), Delta(r)H = -46.7 +/- 3.2 kJ mol(-1), and Delta(r)S = -98.7 +/- 6.5 J mol(-1) K(-1). The enthalpy changes derived from our data are in good agreement with ab initio calculations reported in the literature (which suggest that the adduct structure is planar and involves formation of an N-Cl sigma-bond). In conjunction with the well-known heats of formation of atomic chlorine and pyridine, the above Delta(r)H values lead to the following heats of formation for C(5)H(5)N-Cl at 298 K and 0 K: Delta(f)H = 216.0 +/- 4.1 kJ mol(-1), Delta(f)H = 233.4 +/- 4.6 k

  6. A single-arm Phase II validation study of preventing oxaliplatin-induced hypersensitivity reactions by dexamethasone: the AVOID trial

    Directory of Open Access Journals (Sweden)

    Yoshida Y


    Full Text Available Yoichiro Yoshida,1 Keiji Hirata,2 Hiroshi Matsuoka,3 Shigeyoshi Iwamoto,4 Masahito Kotaka,5 Hideto Fujita,6 Naoya Aisu,1 Seiichiro Hoshino,1 Takeo Kosaka,6 Kotaro Maeda,3 Fumiaki Kiyomi,7 Yuichi Yamashita1 1Department of Gastroenterological Surgery, Fukuoka University Faculty of Medicine, Fukuoka, Japan; 2Department of Surgery, Fukuoka Sanno Hospital, Fukuoka, Japan; 3Department of Surgery, Fujita Health University School of Medicine, Toyoake, Japan; 4Department of Surgery, Kansai Medical University Hirakata Hospital, Osaka, Japan; 5Gastrointestinal Cancer Center, Sano Hospital, Kobe, Japan; 6Department of Surgical Oncology, Kanazawa Medical University, Uchinada, Japan; 7Academia, Industry and Government Collaborative Research Institute of Translational Medicine for Life Innovation, Fukuoka University, Fukuoka, Japan Background: Patients with colorectal cancer treated with oxaliplatin are at risk of hypersensitivity reactions, with the incidence estimated to be 12%–20%. Coinfusion of dexamethasone and oxaliplatin could potentially reduce the incidence of these reactions, but oxaliplatin is reported to be incompatible with alkaline compounds in solution. However, in a previous retrospective study we found that the pH of a solution of dexamethasone and oxaliplatin was less than 7.4, and that hypersensitivity to oxaliplatin could have been prevented by coinfusion of dexamethasone. We aimed to evaluate the effectiveness of coinfusion of dexamethasone and oxaliplatin to prevent oxaliplatin-induced hypersensitivity reactions.Patients and methods: The AVOID trial was a prospective, multicenter, open-label, single-arm Phase II trial conducted from January to September 2013. The study included 73 patients who received capecitabine plus oxaliplatin (XELOX or XELOX plus bevacizumab therapy for colorectal cancer. In all patients, oxaliplatin was administered in combination with dexamethasone. The primary outcome measure was the presence of

  7. Photocatalytic Reaction of Gas-Phase Naphthalene on Paint- and Sunscreen-Coated Surfaces


    Ashley, Nicholas A.; McBride, Noelle; Krumholt, Jason; Baker, Breeana; Valsaraj, Kalliat T.


    The uses of metal oxide nanoparticles in modern paint and sunscreen formulations are widespread. Through materials characterization and kinetic experiments, it is demonstrated that fresh surface coatings of paint and sunscreen photocatalytically degrade gaseous naphthalene. The primary metal oxides are TiO2 in the form of the rutile phase in paint and as anatase in sunscreen formulations. Other metal oxides present are Al2O3 and ZnO. Several organic fillers that are photochemically active are...

  8. Is the Gas-phase OH+H2CO Reaction a Source of HCO in Interstellar Cold Dark Clouds? A Kinetic, Dynamic, and Modeling Study (United States)

    Ocaña, A. J.; Jiménez, E.; Ballesteros, B.; Canosa, A.; Antiñolo, M.; Albaladejo, J.; Agúndez, M.; Cernicharo, J.; Zanchet, A.; del Mazo, P.; Roncero, O.; Aguado, A.


    The chemical kinetics of neutral-neutral gas-phase reactions at ultralow temperatures is a fascinating research subject with important implications on the chemistry of complex organic molecules in the interstellar medium (T ˜ 10-100 K). Scarce kinetic information is currently available for these kinds of reactions at T environments are also addressed.

  9. Muonic Chemistry in Condensed Matter

    CERN Multimedia


    When polarized muons (@m|+) stop in condensed matter, muonic atoms are formed in the final part of their range, and direct measurements of the @m|+-spin polarization are possible via the asymmetric decay into positrons. The hyperfine interaction determines the characteristic precession frequencies of the @m|+ spin in muonium, @w(Mu). Such frequencies can be altered by the interactions of the muonium's electron spin with the surrounding medium. The measurement of @w(Mu) in a condensed system is known often to provide unique information regarding the system. \\\\ \\\\ In particular, the use of muonium atoms as a light isotope of the simple reactive radical H|0 allows the investigation of fast reactions of radicals over a typical time scale 10|-|9~@$<$~t~@$<$~10|-|5~sec, which is determined by the instrumental resolution at one end and by the @m|+ lifetime at the other. \\\\ \\\\ In biological macromolecules transient radicals, such as the constituents of DNA itself, exist on a time scale of sub-microseconds, acco...

  10. Formation Time of a Fermion Pair Condensate


    Zwierlein, M. W.; Schunck, C. H.; Stan, C. A.; Raupach, S. M. F.; Ketterle, W.


    The formation time of a condensate of fermionic atom pairs close to a Feshbach resonance was studied. This was done using a phase-shift method in which the delayed response of the many-body system to a modulation of the interaction strength was recorded. The observable was the fraction of condensed molecules in the cloud after a rapid magnetic field ramp across the Feshbach resonance. The measured response time was slow compared to the rapid ramp, which provides final proof that the molecular...


    Directory of Open Access Journals (Sweden)

    Jan Havlík


    Full Text Available This paper presents an analysis of heat transfer in the process of condensation of water vapor in a vertical shell-and-tube condenser. We analyze the use of the Nusselt model for calculating the condensation heat transfer coefficient (HTC inside a vertical tube and the Kern, Bell-Delaware and Stream-flow analysis methods for calculating the shell-side HTC from tubes to cooling water. These methods are experimentally verified for a specific condenser of waste process vapor containing air. The operating conditions of the condenser may be different from the assumptions adopted in the basic Nusselt theory. Modifications to the Nusselt condensation model are theoretically analyzed.

  12. The oxygen reduction reaction at the three-phase boundary: nanoelectrodes modified with Ag nanoclusters. (United States)

    Clausmeyer, Jan; Botz, Alexander; Öhl, Denis; Schuhmann, Wolfgang


    Silver nanoclusters are deposited on bifunctional Θ-shaped nanoelectrodes consisting of a carbon nanoelectrode combined with a hollow nanopipette. The Θ-nanoelectrodes are used as model systems to study interfacial mass transport in gas diffusion electrodes and in particular oxygen-depolarized cathodes (ODC) for the oxygen reduction reaction (ORR) in chlor-alkali electrolysers. By local delivery of O2 gas to the electroactive Ag nanoclusters through the adjacent nanopipette, enhanced currents for the ORR at the Ag nanoparticles are recorded which are not accountable when considering the low solubility and slow diffusion of O2 in highly alkaline media. Instead, local oversaturation of O2 leads to current enhancement at the Ag nanoclusters. Due to the intrinsic high mass transport rates at the nanometric electrodes accompanied by local delivery of reactants, the method generally allows to study electrochemical reactions at single nanoparticles beyond the limitations induced by slow diffusion and low reactant concentration. Kinetic and mechanistic information, for instance derived from Tafel slopes, can be obtained from kinetic regimes not accessible to standard techniques.

  13. Kinetic study of the gas-phase reaction of atomic chlorine with a series of aldehydes

    Directory of Open Access Journals (Sweden)

    D. Rodríguez


    Full Text Available The reactions of Cl atoms with a series of unsaturated aldehydes have been investigated for the first time using a relative method. In order to obtain additional information for a qualitative structure versus reactivity discussion, we have also determined the rate coefficients for the reactions of atomic chlorine with their respective saturated aldehydes. These relative measurements were performed at room temperature and atmospheric pressure of air and N2, by using ethane, propene and 1-butene as reference compounds. The weighted average relative rate constants obtained, kCl±2σ (in units of cm3 molecule−1 s−1 were: trans-2-pentenal (1.31±0.19×10−10; trans-2-hexenal (1.92±0.22×10−10; trans-2-heptenal (2.40±0.29×10−10; n-pentanal (2.56±0.27×10−10; n-hexanal (2.88±0.37×10−10; n-heptanal (3.00±0.34×10−10. Finally, results and atmospheric implications are discussed and compared with the reactivity with OH and NO3 radicals.

  14. Advances in synthetic optically active condensation polymers - A review

    Directory of Open Access Journals (Sweden)


    Full Text Available The study of optically active polymers is a very active research field, and these materials have exhibited a number of interesting properties. Much of the attention in chiral polymers results from the potential of these materials for several specialized utilizations that are chiral matrices for asymmetric synthesis, chiral stationary phases for the separation of racemic mixtures, synthetic molecular receptors and chiral liquid crystals for ferroelectric and nonlinear optical applications. Recently, highly efficient methodologies and catalysts have been developed to synthesize various kinds of optically active compounds. Some of them can be applied to chiral polymer synthesis. In a few synthetic approaches for optically active polymers, chiral monomer polymerization has essential advantages in applicability of monomer, apart from both asymmetric polymerization of achiral or prochiral monomers and enantioselective polymerization of a racemic monomer mixture. The following are the up to date successful approaches to the chiral synthetic polymers by condensation polymerization reaction of chiral monomers.

  15. Extending the scope of 'in silico experiments': Theoretical approaches for the investigation of reaction mechanisms, nucleation events and phase transitions

    Directory of Open Access Journals (Sweden)

    Dirk Zahn et al


    Full Text Available The investigation of the atomistic mechanisms of processes in complex systems constitutes a major challenge to both theory and experiment. While experimental studies offer a wide variety of insights at the macroscopic scale, the atomistic level of detail often remains elusive. On the other hand, molecular simulation approaches may easily achieve microscopic resolution and hence appear particularly suited for detailed mechanistic analyses. However, the computational effort is typically quite considerable and in many cases special simulation strategies are needed to make simulations possible. This review is dedicated to special approaches for tackling the time/length-scale problem inherent to molecular dynamics simulations. Employing these techniques opened a series of new perspectives. The latter are illustrated with the example of recent simulation studies of the atomistic mechanisms involved in complex processes like crystal nucleation, phase transitions and reactions in solution. Along this line, we discuss the reaction mechanisms for He insertion into C60 fullerenes, nucleation events and domain morphogenesis in pressure-induced phase transitions in solids and ion aggregation from solution.

  16. Detachment of CVD-grown graphene from single crystalline Ni films by a pure gas phase reaction (United States)

    Zeller, Patrick; Henß, Ann-Kathrin; Weinl, Michael; Diehl, Leo; Keefer, Daniel; Lippmann, Judith; Schulz, Anne; Kraus, Jürgen; Schreck, Matthias; Wintterlin, Joost


    Despite great previous efforts there is still a high need for a simple, clean, and upscalable method for detaching epitaxial graphene from the metal support on which it was grown. We present a method based on a pure gas phase reaction that is free of solvents and polymer supports and avoids mechanical transfer steps. The graphene was grown on 150 nm thick, single crystalline Ni(111) films on Si(111) wafers with YSZ buffer layers. Its quality was monitored by using low energy electron diffraction and scanning tunneling microscopy. The gas phase etching uses a chemical transport reaction, the so-called Mond process, based on the formation of gaseous nickel tetracarbonyl in ~ 1 bar of CO at ~ 75 °C and by adding small amounts of sulfide catalysts. X-ray photoelectron spectroscopy, Raman spectroscopy and scanning electron microscopy were used to characterize the detached graphene. It was found that the method successfully removes the nickel from underneath the graphene layer, so that the graphene lies on the insulating oxide buffer layer. Small residual particles of nickel sulfide and cracks in the obtained graphene layer were identified. The defect concentrations were comparable to graphene samples obtained by wet chemical etching and by the bubbling transfer.

  17. Development of Flow-Through Polymeric Membrane Reactor for Liquid Phase Reactions: Experimental Investigation and Mathematical Modeling

    Directory of Open Access Journals (Sweden)

    Endalkachew Chanie Mengistie


    Full Text Available Incorporating metal nanoparticles into polymer membranes can endow the membranes with additional functions. This work explores the development of catalytic polymer membrane through synthesis of palladium nanoparticles based on the approaches of intermatrix synthesis (IMS inside surface functionalized polyethersulfone (PES membrane and its application to liquid phase reactions. Flat sheet PES membranes have been successfully modified via UV-induced graft polymerization of acrylic acid monomer. Palladium nanoparticles have been synthesized by chemical reduction of palladium precursor loaded on surface modified membranes, an approach to the design of membranes modified with nanomaterials. The catalytic performances of the nanoparticle incorporated membranes have been evaluated by the liquid phase reduction of p-nitrophenol using NaBH4 as a reductant in flow-through membrane reactor configuration. The nanocomposite membranes containing palladium nanoparticles were catalytically efficient in achieving a nearly 100% conversion and the conversion was found to be dependent on the flux, amount of catalyst, and initial concentration of nitrophenol. The proposed mathematical model equation represents satisfactorily the reaction and transport phenomena in flow-through catalytic membrane reactor.

  18. Thermochemistry of the Reaction of SF6 with Gas-Phase Hydrated Electrons: A Benchmark for Nanocalorimetry. (United States)

    Akhgarnusch, Amou; Höckendorf, Robert F; Beyer, Martin K


    The reaction of sulfur hexafluoride with gas-phase hydrated electrons (H2O)n(-), n ≈ 60-130, is investigated at temperatures T = 140-300 K by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. SF6 reacts with a temperature-independent rate of 3.0 ± 1.0 × 10(-10) cm(3) s(-1) via exclusive formation of the hydrated F(-) anion and the SF5(•) radical, which evaporates from the cluster. Nanocalorimetry yields a reaction enthalpy of ΔHR,298K = 234 ± 24 kJ mol(-1). Combined with literature thermochemical data from bulk aqueous solution, these result in an F5S-F bond dissociation enthalpy of ΔH298K = 455 ± 24 kJ mol(-1), in excellent agreement with all high-level quantum chemical calculations in the literature. A combination with gas-phase literature thermochemistry also yields an experimental value for the electron affinity of SF5(•), EA(SF5(•)) = 4.27 ± 0.25 eV.

  19. Condensed matter physics

    CERN Document Server

    Isihara, A


    More than a graduate text and advanced research guide on condensed matter physics, this volume is useful to plasma physicists and polymer chemists, and their students. It emphasizes applications of statistical mechanics to a variety of systems in condensed matter physics rather than theoretical derivations of the principles of statistical mechanics and techniques. Isihara addresses a dozen different subjects in separate chapters, each designed to be directly accessible and used independently of previous chapters. Topics include simple liquids, electron systems and correlations, two-dimensional

  20. The effect of salmeterol and salbutamol on mediator release and skin responses in immediate and late phase allergic cutaneous reactions. (United States)

    Petersen, L J; Skov, P S


    Salmeterol is a long-acting beta2-agonist which in animal studies has been shown to possess anti-inflammatory effects on early (EAR) and late (LPR) phase allergic responses. To evaluate the anti-inflammatory effects of intradermally injected salmeterol and salbutamol on clinical and biochemical EAR and LPR in human skin. Measurement of wheal and flare reactions to allergen, codeine, and histamine, and LPR (induration) to allergen. Assessment of histamine and prostaglandin D2 (PGD2) release by microdialysis technique in EAR, and measurement of mediators in LPR by suction blister technique. Both beta2-agonists inhibited allergen-induced histamine release and wheal and flare reactions with maximum inhibition of 40-50% at 10(-6) M, a concentration which reduced PGD2 synthesis by approximately 55%. Histamine release by codeine and skin reactions to codeine and histamine were not or only marginally reduced. Salmeterol and salbutamol (10(-6) M) inhibited clinical LPR at 6 h by 71% and 48%, Except for the clinical LPR, no statistical differences were found between the two drugs on any parameters. None of the drugs inhibited levels of histamine, tryptase, myeloperoxidase, or eosinophil cationic protein in LPR. Salmeterol and salbutamol inhibited allergen-induced skin responses, and reduced mediator release in EAR but not LPR. In general, the anti-inflammatory effects of salmeterol did not differ from those induced by salbutamol.

  1. Compositional evolution of particle-phase reaction products and water in the heterogeneous OH oxidation of model aqueous organic aerosols (United States)

    Chim, Man Mei; Cheng, Chiu Tung; Davies, James F.; Berkemeier, Thomas; Shiraiwa, Manabu; Zuend, Andreas; Nin Chan, Man


    Organic compounds present at or near the surface of aqueous droplets can be efficiently oxidized by gas-phase OH radicals, which alter the molecular distribution of the reaction products within the droplet. A change in aerosol composition affects the hygroscopicity and leads to a concomitant response in the equilibrium amount of particle-phase water. The variation in the aerosol water content affects the aerosol size and physicochemical properties, which in turn governs the oxidation kinetics and chemistry. To attain better knowledge of the compositional evolution of aqueous organic droplets during oxidation, this work investigates the heterogeneous OH-radical-initiated oxidation of aqueous methylsuccinic acid (C5H8O4) droplets, a model compound for small branched dicarboxylic acids found in atmospheric aerosols, at a high relative humidity of 85 % through experimental and modeling approaches. Aerosol mass spectra measured by a soft atmospheric pressure ionization source (Direct Analysis in Real Time, DART) coupled with a high-resolution mass spectrometer reveal two major products: a five carbon atom (C5) hydroxyl functionalization product (C5H8O5) and a C4 fragmentation product (C4H6O3). These two products likely originate from the formation and subsequent reactions (intermolecular hydrogen abstraction and carbon-carbon bond scission) of tertiary alkoxy radicals resulting from the OH abstraction occurring at the methyl-substituted carbon site. Based on the identification of the reaction products, a kinetic model of oxidation (a two-product model) coupled with the Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model is built to simulate the size and compositional changes of aqueous methylsuccinic acid droplets during oxidation. Model results show that at the maximum OH exposure, the droplets become slightly more hygroscopic after oxidation, as the mass fraction of water is predicted to increase from 0.362 to 0.424; however, the

  2. Compositional evolution of particle-phase reaction products and water in the heterogeneous OH oxidation of model aqueous organic aerosols

    Directory of Open Access Journals (Sweden)

    M. M. Chim


    Full Text Available Organic compounds present at or near the surface of aqueous droplets can be efficiently oxidized by gas-phase OH radicals, which alter the molecular distribution of the reaction products within the droplet. A change in aerosol composition affects the hygroscopicity and leads to a concomitant response in the equilibrium amount of particle-phase water. The variation in the aerosol water content affects the aerosol size and physicochemical properties, which in turn governs the oxidation kinetics and chemistry. To attain better knowledge of the compositional evolution of aqueous organic droplets during oxidation, this work investigates the heterogeneous OH-radical-initiated oxidation of aqueous methylsuccinic acid (C5H8O4 droplets, a model compound for small branched dicarboxylic acids found in atmospheric aerosols, at a high relative humidity of 85 % through experimental and modeling approaches. Aerosol mass spectra measured by a soft atmospheric pressure ionization source (Direct Analysis in Real Time, DART coupled with a high-resolution mass spectrometer reveal two major products: a five carbon atom (C5 hydroxyl functionalization product (C5H8O5 and a C4 fragmentation product (C4H6O3. These two products likely originate from the formation and subsequent reactions (intermolecular hydrogen abstraction and carbon–carbon bond scission of tertiary alkoxy radicals resulting from the OH abstraction occurring at the methyl-substituted carbon site. Based on the identification of the reaction products, a kinetic model of oxidation (a two-product model coupled with the Aerosol Inorganic–Organic Mixtures Functional groups Activity Coefficients (AIOMFAC model is built to simulate the size and compositional changes of aqueous methylsuccinic acid droplets during oxidation. Model results show that at the maximum OH exposure, the droplets become slightly more hygroscopic after oxidation, as the mass fraction of water is predicted to increase from

  3. Tachyon condensation due to domain-wall annihilation in Bose-Einstein condensates. (United States)

    Takeuchi, Hiromitsu; Kasamatsu, Kenichi; Tsubota, Makoto; Nitta, Muneto


    We show theoretically that a domain-wall annihilation in two-component Bose-Einstein condensates causes tachyon condensation accompanied by spontaneous symmetry breaking in a two-dimensional subspace. Three-dimensional vortex formation from domain-wall annihilations is considered a kink formation in subspace. Numerical experiments reveal that the subspatial dynamics obey the dynamic scaling law of phase-ordering kinetics. This model is experimentally feasible and provides insights into how the extra dimensions influence subspatial phase transition in higher-dimensional space.

  4. The effect of solid phase reactions on the ballistic properties of propellants (United States)

    Schmidt, W. G.


    The combustion of NH4ClO4 composite propellants has been studied between 15 and 3000 psi. The emphasis in the program has been on determining the mechanisms by which the fuel components influence the burning rate of the composites. In order to have flexibility in the choice and concentration of the fuel component all combustion experiments were performed with pressed power strands. The fuels studied included those which affected the combustion mechanism of the composite primarily through their effect on: (1) the oxidizer decomposition mechanism and (2) the composite surface temperature. The combustion of pure and doped NH4ClO4 was studied using both pressed powder strands and pressed end burning motor grains. The experimental approach has been essentially a chemical one with emphasis on perturbing those reactions which occur on or immediately adjacent to the surface (zone of influence) of the composite.

  5. Augmented feedback reduces ground reaction forces in the landing phase of the volleyball spike jump. (United States)

    Cronin, John B; Bressel, Eadric; Fkinn, Loren


    Frequency and magnitude of ground reaction forces (GRF) have been implicated in causing injuries such as "jumpers knee." To investigate whether a single session of augmented feedback concerning landing technique would decrease GRF. Pretest posttest experimental design. University biomechanics laboratory. Fifteen female Division 1 intercollegiate volleyball players. Participants were required to land on a force platform after spiking a volleyball from a four-step approach before and after an intervention involving visual and aural augmented feedback on correct jumping and landing technique. Mediolateral (ML), anterioposterior (AP), and vertical (V) GRF normalized to body weight (BW). Augmented feedback was found to significantly (P = 0.01) decrease VGRF by 23.6% but not ML (25%, P = 0.16) and AP (4.9%, P = 0.40) peak GRF. A single session of augmented feedback may be effective in reducing VGRF in collegiate athletes.

  6. Gas-Phase Photocatalytic Oxidation of Dimethylamine: The Reaction Pathway and Kinetics

    Directory of Open Access Journals (Sweden)

    Anna Kachina


    Full Text Available Gas-phase photocatalytic oxidation (PCO and thermal catalytic oxidation (TCO of dimethylamine (DMA on titanium dioxide was studied in a continuous flow simple tubular reactor. Volatile PCO products of DMA included ammonia, formamide, carbon dioxide, and water. Ammonia was further oxidized in minor amounts to nitrous oxide and nitrogen dioxide. Effective at 573 K, TCO resulted in the formation of ammonia, hydrogen cyanide, carbon monoxide, carbon dioxide, and water. The PCO kinetic data fit well to the monomolecular Langmuir-Hinshelwood model, whereas TCO kinetic behaviour matched the first-order process. No deactivation of the photocatalyst during the multiple long-run experiments was observed.


    Energy Technology Data Exchange (ETDEWEB)

    Enright, R; Miljkovic, N; Alvarado, JL; Kim, K; Rose, JW


    In this review we cover recent developments in the area of surface-enhanced dropwise condensation against the background of earlier work. The development of fabrication techniques to create surface structures at the micro-and nanoscale using both bottom-up and top-down approaches has led to increased study of complex interfacial phenomena. In the heat transfer community, researchers have been extensively exploring the use of advanced surface structuring techniques to enhance phase-change heat transfer processes. In particular, the field of vapor-to-liquid condensation and especially that of water condensation has experienced a renaissance due to the promise of further optimizing this process at the micro-and nanoscale by exploiting advances in surface engineering developed over the last several decades.

  8. Simple Simulations of DNA Condensation

    Energy Technology Data Exchange (ETDEWEB)



    Molecular dynamics simulations of a simple, bead-spring model of semiflexible polyelectrolytes such as DNA are performed. All charges are explicitly treated. Starting from extended, noncondensed conformations, condensed structures form in the simulations with tetravalent or trivalent counterions. No condensates form or are stable for divalent counterions. The mechanism by which condensates form is described. Briefly, condensation occurs because electrostatic interactions dominate entropy, and the favored Coulombic structure is a charge ordered state. Condensation is a generic phenomena and occurs for a variety of polyelectrolyte parameters. Toroids and rods are the condensate structures. Toroids form preferentially when the molecular stiffness is sufficiently strong.

  9. Cloud Condensation in Titan's Lower Stratosphere (United States)

    Romani, Paul N.; Anderson, Carrie M.


    A 1-D condensation model is developed for the purpose of reproducing ice clouds in Titan's lower stratosphere observed by the Composite Infrared Spectrometer (CIRS) onboard Cassini. Hydrogen cyanide (HCN), cyanoacetylene (HC3N), and ethane (C2H6) vapors are treated as chemically inert gas species that flow from an upper boundary at 500 km to a condensation sink near Titan's tropopause (-45 km). Gas vertical profiles are determined from eddy mixing and a downward flux at the upper boundary. The condensation sink is based upon diffusive growth of the cloud particles and is proportional to the degree of supersaturation in the cloud formation regIOn. Observations of the vapor phase abundances above the condensation levels and the locations and properties of the ice clouds provide constraints on the free parameters in the model. Vapor phase abundances are determined from CIRS mid-IR observations, whereas cloud particle sizes, altitudes, and latitudinal distributions are derived from analyses of CIRS far-IR observations of Titan. Specific cloud constraints include: I) mean particle radii of2-3 J.lm inferred from the V6 506 cm- band of HC3N, 2) latitudinal abundance distributions of condensed nitriles, inferred from a composite emission feature that peaks at 160/cm , and 3) a possible hydrocarbon cloud layer at high latitudes, located near an altitude of 60 km, which peaks between 60 and 80 cm l . Nitrile abundances appear to diminish substantially at high northern latitudes over the time period 2005 to 2010 (northern mid winter to early spring). Use of multiple gas species provides a consistency check on the eddy mixing coefficient profile. The flux at the upper boundary is the net column chemical production from the upper atmosphere and provides a constraint on chemical pathways leading to the production of these compounds. Comparison of the differing lifetimes, vapor phase transport, vapor phase loss rate, and particle sedimentation, sheds light on temporal stability

  10. Mg2+-induced DNA compaction, condensation, and phase separation in gene delivery vehicles based on zwitterionic phospholipids: a dynamic light scattering and surface-enhanced Raman spectroscopic study. (United States)

    Süleymanoğlu, Erhan


    Despite the significant efforts towards applying improved non-destructive and label-free measurements of biomolecular structures of lipid-based gene delivery vectors, little is achieved in terms of their structural relevance in gene transfections. Better understanding of structure-activity relationships of lipid-DNA complexes and their gene expression efficiencies thus becomes an essential issue. Raman scattering offers a complimentary measurement technique for following the structural transitions of both DNA and lipid vesicles employed for their transfer. This work describes the use of SERS coupled with light scattering approaches for deciphering the bioelectrochemical phase formations between nucleic acids and lipid vesicles within lipoplexes and their surface parameters that could influence both the uptake of non-viral gene carriers and the endocytic routes of interacting cells. As promising non-viral alternatives of currently employed risky viral systems or highly cytotoxic cationic liposomes, complexations of both nucleic acids and zwitterionic lipids in the presence of Mg 2+ were studied applying colloidal Ag nanoparticles. It is shown that the results could be employed in further conformational characterizations of similar polyelectrolyte gene delivery systems.

  11. Phase Reactions Between Refractory and High-Acidic Synthetic CaO-Ferronickel Slag (United States)

    Sagadin, Christoph; Luidold, Stefan; Wagner, Christoph; Spanring, Alfred; Kremmer, Thomas


    Interactions between high melting synthetic ferronickel slags with acidic character and MgO as refractory were investigated. In order to facilitate the complex composition of real ferronickel slag, a synthetic slag of SiO2-MgO-Fe2O3-CaO was used. The practical corrosion tests of the MgO refractory were performed in a hot-stage microscope at temperatures of 1650°C under a CO/CO2 atmosphere for process-oriented conditions. The formed phases between slag and magnesia substrate were analyzed by scanning electron microscope analysis. The results show that, by penetrating the slag into the refractory, the melt dissolves the magnesia and forms Mg- and Ca silicates. Furthermore, a diffusion of Fe from the slag into the magnesia grains can be observed and a transformation to magnesiowustite occurs. Thermodynamic phase calculations using FactSage software confirmed the generation of these minerals. The combination of practical testing and thermodynamic calculations should ultimately provide a path for improving the refractory lifetime and performance.

  12. Colloidal polymer particles as catalyst carriers and phase transfer agents in multiphasic hydroformylation reactions. (United States)

    Peral, D; Stehl, D; Bibouche, B; Yu, H; Mardoukh, J; Schomäcker, R; Klitzing, R von; Vogt, D


    Colloidal particles have been used to covalently bind ligands for the heterogenization of homogeneous catalysts. The replacement of the covalent bonds by electrostatic interactions between particles and the catalyst could preserve the selectivity of a truly homogeneous catalytic process. Functionalized polymer particles with trimethylammonium moieties, dispersed in water, with a hydrophobic core and a hydrophilic shell have been synthesized by emulsion polymerization and have been thoroughly characterized. The ability of the particles with different monomer compositions to act as catalyst carriers has been studied. Finally, the colloidal dispersions have been applied as phase transfer agents in the multiphasic rhodium-catalyzed hydroformylation of 1-octene. The hydrodynamic radius of the particles has been shown to be around 100 nm, and a core-shell structure could be observed by atomic force microscopy. The polymer particles were proven to act as carriers for the water-soluble hydroformylation catalyst, due to electrostatic interaction between the functionalized particles bearing ammonium groups and the sulfonated ligands of the catalyst. The particles were stable under the hydroformylation conditions and the aqueous catalyst phase could be recycled three times. Copyright © 2017 Elsevier Inc. All rights reserved.

  13. Electrons in Condensed Matter

    Indian Academy of Sciences (India)

    entire liquid or solid. The variety of electronic behaviour which ... sity of electronic behaviour in condensed matter, ego ferro- ..... a big dog? We do not know the reasons yet. As it turns out for many fundamentally interesting phenomena, colossal magneto- resistance may also find applications, this time in magnetic recording.

  14. Bose-Einstein Condensation

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 5; Issue 4. Bose–Einstein Condensation - Birds of a Feather Flock Together. Rajaram Nityananda. General Article Volume 5 Issue 4 April 2000 pp 46-51. Fulltext. Click here to view fulltext PDF. Permanent link:

  15. Electrons in Condensed Matter

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 2; Issue 12. Electrons in Condensed Matter. T V Ramakrishnan. General Article Volume 2 Issue 12 December 1997 pp 17-32. Fulltext. Click here to view fulltext PDF. Permanent link: ...

  16. Bose-Einstein Condensation

    Indian Academy of Sciences (India)

    gas of photons which explained Planck's law for thermal radiation at one ... their first application. Seventy years later they are being used in atomic physics laboratories all over the world. Everybody is talking about Bose-Einstein condensation. This ... distribution of the position of any particle in the gas is a constant function ...

  17. Bose-Einstein Condensation

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 10; Issue 12. Bose-Einstein Condensation - Birds of a Feather Flock Together. Rajaram Nityananda. Volume 10 Issue 12 December 2005 pp 142-147. Fulltext. Click here to view fulltext PDF. Permanent link:

  18. Condensed-Matter Physics. (United States)

    Hirsch, Jorge E.; Scalapino, Douglas J.


    Discusses ways computers are being used in condensed-matter physics by experimenters and theorists. Experimenters use them to control experiments and to gather and analyze data. Theorists use them for detailed predictions based on realistic models and for studies on systems not realizable in practice. (JN)

  19. Modular invariant gaugino condensation

    Energy Technology Data Exchange (ETDEWEB)

    Gaillard, M.K.


    The construction of effective supergravity lagrangians for gaugino condensation is reviewed and recent results are presented that are consistent with modular invariance and yield a positive definite potential of the noscale type. Possible implications for phenomenology are briefly discussed. 29 refs.

  20. Amphiphilic phase-transforming catalysts for transesterification of triglycerides (United States)

    Nawaratna, Gayan Ivantha

    Heterogeneous catalytic reactions that involve immiscible liquid-phase reactants are challenging to conduct due to limitations associated with mass transport. Nevertheless, there are numerous reactions such as esterification, transesterification, etherification, and hydrolysis where two immiscible liquid reactants (such as polar and non-polar liquids) need to be brought into contact with a catalyst. With the intention of alleviating mass transport issues associated with such systems but affording the ability to separate the catalyst once the reaction is complete, the overall goal of this study is geared toward developing a catalyst that has emulsification properties as well as the ability to phase-transfer (from liquid-phase to solid-phase) while the reaction is ongoing and evaluating the effectiveness of such a catalytic process in a practical reaction. To elucidate this concept, the transesterification reaction was selected. Metal-alkoxides that possess acidic and basic properties (to catalyze the reaction), amphiphilic properties (to stabilize the alcohol/oil emulsion) and that can undergo condensation polymerization when heated (to separate as a solid subsequent to the completion of the reaction) were used to test the concept. Studies included elucidating the effect of metal sites and alkoxide sites and their concentration effects on transesterification reaction, effect of various metal alkoxide groups on the phase stability of the reactant system, and kinetic effects of the reaction system. The studies revealed that several transition-metal alkoxides, especially, titanium and yttrium based, responded positively to this reaction system. These alkoxides were able to be added to the reaction medium in liquid phase and were able to stabilize the alcohol/oil system. The alkoxides were selective to the transesterification reaction giving a range of ester yields (depending on the catalyst used). It was also observed that transition-metal alkoxides were able to be

  1. Experimental Investigation of Flow Condensation in Microgravity (United States)

    Lee, Hyoungsoon; Park, Ilchung; Konishi, Christopher; Mudawar, Issam; May, Rochelle I.; Juergens, Jeffery R.; Wagner, James D.; Hall, Nancy R.; Nahra, Henry K.; Hasan, Mohammed M.; hide


    Future manned missions to Mars are expected to greatly increase the space vehicle's size, weight, and heat dissipation requirements. An effective means to reducing both size and weight is to replace single-phase thermal management systems with two-phase counterparts that capitalize upon both latent and sensible heat of the coolant rather than sensible heat alone. This shift is expected to yield orders of magnitude enhancements in flow boiling and condensation heat transfer coefficients. A major challenge to this shift is a lack of reliable tools for accurate prediction of two-phase pressure drop and heat transfer coefficient in reduced gravity. Developing such tools will require a sophisticated experimental facility to enable investigators to perform both flow boiling and condensation experiments in microgravity in pursuit of reliable databases. This study will discuss the development of the Flow Boiling and Condensation Experiment (FBCE) for the International Space Station (ISS), which was initiated in 2012 in collaboration between Purdue University and NASA Glenn Research Center. This facility was recently tested in parabolic flight to acquire condensation data for FC-72 in microgravity, aided by high-speed video analysis of interfacial structure of the condensation film. The condensation is achieved by rejecting heat to a counter flow of water, and experiments were performed at different mass velocities of FC-72 and water and different FC-72 inlet qualities. It is shown that the film flow varies from smooth-laminar to wavy-laminar and ultimately turbulent with increasing FC-72 mass velocity. The heat transfer coefficient is highest near the inlet of the condensation tube, where the film is thinnest, and decreases monotonically along the tube, except for high FC-72 mass velocities, where the heat transfer coefficient is enhanced downstream. This enhancement is attributed to both turbulence and increased interfacial waviness. One-ge correlations are shown to

  2. Compositional Simulation of a Refinery Coker Furnace - An Industrial Example of Two-Phase Flow with Chemical Reaction

    Directory of Open Access Journals (Sweden)

    Sigurd Skogestad


    Full Text Available A computer program (KOKSOVN has been developed for compositional steady-state simulation of a refinery delayed coker furnace. The main objective of this work has been to establish a tool for studying the effects that influence the deposition of coke on the inside walls of the tubes in order to maximize the time of operation (cycle time between each cleaning of the tubes with a resulting stop in production. The program basically consists of a standard integration package which steps along the reactor (or pipeline while solving the vapour-liquid equilibrium (VLE and estimating physical properties for each step. Using a modular approach in the development, the resulting computer program has some general features which make it a possible simulation tool for any non-adiabatic plug flow reactor with two-phase flow. Depending on the chemical system, the routines for thermophysical and transport properties, phase equilibria and chemical reaction may be replaced by other methods. The program may also be used to simulate a pipeline with one or two-phase flow. Since, however, the total composition in this case is constant, it would probably be more efficient to use tables based on the pressure values, instead of performing tedious VLE calculations along the pipeline as is done in the present program.

  3. Approaching Bose-Einstein condensation

    Energy Technology Data Exchange (ETDEWEB)

    Ferrari, Loris, E-mail: [Department of Physics of the University, Viale B. Pichat, 6/2, 40127, Bologna (Italy)


    Bose-Einstein condensation (BEC) is discussed at the level of an advanced course of statistical thermodynamics, clarifying some formal and physical aspects that are usually not covered by the standard pedagogical literature. The non-conventional approach adopted starts by showing that the continuum limit, in certain cases, cancels out the crucial role of the bosonic ground level. If so, a correct treatment of the problem, including the ground level population N{sub 0} by construction, leads to BEC in a straightforward way. For a density of states of the form G({epsilon}){approx}{epsilon}{sup {gamma}}, the chemical potential {mu} is explicitly calculated as a function of the temperature T and of the number N of bosons, for various significant values of the positive exponent {gamma}. In the thermodynamic limit, in which the boson number N diverges and BEC is a sharp process, the chemical potential {mu} is a singular function of T at the critical temperature T{sub B}, determined by an appropriate critical exponent. The condensate population N{sub 0} is studied analytically and numerically as a function of the temperature, for various values of N and for different {gamma}. This provides an accurate description of the way BEC approaches the character of a sharp phase transition. Some aspects of the real experiments on BEC, involving a finite number of bosons, are also illustrated.

  4. Structure of vacuum Cu-Ta condensates (United States)

    Zubkov, A. I.; Zubarev, E. N.; Sobol', O. V.; Hlushchenko, M. A.; Lutsenko, E. V.


    The structure of vacuum condensate foils (separated from substrates) of the binary Cu-Ta system has been investigated both in the initial condensed state and after annealings at temperatures of up to 1000°C. It has been shown that the alloying of a vapor flow of the matrix metal (copper) with tantalum to 0.5 at % makes it possible to reduce the grain size from 3 μm to 50 nm. Depending on the tantalum concentration, condensates exhibit a broad spectrum of structural states, i.e., single- and two-phase, a supersaturated solution of tantalum in the fcc lattice of copper, etc. The structure of the objects possesses a high thermal stability. The temperature of the start of grain growth in the copper matrix depends on the tantalum content and can reach 900°C. The dispersion of the structure of copper condensates and its thermal stability is due to the formation of segregates of tantalum atoms at the boundaries of grains of the copper matrix both in the process of condensation and upon subsequent annealing.

  5. A superheated Bose-condensed gas (United States)

    Gaunt, Alexander L.; Fletcher, Richard J.; Smith, Robert P.; Hadzibabic, Zoran


    Our understanding of various states of matter usually relies on the assumption of thermodynamic equilibrium. However, the transitions between different phases of matter can be strongly affected by non-equilibrium phenomena. Here we demonstrate and explain an example of non-equilibrium stalling of a continuous, second-order phase transition. We create a superheated atomic Bose gas, in which a Bose-Einstein condensate (BEC) persists above the equilibrium critical temperature, Tc, if its coupling to the surrounding thermal bath is reduced by tuning interatomic interactions. For vanishing interactions the BEC persists in the superheated regime for a minute. However, if strong interactions are suddenly turned on, it rapidly boils away. Our observations can be understood within a two-fluid picture, treating the condensed and thermal components of the gas as separate equilibrium systems with a tunable inter-component coupling. We experimentally reconstruct a non-equilibrium phase diagram of our gas, and theoretically reproduce its main features.

  6. From dimer to condensed phases at extreme conditions: accurate predictions of the properties of water by a Gaussian charge polarizable model. (United States)

    Paricaud, Patrice; Predota, Milan; Chialvo, Ariel A; Cummings, Peter T


    Water exhibits many unusual properties that are essential for the existence of life. Water completely changes its character from ambient to supercritical conditions in a way that makes it possible to sustain life at extreme conditions, leading to conjectures that life may have originated in deep-sea vents. Molecular simulation can be very useful in exploring biological and chemical systems, particularly at extreme conditions for which experiments are either difficult or impossible; however this scenario entails an accurate molecular model for water applicable over a wide range of state conditions. Here, we present a Gaussian charge polarizable model (GCPM) based on the model developed earlier by Chialvo and Cummings [Fluid Phase Equilib. 150, 73 (1998)] which is, to our knowledge, the first that satisfies the water monomer and dimer properties, and simultaneously yields very accurate predictions of dielectric, structural, vapor-liquid equilibria, and transport properties, over the entire fluid range. This model would be appropriate for simulating biological and chemical systems at both ambient and extreme conditions. The particularity of the GCPM model is the use of Gaussian distributions instead of points to represent the partial charges on the water molecules. These charge distributions combined with a dipole polarizability and a Buckingham exp-6 potential are found to play a crucial role for the successful and simultaneous predictions of a variety of water properties. This work not only aims at presenting an accurate model for water, but also at proposing strategies to develop classical accurate models for the predictions of structural, dynamic, and thermodynamic properties.

  7. Investigating tunable KRb gases and Bose-Einstein condensates

    DEFF Research Database (Denmark)

    Jørgensen, Nils Byg


    We present the production of dual-species Bose-Einstein condensates of 39K and 87Rb with tunable interactions. A dark spontaneous force optical trap was used for 87Rb to reduce the losses in 39K originating from light-assisted collisions in the magneto optical trapping phase. Using sympathetic...... for dual-species condensates with tunable interactions. Employing the dual-species condensates, the miscible to immiscible phase transition was investigated. By applying an empirical model, the transition was used to determine the background scattering length. Two species quantum gases with tunable...

  8. Solid-Phase Iminium Cyclization Reactions for the Synthesis of Natural Product-Like Diketopiperazines

    DEFF Research Database (Denmark)

    Petersen, Rico

    -suited for the synthesis of diastereoisomeric mixtures of 2,5-diketopiperazino[6,1-a]tetrahydroisoquinolines in high purities (74 to 90%), allowing for the separation of the cis-diastereoisomers. The route based on glyoxylic acid was found to be cis-stereoselective (1:2) generating the 2,5-diketopiperazino[6,1-a......The development of methodology for the solid-phase synthesis of fused 2,5-diketopiperazines with an emphasis on structural and stereochemical control, has been accomplished through two different approaches. The first approach was based on a highly trans-stereoselective (82% d.e.) intramolecular N...... formation to close the second ring. In the first approach, four different methods for accessing the glyoxylamide cyclization precursor were developed; oxidative cleavage of a serine, dihydroxylation/oxidative cleavage of an acrylamide, oxidation of a glycolamide and acidic release from a diethoxy acetamide...

  9. In search of efficient catalysts and appropriate reaction conditions for gas phase nitration of benzene

    Directory of Open Access Journals (Sweden)

    Anton P. Koskin


    Full Text Available The present paper is dedicated to the development of a method for the nitrobenzene production using solid acid catalysts, as an alternative to industrial nitration, based on a mixture of concentrated acids. The influence of key parameters of the nitration process (temperature, reagent flow rate, nitrating agent concentration etc. on the conversion of the initial substrate, the degree of decomposition of nitric acid and the quantity of resulting oxygenates was studied. Recommendations for the selection of effective catalytic systems (high content of Brønsted acid sites with Ho < −4, high specific surface and resistance to HNO3 were developed and the best conditions for process reactions (temperature 200 °C, aqueous solution of nitric acid with concentration of 30 wt%, “nitric acid:benzene” ratio = 0.76 were found. A method for regeneration of the catalytic activity without unloading the catalyst was proposed. As an example, MoO3/SiO2 sample was tested in a dual-mode nitration/regeneration process, which allowed us to increase the flow rates of reagents and obtain catalyst efficiency of up to STY = 4.09 g/(gcat ⋅ h. Several of the most promising catalysts (MoO3/SiO2, WO3/ZrO2 and Nafion/support composite for the process were tested in identical conditions.

  10. Control of chemical reactions with electron beams; Kontrolle chemischer Reaktionen mit Elektronenstrahlung

    Energy Technology Data Exchange (ETDEWEB)

    Boehler, Esther


    Interaction between low-energy electrons and molecules can lead to dissociative electron attachment (DEA) or dissociative ionization (DI). In condensed matter, the resulting reactive fragments can attack adjacent molecules to yield larger products. In this thesis, reactions initiated by DEA to acetonitrile in condensed phase have been compared to the known gas phase fragmentation channels. Also, gas phase DEA experiments have been performed on chlorosilanes to study the effect of a variation of the organic ligands on the energy of their molecular orbitals and reactivity in DEA processes. Furthermore, hydroamination reactions induced by DI for different alkenes and amines have been investigated. A similar reaction of ammonia and carbon monoxide was shown to produce formamide (HCONH2), which is the smallest molecule to contain a peptide bond and thus represents an important building block of biologically relevant substances.

  11. Aqueous-Phase Reactions of Isoprene with Sulfoxy Radical Anions as a way of Wet Aerosol Formation in the Atmosphere (United States)

    Kuznietsova, I.; Rudzinski, K. J.; Szmigielski, R.; Laboratory of the Environmental Chemistry


    Atmospheric aerosols exhibit an important role in the environment. They have implications on human health and life, and - in the larger scale - on climate, the Earth's radiative balance and the cloud's formation. Organic matter makes up a significant fraction of atmospheric aerosols (~35% to ~90%) and may originate from direct emissions (primary organic aerosol, POA) or result from complex physico-chemical processes of volatile organic compounds (secondary organic aerosol, SOA). Isoprene (2-methyl-buta-1,3-diene) is one of the relevant volatile precursor of ambient SOA in the atmosphere. It is the most abundant non-methane hydrocarbon emitted to the atmosphere as a result of living vegetation. According to the recent data, the isoprene emission rate is estimated to be at the level of 500 TgC per year. While heterogeneous transformations of isoprene have been well documented, aqueous-phase reactions of this hydrocarbon with radical species that lead to the production of new class of wet SOA components such as polyols and their sulfate esters (organosulfates), are still poorly recognized. The chain reactions of isoprene with sulfoxy radical-anions (SRA) are one of the recently researched route leading to the formation of organosulfates in the aqueous phase. The letter radical species originate from the auto-oxidation of sulfur dioxide in the aqueous phase and are behind the phenomenon of atmospheric acid rain formation. This is a complicated chain reaction that is catalyzed by transition metal ions, such as manganese(II), iron(III) and propagated by sulfoxy radical anions . The presented work addresses the chemical interaction of isoprene with sulfoxy radical-anions in the water solution in the presence of nitrite ions and nitrous acid, which are important trace components of the atmosphere. We showed that nitrite ions and nitrous acid significantly altered the kinetics of the auto-oxidation of SO2 in the presence of isoprene at different solution acidity from 2 to 8

  12. Substantial Cd-Cd bonding in Ca6PtCd11: a condensed intermetallic phase built of pentagonal Cd7 and rectangular Cd4/2Pt pyramids. (United States)

    Gulo, Fakhili; Samal, Saroj L; Corbett, John D


    The novel intermetallic Ca6PtCd11 is orthorhombic, Pnma, Z = 4, with a = 18.799(2) Å, b = 5.986(1) Å, c = 15.585(3) Å. The heavily condensed network contains three types of parallel cadmium chains: apically strongly interbonded Cd7 pentagonal bipyramids, linear Cd arrays, and rectangular Cd4/2Pt pyramids. All of the atoms have 11-13 neighbors. Calculations by means of the linear muffin-tin orbitals method in the atomic spheres approximation indicate that some Cd-Cd interactions correspond to notably high Hamilton populations (1.07 eV per average bond) whereas the Ca-Ca covalent interactions (integrated crystal orbital Hamiltonian population) are particularly small (0.17 eV/bond). (Pt-Cd interactions are individually greater but much less in aggregate.) The Ca-Ca separations are small, appreciably less than the single bond metallic diameters, and unusually uniform (Δ = 0.14 Å). The Cd atoms make major contributions to the stability of the phase via substantial 5s and 5p bonding, which include back-donation of Cd 5s, 5p and Pt 5d into Ca 3d states in the principal bonding modes for Ca-Cd and Ca-Pt. Bonding Ca-Ca, Ca-Cd, and Cd-Cd states remain above EF, and some relative oxidation of Ca in this structure seems probable. Ca6PtCd11 joins a small group of other phases in which Cd clustering and Cd-Cd bonding are important.

  13. An overview of dehydration, aldol-condensation and hydrogenation processes for production of liquid alkanes from biomass-derived carbohydrates

    Energy Technology Data Exchange (ETDEWEB)

    Chheda, Juben N.; Dumesic, James A. [University of Wisconsin-Madison, Department of Chemical and Biological Engineering, Madison, WI 53706 (United States)


    We present results for the conversion of carbohydrate feedstocks to liquid alkanes by the combination of dehydration, aldol-condensation/hydrogenation, and dehydration/hydrogenation processing. With respect to the first dehydration step, we demonstrate that HMF can be produced in good selectivity from abundantly available polysaccharides (such as inulin, sucrose) containing fructose monomer units using a biphasic batch reactor system. The reaction system can be optimized to achieve good yields to 5-hydroxymethylfurfural (HMF) from fructose by varying the contents of aqueous-phase modifiers such as dimethylsulfoxide (DMSO) and 1-methyl-2-pyrrolidinone (NMP). Regarding the aldol-condensation/hydrogenation step, we present the development of stable, solid base catalysts in aqueous environments. We address the effects of various reaction parameters such as the molar ratio of reactants and temperature on overall product yield for sequential aldol-condensation and hydrogenation steps. Overall, our results show that it is technically possible to convert carbohydrate feedstocks to produce liquid alkanes by the combination of dehydration, aldol-condensation/hydrogenation, and dehydration/hydrogenation processing; however, further optimization of these processes is required to decrease the overall number of separate steps (and reactors) required in this conversion. (author)

  14. First Principles Based Simulation of Reaction-Induced Phase Transition in Hydrogen Storage and Other Materials

    Energy Technology Data Exchange (ETDEWEB)

    Ge, Qingfeng [Southern Illinois Univ., Carbondale, IL (United States)


    This major part of this proposal is simulating hydrogen interactions in the complex metal hydrides. Over the period of DOE BES support, key achievements include (i) Predicted TiAl3Hx as a precursor state for forming TiAl3 through analyzing the Ti-doped NaAlH4 and demonstrated its catalytic role for hydrogen release; (ii) Explored the possibility of forming similar complex structures with other 3d transition metals in NaAlH4 as well as the impact of such complex structures on hydrogen release/uptake; (iii) Demonstrated the role of TiAl3 in hydriding process; (iv) Predicted a new phase of NaAlH4 that links to Na3AlH6 using first-principles metadynamics; (v) Examined support effect on hydrogen release from supported/encapsulated NaAlH4; and (vi) Expanded research scope beyond hydrogen storage. The success of our research is documented by the peer-reviewed publications.

  15. Phase diagram and complex patterns in the modeling of the bromate-oxalic acid-Ce-acetone oscillating reaction

    Directory of Open Access Journals (Sweden)

    Janaina A. M. Pereira


    Full Text Available Simulations have been carried out on the bromate - oxalic acid - Ce(IV - acetone oscillating reaction, under flow conditions, using Field and Boyd's model (J. Phys. Chem. 1985, 89, 3707. Many different complex dynamic behaviors were found, including simple periodic oscillations, complex periodic oscillations, quasiperiodicity and chaos. Some of these complex oscillations can be understood as belonging to a Farey sequence. The many different behaviors were systematized in a phase diagram which shows that some regions of complex patterns were nested with one inside the other. The existence of almost all known dynamic behavior for this system allows the suggestion that it can be used as a model for some very complex phenomena that occur in biological systems.

  16. The effect of salmeterol and salbutamol on mediator release and skin responses in immediate and late phase allergic cutaneous reactions

    DEFF Research Database (Denmark)

    Petersen, Lars Jelstrup; Skov, P S


    BACKGROUND: Salmeterol is a long-acting beta2-agonist which in animal studies has been shown to possess anti-inflammatory effects on early (EAR) and late (LPR) phase allergic responses. PURPOSE: To evaluate the anti-inflammatory effects of intradermally injected salmeterol and salbutamol......, myeloperoxidase, or eosinophil cationic protein in LPR. CONCLUSIONS: Salmeterol and salbutamol inhibited allergen-induced skin responses, and reduced mediator release in EAR but not LPR. In general, the anti-inflammatory effects of salmeterol did not differ from those induced by salbutamol....... on clinical and biochemical EAR and LPR in human skin. METHODS: Measurement of wheal and flare reactions to allergen, codeine, and histamine, and LPR (induration) to allergen. Assessment of histamine and prostaglandin D2 (PGD2) release by microdialysis technique in EAR, and measurement of mediators in LPR...

  17. Comparative analysis of the gas-phase reactions of cylindrospermopsin and the difference in the alkali metal cation mobility. (United States)

    Dörr, Felipe Augusto; Tomaz, José Carlos; Lopes, Norberto Peporine; Pinto, Ernani


    Cylindrospermopsin (CYN) belongs to a group of toxins produced by several strains of freshwater cyanobacteria. It is a compact zwitterionic molecule composed of a uracil section and a tricyclic guanidinium portion with a primarily hepatotoxic effect. Using low multi-stage and high-resolution mass spectrometry, the gas-phase reactions of this toxin have been investigated. Our data show that collision-induced dissociation (CID) spectra of CYN are dominated by neutral losses, and three major initial fragmentation pathways are clearly distinguishable. Interestingly, comparative analysis of protonated and cationizated molecules showed a significant difference in the balance of the SO3 and terminal ring elimination. These data indicate that the differential ion mobility of H+, Li+, Na+ and K+ leads to different fragmentation pathways, giving rise to mass spectra with different profiles.

  18. Reversed-phase ion-pair liquid chromatographic method for determination of reaction equilibria involving ionic species: exemplification of the method using ligand substitution reactions of ethylenediaminetetraacetatochromium(III) ion with acetate and phosphate ions. (United States)

    Sato, Emiko; Miya, Seiko; Saitoh, Kazunori; Saito, Shingo; Shibukawa, Masami


    A reversed-phase ion-pair liquid chromatographic method is presented for the determination of reaction equilibria involving ionic species of the same charge sign as reactant and product compounds. It has been demonstrated that ion-exchange chromatography or reversed-phase ion-pair chromatography is a useful tool for the determination of equilibrium constants of chemical reactions involving ionic species such as metal complexation reactions. Previous work with these methods has been based on the assumption that the limiting retention factors of the reactant and product species are constant independent of concentration of the chemical species (X) in the mobile phase, which reacts with the analyte compound. However, when all the reactant and product species are ions of the same charge sign as that of the species X, it is virtually impossible to apply these methods to the equilibrium constant determination because the retention factors of both the reactant and product species may depend on the concentration of X. In this study, an alternative approach was developed that estimates the limiting retention factors of ionic species from the dependence of the retention factor on the ionic strength of the mobile phase. Ligand substitution reactions of ethylenediaminetetraacetatochromium(III) ion with acetate and phosphate ions were used as model reactions to test this method. The equilibrium constants determined by this method are in good agreement with those obtained by a UV-visible spectrophotometric method. Copyright © 2010 Elsevier B.V. All rights reserved.

  19. Condensing Organic Aerosols in a Microphysical Model (United States)

    Gao, Y.; Tsigaridis, K.; Bauer, S.


    The condensation of organic aerosols is represented in a newly developed box-model scheme, where its effect on the growth and composition of particles are examined. We implemented the volatility-basis set (VBS) framework into the aerosol mixing state resolving microphysical scheme Multiconfiguration Aerosol TRacker of mIXing state (MATRIX). This new scheme is unique and advances the representation of organic aerosols in models in that, contrary to the traditional treatment of organic aerosols as non-volatile in most climate models and in the original version of MATRIX, this new scheme treats them as semi-volatile. Such treatment is important because low-volatility organics contribute significantly to the growth of particles. The new scheme includes several classes of semi-volatile organic compounds from the VBS framework that can partition among aerosol populations in MATRIX, thus representing the growth of particles via condensation of low volatility organic vapors. Results from test cases representing Mexico City and a Finish forrest condistions show good representation of the time evolutions of concentration for VBS species in the gas phase and in the condensed particulate phase. Emitted semi-volatile primary organic aerosols evaporate almost completely in the high volatile range, and they condense more efficiently in the low volatility range.

  20. Cyclosporine A eye drops inhibit the early-phase reaction in a type-I allergic conjunctivitis model in mice. (United States)

    Shii, Daisuke; Oda, Tomoko; Shinomiya, Katsuhiko; Katsuta, Osamu; Nakamura, Masatsugu


    The effects of cyclosporine A eye drops on the early-phase reaction were investigated in a type-I allergic conjunctivitis model. Mice were actively sensitized with ragweed (RW) absorbed on aluminium hydroxide gel and challenged with RW for 10 days (single challenge model) or 10-14 days (repetitive challenge model) after the first sensitization. For the evaluation of itching, ovalbumin was used as an antigen instead of RW. The effects of cyclosporine A eye drops on increased vascular permeability, mast cell degranulation, and itching were evaluated and compared with those of other anti-allergic eye drops. In the single challenge model, cyclosporine A eye drops significantly inhibited the increase in vascular permeability and histological evaluations showed suppressed degranulation of mast cells. Disodium cromoglycate (DSCG) eye drops showed only a slight tendency to inhibit the increase in both pathophysiological parameters. Ketotifen or betamethasone eye drops significantly inhibited the increase in vascular permeability. The order of potency in the single challenge model was ketotifen > cyclosporine A > betamethasone. In the repetitive challenge model, cyclosporine A eye drops significantly inhibited the increase in vascular permeability and DSCG eye drops showed only slight inhibition. Ketotifen or betamethasone significantly inhibited the increase in vascular permeability. The order of potency in the repetitive challenge model was cyclosporine A > betamethasone > ketotifen. The effect of cyclosporine A eye drops on the itch-scratch response was studied. Cyclosporine A and DSCG significantly reduced the itch-scratch response in the single and repetitive challenge models; the effect of cyclosporine A in the repetitive challenge model was more potent than in the single challenge model. Those results suggest that administration of cyclosporine A eye drops inhibit the early-phase reaction in type-I allergic conjunctivitis, which may be mediated by the suppression of

  1. Immunological and clinical factors associated with adverse systemic reactions during the build-up phase of honeybee venom immunotherapy. (United States)

    Korošec, P; Žiberna, K; Šilar, M; Dežman, M; Čelesnik Smodiš, N; Rijavec, M; Kopač, P; Eržen, R; Lalek, N; Bajrović, N; Košnik, M; Zidarn, M


    Adverse systemic reactions (SRs) are more common in honeybee venom immunotherapy (VIT) than in wasp VIT. Factors that might be associated with SRs during the honeybee VIT are poorly understood. Our aim was to evaluate risk factors for SRs during the build-up phase of honeybee venom immunotherapy. We included 93 patients who underwent ultra-rush honeybee VIT. The adverse SRs and their severity was compared to various immunological (sIgE, tIgE, basophil CD63 response, baseline tryptase, and skin tests), patient-specific (age, sex, cardiovascular conditions and medications, and other allergic diseases), and sting-specific factors (anaphylaxis severity, time interval to onset of symptoms, and absence of cutaneous symptoms). Twenty-three patients (24.7%) experienced mild SRs and 13 patients (14%) severe SRs. In five patients with severe SRs, the build-up was stopped. High basophil allergen sensitivity, evaluated as dose-response curve metrics of EC15, EC50, CD-sens, AUC, or the response to submaximal 0.01 μg/mL of venom concentration, was the most significant risk factor and only independent predictor of severe SRs and/or build-up stop. Time interval of build-up phase of honeybee VIT. Possibly role was also showed for short latency to filed sting reaction and low sIgE to rApi m1. Before honeybee VIT, measurement of basophil allergen sensitivity should be used to identify patients with a high risk for severe side-effects. © 2015 John Wiley & Sons Ltd.

  2. Statistical physics and condensed matter

    Energy Technology Data Exchange (ETDEWEB)



    This document is divided into 4 sections: 1) General aspects of statistical physics. The themes include: possible geometrical structures of thermodynamics, the thermodynamical foundation of quantum measurement, transport phenomena (kinetic theory, hydrodynamics and turbulence) and out of equilibrium systems (stochastic dynamics and turbulence). The techniques involved here are typical of applied analysis: stability criteria, mode decomposition, shocks and stochastic equations. 2) Disordered, glassy and granular systems: statics and dynamics. The complexity of the systems can be studied through the structure of their phase space. The geometry of this phase space is studied in several works: the overlap distribution can now be computed with a very high precision; the boundary energy between low lying states does not behave like in ordinary systems; and the Edward's hypothesis of equi-probability of low lying metastable states is invalidated. The phenomenon of aging, characteristic of glassy dynamics, is studied in several models. Dynamics of biological systems or of fracture is shown to bear some resemblance with that of disordered systems. 3) Quantum systems. The themes include: mesoscopic superconductors, supersymmetric approach to strongly correlated electrons, quantum criticality and heavy fermion compounds, optical sum rule violation in the cuprates, heat capacity of lattice spin models from high-temperature series expansion, Lieb-Schultz-Mattis theorem in dimension larger than one, quantum Hall effect, Bose-Einstein condensation and multiple-spin exchange model on the triangular lattice. 4) Soft condensed matter and biological systems. Path integral representations are invaluable to describe polymers, proteins and self-avoiding membranes. Using these methods, problems as diverse as the titration of a weak poly-acid by a strong base, the denaturation transition of DNA or bridge-hopping in conducting polymers have been addressed. The problems of RNA folding

  3. functional site: Study towards benzoin condensation and Baylis ...

    Indian Academy of Sciences (India)

    benzimidazolium salts were synthesized in very good yield. Subsequently, these ... products were observed in good yield. Similarly, the ...... good yields. The new molecules 3a–8a were used as organocatalysts in benzoin condensation reactions. Cat- alyst 3a was very selective towards benzoin condensa- tion reaction ...

  4. Morphology of self assembled monolayers using liquid phase reaction on silica and their effect on the morphology of adsorbed insulin (United States)

    Sharma, Indu; Pattanayek, Sudip K.; Aggarwal, Varsha; Ghosh, Subhasis


    The effect of roughness of two different categories of self-assembled monolayers (SAMs) with propyl amine and propyl groups respectively on the morphology of adsorbed insulin is observed. SAMs are obtained by liquid phase reaction of silica with organo silane coupling agents (SCA). The influence of the morphology and physical characteristics of the SAMs on the reaction time and concentration of the modifiers are explored. We have tested three SCA containing propyl amine with varying groups linked to Si present on it. In addition, we have used a silane coupling agent to prepare SAM of methyl head group. The approach of these molecules towards the surface depends on the head group and the groups linked to Si of the SCA. The morphology of the surfaces is analysed using power spectral density distribution (PSD), skewness, ellipsometry thickness and surface energy. Both chemical nature and physical morphology of the adsorbent influence the morphology of the adsorbed insulin. In general, a low number of aggregates of big size are formed on the surfaces obtained from low concentration of SAMs, while a higher number but of smaller size of aggregates are formed over surfaces obtained from 1% concentration of SAMs modifiers. The peak to valley ratio of the aggregates of insulin is strongly influenced by the size of grains of SCA over the adsorbent.

  5. Gas-Phase Reactions of Glyceraldehyde and 1,3-Dihydroxyacetone as Models for Levoglucosan Conversion during Biomass Gasification. (United States)

    Fukutome, Asuka; Kawamoto, Haruo; Saka, Shiro


    Levoglucosan, the major intermediate in wood gasification, is decomposed selectively to C1/C2 fragments at 550-600 °C. Kinetic analyses suggest that radical chain mechanisms with the involvement of short-lived carbonyl intermediates explain the lower production of larger fragments. To address this hypothesis, the gas-phase reactivities of glyceraldehyde (Gald), 1,3-dihydroxyacetone (DHA), and glycerol, as simple C3 model compounds, were compared at 400-800 °C under N2 flow at residence times of 0.9-1.4 s. Retro-aldol fragmentation and dehydration proceeded for the pyrolysis of Gald/DHA at 400 °C, far below the 600 °C decomposition point of glycerol. Pyrolysis of Gald/DHA generated exclusively syngas (CO and H2). On the basis of the results of theoretical calculations, the effects of carbonyl intermediates on reactivity were explained by postulating uni- and bimolecular reactions, although the bimolecular reactions became less effective at elevated temperatures. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Spin-unrestricted random-phase approximation with range separation: Benchmark on atomization energies and reaction barrier heights

    CERN Document Server

    Mussard, Bastien; Angyan, Janos; Toulouse, Julien


    We consider several spin-unrestricted random-phase approximation (RPA) variants for calculating correlation energies, with and without range separation, and test them on datasets of atomization energies and reaction barrier heights. We show that range separation greatly improves the accuracy of all RPA variants for these properties. Moreover, we show that a RPA variant with exchange, hereafter referred to as RPAx-SO2, first proposed by Sz-abo and Ostlund [A. Szabo and N. S. Ostlund, J. Chem. Phys. 67, 4351 (1977)] in a spin-restricted closed-shell formalism, and extended here to a spin-unrestricted formalism, provides on average the most accurate range-separated RPA variant for atomization energies and reaction barrier heights. Since this range-separated RPAx-SO2 method had already been shown to be among the most accurate range-separated RPA variants for weak intermolecular interactions [J. Toulouse, W. Zhu, A. Savin, G. Jansen, and J. G. {\\'A}ngy{\\'a}n, J. Chem. Phys. 135, 084119 (2011)], this works confirms...

  7. LSENS, a general chemical kinetics and sensitivity analysis code for homogeneous gas-phase reactions. 2: Code description and usage (United States)

    Radhakrishnan, Krishnan; Bittker, David A.


    LSENS, the Lewis General Chemical Kinetics Analysis Code, has been developed for solving complex, homogeneous, gas-phase chemical kinetics problems and contains sensitivity analysis for a variety of problems, including nonisothermal situations. This report is part 2 of a series of three reference publications that describe LSENS, provide a detailed guide to its usage, and present many example problems. Part 2 describes the code, how to modify it, and its usage, including preparation of the problem data file required to execute LSENS. Code usage is illustrated by several example problems, which further explain preparation of the problem data file and show how to obtain desired accuracy in the computed results. LSENS is a flexible, convenient, accurate, and efficient solver for chemical reaction problems such as static system; steady, one-dimensional, inviscid flow; reaction behind incident shock wave, including boundary layer correction; and perfectly stirred (highly backmixed) reactor. In addition, the chemical equilibrium state can be computed for the following assigned states: temperature and pressure, enthalpy and pressure, temperature and volume, and internal energy and volume. For static problems the code computes the sensitivity coefficients of the dependent variables and their temporal derivatives with respect to the initial values of the dependent variables and/or the three rate coefficient parameters of the chemical reactions. Part 1 (NASA RP-1328) derives the governing equations describes the numerical solution procedures for the types of problems that can be solved by lSENS. Part 3 (NASA RP-1330) explains the kinetics and kinetics-plus-sensitivity-analysis problems supplied with LSENS and presents sample results.

  8. Energy-decomposition analysis of ion-neutral complexes along reaction coordinates of unimolecular proton-transfer reaction in gas phase: Comparison between 2-butanol radical ion and protonated 2-ethoxypropane ion (United States)

    Sugimura, Natsuhiko; Igarashi, Yoko; Aoyama, Reiko; Shibue, Toshimichi


    An energy-decomposition analysis clarified the physical origins that change in gas-phase unimolecular proton-transfer reactions via ion-neutral complexes of the 2-butanol radical ion and protonated 2-ethoxypropane ion. In the bond cleavage and new bond-formation parts of the reaction coordinates, exchange and polarization energies provide a major source of the attraction. In the ion-neutral complex-formation part of the reaction coordinate, different major attractive sources, dispersion, and electrostatic energies were observed. The physical origins of weak interaction in the ion-neutral complexes were affected by the local charges and distances between the ion moieties and the neutral moieties.

  9. Recovery of condensate water quality in power generator's surface condenser (United States)

    Kurniawan, Lilik Adib


    In PT Badak NGL Plant, steam turbines are used to drive major power generators, compressors, and pumps. Steam exiting the turbines is condensed in surface condensers to be returned to boilers. Therefore, surface condenser performance and quality of condensate water are very important. One of the recent problem was caused by the leak of a surface condenser of Steam Turbine Power Generator. Thesteam turbine was overhauled, leaving the surface condenser idle and exposed to air for more than 1.5 years. Sea water ingress due to tube leaks worsens the corrosionof the condenser shell. The combination of mineral scale and corrosion product resulting high conductivity condensate at outlet condenser when we restarted up, beyond the acceptable limit. After assessing several options, chemical cleaning was the best way to overcome the problem according to condenser configuration. An 8 hour circulation of 5%wt citric acid had succeed reducing water conductivity from 50 μmhos/cm to below 5 μmhos/cm. The condensate water, then meets the required quality, i.e. pH 8.3 - 9.0; conductivity ≤ 5 μmhos/cm, therefore the power generator can be operated normally without any concern until now.

  10. Mechanochemical Knoevenagel condensation investigated in situ

    Directory of Open Access Journals (Sweden)

    Sebastian Haferkamp


    Full Text Available The mechanochemical Knoevenagel condensation of malononitrile with p-nitrobenzaldehyde was studied in situ using a tandem approach. X-ray diffraction and Raman spectroscopy were combined to yield time-resolved information on the milling process. Under solvent-free conditions, the reaction leads to a quantitative conversion to p-nitrobenzylidenemalononitrile within 50 minutes. The in situ data indicate that the process is fast and proceeds under a direct conversion. After stopping the milling process, the reaction continues until complete conversion. The continuous and the stopped milling process both result in crystalline products suitable for single crystal X-ray diffraction.

  11. Gas phase formation of extremely oxidized pinene reaction products in chamber and ambient air

    Directory of Open Access Journals (Sweden)

    M. Ehn


    Full Text Available High molecular weight (300–650 Da naturally charged negative ions have previously been observed at a boreal forest site in Hyytiälä, Finland. The long-term measurements conducted in this work showed that these ions are observed practically every night between spring and autumn in Hyytiälä. The ambient mass spectral patterns could be reproduced in striking detail during additional measurements of α-pinene (C10H16 oxidation at low-OH conditions in the Jülich Plant Atmosphere Chamber (JPAC. The ions were identified as clusters of the nitrate ion (NO3 and α-pinene oxidation products reaching oxygen to carbon ratios of 0.7–1.3, while retaining most of the initial ten carbon atoms. Attributing the ions to clusters instead of single molecules was based on additional observations of the same extremely oxidized organics in clusters with HSO4 (Hyytiälä and C3F5O2 (JPAC. The most abundant products in the ion spectra were identified as C10H14O7, C10H14O9, C10H16O9, and C10H14O11. The mechanism responsible for forming these molecules is still not clear, but the initial reaction is most likely ozone attack at the double bond, as the ions are mainly observed under dark conditions. β-pinene also formed highly oxidized products under the same conditions, but less efficiently, and mainly C9 compounds which were not observed in Hyytiälä, where β-pinene on average is 4–5 times less abundant than α-pinene. Further, to explain the high O/C together with the relatively high H/C, we propose that geminal diols and/or hydroperoxide groups may be important. We estimate that the night-time concentration of the sum of the neutral extremely oxidized products is on the order of 0.1–1 ppt (~10

  12. Insights into secondary organic aerosol formed via aqueous-phase reactions of phenolic compounds based on high resolution mass spectrometry (United States)

    Sun, Y. L.; Zhang, Q.; Anastasio, C.; Sun, J.


    Recent work has shown that aqueous-phase reactions of phenolic compounds - phenol (C6H6O), guaiacol (C7H8O2), and syringol (C8H10O3) - can form secondary organic aerosol (SOA) at high yields. Here we examine the chemical characteristics of this SOA and its formation mechanisms using a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-AMS), an Ion Chromatography system (IC), and a Total Organic Carbon (TOC) analyzer. The phenolic SOA are highly oxygenated with oxygen-to-carbon (O/C) ratios in the range of 0.80-1.06 and carbon oxidation states (=2×O/C-H/C) between -0.14 and +0.47. The organic mass-to-carbon (OM/OC) ratios determined by the HR-AMS (=2.21-2.55) agree well with values determined based on the SOA mass measured gravimetrically and the OC mass from the TOC analyzer. Both the O/C and OM/OC ratios of the phenolic SOA are similar to the values observed for ambient low-volatility oxygenated/secondary OA (LV-OOA). Oxalate is a minor, but ubiquitous, component of the SOA formed from all three phenolic precursors, accounting for 1.4-5.2% of the SOA mass, with generally higher yields in experiments with H2O2 added as an OH source compared to without. The AMS spectra show evidence for the formation of syringol and guaiacol dimers and higher oligomers via C-C and C-O coupling of phenoxyl radicals, which are formed through oxidation pathways such as abstraction of the phenolic hydrogen atom or OH addition to the aromatic ring. This latter pathway leads to hydroxylation of the aromatic ring, which is one mechanism that increases the degree of oxidation of the SOA products. Compared to direct photochemical reactions of the phenols, OH-initiated reactions favor the formation of smaller oxidation products but less dimers or higher oligomers. Two unique and prominent ions in the syringol and guaiacol SOA spectra, m/z 306 (C16H18O6+) and m/z 246 (C14H14O4+), respectively, are observed in ambient aerosols significantly influenced by wood combustion and fog

  13. Stability of lithium superoxide LiO2 in the gas phase: computational study of dimerization and disproportionation reactions. (United States)

    Bryantsev, Vyacheslav S; Blanco, Mario; Faglioni, Francesco


    Knowledge of the precise molecular mechanisms during the discharge and recharge processes in the lithium-air battery is critical for achieving desired improvements in specific capacity, current density, and cyclability. The initial oxygen reduction product formed in the presence of Li(+) ions is lithium superoxide LiO(2). In this study, we report the computed structures and thermodynamic parameters of LiO(2) dimerization in the gas phase, which enables us to provide a baseline for the reaction free energy profile of the subsequent disproportionation of (LiO(2))(2) to lithium peroxide Li(2)O(2) and O(2). Our calculations identified several low-lying (LiO(2))(2) dimers, with the singlet bipyramidal structure giving IR bands that are consistent with the characteristic IR vibration frequencies of (LiO(2))(2) in the oxygen matrix at T = 15-40 K. The activation barrier for (LiO(2))(2) = Li(2)O(2)+O(2) is 10.9 kcal/mol at the UCCSD(T)/CBS level (T = 298 K), suggesting that in the gas phase LiO(2) and its aggregates could only be observed at low temperatures.

  14. Separation of molecular constituents from a humic acid by solid-phase extraction following a transesterification reaction. (United States)

    Fiorentino, Gabriella; Spaccini, Riccardo; Piccolo, Alessandro


    A selective removal of humic constituents involved in ester groups was conducted by a boron trifluoride-methanol transesterification reaction after removal of structurally unbound lipids. An analytical separation of subfractions containing specific classes of compound liberated from the humic matrix simplifies their identification by gas chromatography-mass spectrometry. We compared the traditional liquid-liquid separation into phenolic and aliphatic fractions with the modern and versatile fractionation technique using solid-phase extraction (SPE) on aminopropyl-bonded phases. Our results showed that both methods ensured separation of the same compounds, such as di- and tri-hydroxyalkanoic acids, alpha-, beta- and omega-hydroxy fatty acids, alkanoic acids, alpha,omega-alkanedioic acids, n-alkanols, phenolic acids and sterols. Moreover, the SPE method not only provided a larger recovery of compounds, but involved smaller sample and solvent requirements, and larger ease and rapidity of sample handling than the traditional liquid-liquid separation. The SPE method should be thus recommended in structural studies of natural organic matter.

  15. Polymorphism of Lysozyme Condensates. (United States)

    Safari, Mohammad S; Byington, Michael C; Conrad, Jacinta C; Vekilov, Peter G


    Protein condensates play essential roles in physiological processes and pathological conditions. Recently discovered mesoscopic protein-rich clusters may act as crucial precursors for the nucleation of ordered protein solids, such as crystals, sickle hemoglobin polymers, and amyloid fibrils. These clusters challenge settled paradigms of protein condensation as the constituent protein molecules present features characteristic of both partially misfolded and native proteins. Here we employ the antimicrobial enzyme lysozyme and examine the similarities between mesoscopic clusters, amyloid structures, and disordered aggregates consisting of chemically modified protein. We show that the mesoscopic clusters are distinct from the other two classes of aggregates. Whereas cluster formation and amyloid oligomerization are both reversible, aggregation triggered by reduction of the intramolecular S-S bonds is permanent. In contrast to the amyloid structures, protein molecules in the clusters retain their enzymatic activity. Furthermore, an essential feature of the mesoscopic clusters is their constant radius of less than 50 nm. The amyloid and disordered aggregates are significantly larger and rapidly grow. These findings demonstrate that the clusters are a product of limited protein structural flexibility. In view of the role of the clusters in the nucleation of ordered protein solids, our results suggest that fine-tuning the degree of protein conformational stability is a powerful tool to control and direct the pathways of protein condensation.

  16. Pair condensation in massless scalar electrodynamics (United States)

    Hey, Anthony J. G.; Mandula, Jeffrey E.


    Motivated by the instabilities of the vacuum to bound-state pair production at large coupling in both abelian and non-abelian gauge theories, we examine the stability of the vacuum of a constrained version of massless scalar electrodynamics to the formation of a scalar pair condensate. The trial states are constructed by analogy with the BCS ground state of super-conductivity and are such that the vacuum expectation value of the scalar field vanishes. Analysis of the minimization equation for the energy density indicates that there are two phases as a function of the coupling constant. Under the constraint that the vacuum expectation value of the scalar field be zero, we find what, for small coupling, the perturbative vacuum minimizes the energy, while for large coupling a condensate of particle-antiparticle pairs is energetically favored. After discussing the relation of our results to the phase structure of unconstrained scalar electrodynamics, we speculate on possible implications for QCD.

  17. Pair condensation in massless scalar electrodynamics

    Energy Technology Data Exchange (ETDEWEB)

    Hey, A.J.G. (Southampton Univ. (UK). Dept. of Physics); Mandula, J.E. (Washington Univ., St. Louis, MO (USA). Dept. of Physics)


    Motivated by the instabilities of the vacuum to bound-state pair production at large coupling in both abelian and non-abelian gauge theories, we examine the stability of the vacuum of a constrained version of massless scalar electrodynamics to the formation of a scalar pair condensate. The trial states are constructed by analogy with the BCS ground state of super-conductivity and are such that the vacuum expectation value of the scalar field vanishes. Analysis of the minimization equation for the energy density indicates that there are two phases as a function of the coupling constant. Under the constraint that the vacuum expectation value of the scalar field be zero, we find that, for small coupling, the perturbative vacuum minimizes the energy, while for large coupling a condensate of particle-antiparticle pairs is energetically favored. After discussing the relation of our results to the phase structure of unconstrained scalar electrodynamics, we speculate on possible implications for QCD.

  18. Electron correlation in molecules and condensed phases

    CERN Document Server

    March, N H


    This reference describes the latest research on correlation effects in the multicenter problems of atoms, molecules, and solids The author utilizes first- and second-order matrices, including the important observable electron density rho(r), and the Green function for discussing quantum computer simulations With its focus on concepts and theories, this volume will benefit experimental physicists, materials scientists, and physical and inorganic chemists as well as graduate students

  19. From the X-rays to a reliable “low cost” computational structure of caffeic acid: DFT, MP2, HF and integrated molecular dynamics-X-ray diffraction approach to condensed phases (United States)

    Lombardo, Giuseppe M.; Portalone, Gustavo; Colapietro, Marcello; Rescifina, Antonio; Punzo, Francesco


    The ability of caffeic acid to act as antioxidant against hyperoxo-radicals as well as its recently found therapeutic properties in the treatment of hepatocarcinoma, still make this compound, more than 20 years later the refinement of its crystal structure, object of study. It belongs to the vast family of humic substances, which play a key role in the biodegradation processes and easily form complexes with ions widely diffused in the environment. This class of compounds is therefore interesting for potential environmental chemistry applications concerning the possible complexation of heavy metals. Our study focused on the characterization of caffeic acid as a starting necessary step, which will be followed in the future by the application of our findings on the study of the properties of caffeate anion interaction with heavy metal ions. To reach this goal, we applied a low cost approach - in terms of computational time and resources - aimed at the achievement of a high resolution, robust and trustable structure using the X-ray single crystal data, recollected with a higher resolution, as touchstone for a detailed check. A comparison between the calculations carried out with density functional theory (DFT), Hartree-Fock (HF) method and post SCF second order Møller-Plesset perturbation method (MP2), at the 6-31G ** level of the theory, molecular mechanics (MM) and molecular dynamics (MD) was performed. As a consequence we explained on one hand the possible reasons for the pitfalls of the DFT approach and on the other the benefits of using a good and robust force field developed for condensed phases, as AMBER, with MM and MD. The reliability of the latter, highlighted by the overall agreement extended up to the anisotropic displacement parameters calculated by means of MD and the ones gathered by X-ray measurements, makes it very promising for the above-mentioned goals.

  20. HPLC, NMR and MALDI-TOF MS Analysis of Condensed Tannins from Lithocarpus glaber Leaves with Potent Free Radical Scavenging Activity

    Directory of Open Access Journals (Sweden)

    Yi Ming Lin


    Full Text Available Using acid-catalyzed degradation in the presence of cysteamine, the condensed tannins from Lithocarpus glaber leaves were characterized, following thiolysis, by means of reversed-phase HPLC, 13C-NMR and matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI-TOF MS analyses. The thiolysis reaction products showed the presence of the procyanidin (PC and prodelphinidin (PD structures. The 13C-NMR spectrum revealed that the condensed tannins were comprised of PD (72.4% and PC (27.6%, and with a greater content of cis configuration rather than the trans configuration of C2–C3. The MALDI-TOF MS analysis proved the presence of PD units, and the maximum degree of polymerization (DP was an undecamer. The antioxidant activity of condensed tannins from L. glaber leaves was evaluated by using a free radical scavenging activity assay.

  1. On Ultrafast Time-Domain TeraHertz Spectroscopy in the Condensed Phase: Linear Spectroscopic Measurements of Hydrogen-Bond Dynamics of Astrochemical Ice Analogs and Nonlinear TeraHertz Kerr Effect Measurements of Vibrational Quantum Beats (United States)

    Allodi, Marco A.

    Much of the chemistry that affects life on planet Earth occurs in the condensed phase. The TeraHertz (THz) or far-infrared (far-IR) region of the electromagnetic spectrum (from 0.1 THz to 10 THz) has been shown to provide unique possibilities in the study of condensed-phase processes. The goal of this work is to expand the possibilities available in the THz region and undertake new investigations of fundamental interest to chemistry. Since we are fundamentally interested in condensed-phase processes, this thesis focuses on two areas where THz spectroscopy can provide new understanding: astrochemistry and solvation science. To advance these fields, we had to develop new instrumentation that would enable the experiments necessary to answer new questions in either astrochemistry or solvation science. We first developed a new experimental setup capable of studying astrochemical ice analogs in both the TeraHertz (THz), or far-Infrared (far-IR), region (0.3 - 7.5 THz; 10 - 250 wavenumbers) and the mid-IR (400 - 4000 wavenumbers). The importance of astrochemical ices lies in their key role in the formation of complex organic molecules, such as amino acids and sugars in space. Thus, the instruments are capable of performing variety of spectroscopic studies that can provide especially relevant laboratory data to support astronomical observations from telescopes such as the Herschel Space Telescope, the Stratospheric Observatory for Infrared Astronomy (SOFIA), and the Atacama Large Millimeter Array (ALMA). The experimental apparatus uses a THz time-domain spectrometer, with a 1750/875 nm plasma source and a GaP detector crystal, to cover the bandwidth mentioned above with 10 GHz (0.3 wavenumber) resolution. Using the above instrumentation, experimental spectra of astrochemical ice analogs of water and carbon dioxide in pure, mixed, and layered ices were collected at different temperatures under high-vacuum conditions with the goal of investigating the structure of the ice

  2. Energy partitioning in polyatomic chemical reactions: Quantum state resolved studies of highly exothermic atom abstraction reactions from molecules in the gas phase and at the gas-liquid interface (United States)

    Zolot, Alexander M.

    This thesis recounts a series of experiments that interrogate the dynamics of elementary chemical reactions using quantum state resolved measurements of gas-phase products. The gas-phase reactions F + HCl → HF + Cl and F + H2O → HF + OH are studied using crossed supersonic jets under single collision conditions. Infrared (IR) laser absorption probes HF product with near shot-noise limited sensitivity and high resolution, capable of resolving rovibrational states and Doppler lineshapes. Both reactions yield inverted vibrational populations. For the HCl reaction, strongly bimodal rotational distributions are observed, suggesting microscopic branching of the reaction mechanism. Alternatively, such structure may result from a quantum-resonance mediated reaction similar to those found in the well-characterized F + HD system. For the H2O reaction, a small, but significant, branching into v = 2 is particularly remarkable because this manifold is accessible only via the additional center of mass collision energy in the crossed jets. Rotationally hyperthermal HF is also observed. Ab initio calculations of the transition state geometry suggest mechanisms for both rotational and vibrational excitation. Exothermic chemical reaction dynamics at the gas-liquid interface have been investigated by colliding a supersonic jet of F atoms with liquid squalane (C30H62), a low vapor pressure hydrocarbon compatible with the high vacuum environment. IR spectroscopy provides absolute HF( v,J) product densities and Doppler resolved velocity component distributions perpendicular to the surface normal. Compared to analogous gas-phase F + hydrocarbon reactions, the liquid surface is a more effective "heat sink," yet vibrationally excited populations reveal incomplete thermal accommodation with the surface. Non-Boltzmann J-state populations and hot Doppler lineshapes that broaden with HF excitation indicate two competing scattering mechanisms: (i) a direct reactive scattering channel

  3. Condenser-free contrast methods for transmitted-light microscopy. (United States)

    Webb, K F


    Phase contrast microscopy allows the study of highly transparent yet detail-rich specimens by producing intensity contrast from phase objects within the sample. Presented here is a generalized phase contrast illumination schema in which condenser optics are entirely abrogated, yielding a condenser-free yet highly effective method of obtaining phase contrast in transmitted-light microscopy. A ring of light emitting diodes (LEDs) is positioned within the light-path such that observation of the objective back focal plane places the illuminating ring in appropriate conjunction with the phase ring. It is demonstrated that true Zernike phase contrast is obtained, whose geometry can be flexibly manipulated to provide an arbitrary working distance between illuminator and sample. Condenser-free phase contrast is demonstrated across a range of magnifications (4-100×), numerical apertures (0.13-1.65NA) and conventional phase positions. Also demonstrated is condenser-free darkfield microscopy as well as combinatorial contrast including Rheinberg illumination and simultaneous, colour-contrasted, brightfield, darkfield and Zernike phase contrast. By providing enhanced and arbitrary working space above the preparation, a range of concurrent imaging and electrophysiological techniques will be technically facilitated. Condenser-free phase contrast is demonstrated in conjunction with scanning ion conductance microscopy (SICM), using a notched ring to admit the scanned probe. The compact, versatile LED illumination schema will further lend itself to novel next-generation transmitted-light microscopy designs. The condenser-free illumination method, using rings of independent or radially-scanned emitters, may be exploited in future in other electromagnetic wavebands, including X-rays or the infrared. © 2014 The Author. Journal of Microscopy published by John Wiley & Sons, Ltd on behalf of the Royal Microscopical Society.

  4. Effect of Five-Finger Shoes on Vertical Ground Reaction Force Loading Rates and Perceived Comfort during the Stance Phase of the Running


    Seyede Zeynab Hoseini; Mansor Eslami


    Objective:  Increased vertical ground reaction force loading rates and lack of comfort footwear in the early stance phase can increase the risk of overuse injuries. The purpose of this study was to investigate the effect of Five-finger shoes on vertical ground reaction force loading rate and perceived comfort during the stance phase of running. Methods: 15 male students (aged 24 ± 5/24 years, weight 75/8 ± 4/61 kg, height 178/6 ± 6/64 cm) were selected. Subjects ...

  5. Are gas-phase reactions of five-coordinate divalent metal ion complexes affected by coordination geometry? (United States)

    Combariza, Marianny Y; Fermann, Justin T; Vachet, Richard W


    Five-coordinate metal complex ions of the type [ML](2+) [where M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II) and L= 1,9-bis(2-pyridyl)-2,5,8-triazanonane (DIEN-(pyr)(2)) and 1,9-bis(2-imidazolyl)-2,5,8-triazanonane (DIEN-(imi)(2)] have been reacted with acetonitrile in the gas phase using a modified quadrupole ion trap mass spectrometer. The kinetics and thermodynamics of these reactions show that the reactivity of these complexes is affected by metal electronic structure and falls into three groups: Mn(II) and Ni(II) complexes are the most reactive, Fe(II) and Co(II) complexes exhibit intermediate reactivity, and Cu(II) and Zn(II) complexes are the least reactive. To help explain the experimental trends in reactivity, theoretical calculations have been used. Due to the relatively large size of the metal complexes involved, we have utilized a two-layered ONIOM method to perform geometry optimizations and single point energy calculations for the [ML](2+) and [ML + CH(3)CN](2+) systems. The calculations show that the reactant five-coordinate complexes ([ML](2+)) exhibit structures that are slightly distorted trigonal bipyramidal geometries, while the six-coordinate complexes ([ML + CH(3)CN](2+)) have geometries that are close to octahedral. The Delta G values obtained from the ONIOM calculations roughly agree with the experimental data, but the calculations fail to completely explain the trends for the different metal complexes. The failure to consider all possible isomers as well as adequately represent pi-d interactions for the metal complexes is the likely cause of this discrepancy. Using the angular overlap model (AOM) to obtain molecular orbital stabilization energies (MOSE) also fails to reproduce the experimental trends when only sigma interactions are considered but succeeds in explaining the trends when pi interactions are taken into account. These results indicate that the pi-donor character of the CH(3)CN plays a subtle, yet important, role in

  6. Sanger DNA-sequencing reactions performed in a solid-phase nanoreactor directly coupled to capillary gel electrophoresis. (United States)

    Soper, S A; Williams, D C; Xu, Y; Lassiter, S J; Zhang, Y; Ford, S M; Bruch, R C


    A miniaturized, solid-phase nanoreactor was developed to prepare Sanger DNA-sequencing ladders which was directly interfaced to a capillary gel electrophoresis system. A biotinylated fragment of the rat brain actin gene (1 kbp) was amplified by PCR and attached to the interior wall of an (aminoalkyl)silane-derivatized fused-silica capillary tube via a biotin/streptavidin/biotin linkage. Coverage of the capillary wall with the biotinylated DNA averaged 77 +/- 10%. Stability of the anchored template under pressure (33 nL/s) and electroosmotic flows (11.3 nL/s) were favorable, requiring rinsing for > 150 h to reduce the surface coverage by only 50%. In addition, the immobilized template was stable toward temperatures required for preparing sequencing ladders, even under cycling conditions. Standard Sanger dideoxynucleotide termination performed in a large-volume (approximately 8 microL) solid-phase reactor using the thermally stable polymerase enzymes Taq and Vent and the polymerases T7 and Bst with off-line slab gel electrophoresis and autoradiographic detection indicated that acceptable fragment generation was achieved only in the case of the thermally stable polymerases. Banding was not apparent for T7 and Bst since all reagents were inserted into the column in a single plug at the beginning of the reaction. A small volume reactor (volume approximately 62 nL) was then used to perform DNA polymerase reactions and was coupled directly to a capillary gel column for separation. The capillary reactor was placed inside a thermocycler to control the temperature during chain extension and was directly connected to the gel column via zero dead volume fused-silica connectors. The complementary DNA fragments generated (C-track only) in the reactor were denatured using heat and directly injected onto the gel-filled capillary for size separation with detection accomplished using near-IR laser-induced fluorescence. Extension and single-base separation resolution of the C

  7. Confinement Contains Condensates

    Energy Technology Data Exchange (ETDEWEB)

    Brodsky, Stanley J.; Roberts, Craig D.; Shrock, Robert; Tandy, Peter C.


    Dynamical chiral symmetry breaking and its connection to the generation of hadron masses has historically been viewed as a vacuum phenomenon. We argue that confinement makes such a position untenable. If quark-hadron duality is a reality in QCD, then condensates, those quantities that have commonly been viewed as constant empirical mass-scales that fill all spacetime, are instead wholly contained within hadrons; i.e., they are a property of hadrons themselves and expressed, e.g., in their Bethe-Salpeter or light-front wave functions. We explain that this paradigm is consistent with empirical evidence, and incidentally expose misconceptions in a recent Comment.

  8. Nanocarbon condensation in detonation (United States)

    Bastea, Sorin


    We analyze the definition of the Gibbs free energy of a nanoparticle in a reactive fluid environment, and propose an approach for predicting the size of carbon nanoparticles produced by the detonation of carbon-rich explosives that regards their condensation as a nucleation process and takes into account absolute entropy effects of the cluster population. The results are consistent with experimental observations and indicate that such entropy considerations are important for determining chemical equilibrium states in energetic materials that contain an excess of carbon. The analysis may be useful for other applications that deal with the nucleation of nanoparticles under reactive conditions.

  9. Topology in Condensed Matter

    CERN Document Server

    Monastyrsky, M I


    This book reports new results in condensed matter physics for which topological methods and ideas are important. It considers, on the one hand, recently discovered systems such as carbon nanocrystals and, on the other hand, new topological methods used to describe more traditional systems such as the Fermi surfaces of normal metals, liquid crystals and quasicrystals. The authors of the book are renowned specialists in their fields and present the results of ongoing research, some of it obtained only very recently and not yet published in monograph form.

  10. Gravitino Condensates in the Early Universe and Inflation

    CERN Document Server

    Mavromatos, Nick E


    We review work on the formation of gravitino condensates via the super-Higgs effect in the early Universe. This is a scenario for both inflating the early universe and breaking local supersymmetry (supergravity), entirely independent of any coupling to external matter. The goldstino mode associated with the breaking of (global) supersymmetry is "eaten" by the gravitino field, which becomes massive (via its own vacuum condensation) and breaks the local supersymmetry (supergravity) dynamically. The most natural association of gravitino condensates with inflation proceeds in an indirect way, via a Starobinsky-inflation-type phase. The higher-order curvature corrections of the (quantum) effective action of gravitino condensates induced by integrating out massive gravitino degrees of freedom in a curved space-time background, in the broken-supergravity phase, are responsible for inducing a scalar mode which inflates the Universe. The scenario is in agreement with Planck data phenomenology in a natural and phenomen...

  11. Gas-Phase Ion-Molecule Reactions of Copper Hydride Anions [CuH2](-) and [Cu2H3](). (United States)

    Zavras, Athanasios; Ghari, Hossein; Ariafard, Alireza; Canty, Allan J; O'Hair, Richard A J


    Gas-phase reactivity of the copper hydride anions [CuH2](-) and [Cu2H3](-) toward a range of neutral reagents has been examined via multistage mass spectrometry experiments in a linear ion trap mass spectrometer in conjunction with isotope labeling studies and Density Functional Theory (DFT) calculations. [CuH2](-) is more reactive than [Cu2H3](-), consistent with DFT calculations, which show it has a higher energy HOMO. Experimentally, [CuH2](-) was found to react with CS2 via hydride transfer to give thioformate (HCS2(-)) in competition with the formation of the organometallic [CuCS2](-) ion via liberation of hydrogen; CO2 via insertion to produce [HCuO2CH](-); methyl iodide and allyl iodide to give I(-) and [CuHI](-); and 2,2,2-trifluoroethanol and 1-butanethiol via protonation to give hydrogen and the product anions [CuH(OCH2CF3)](-) and [CuH(SBu)](-). In contrast, the weaker acid methanol was found to be unreactive. DFT calculations reveal that the differences in reactivity between CS2 and CO2 are due to the lower lying π* orbital of the former, which allows it to accept electron density from the Cu center to form the initial three-membered ring complex intermediate, [H2Cu(η(2)-CS2)](-). In contrast, CO2 undergoes the barrierless side-on hydride transfer promoted by the high electronegativity of the oxygen atoms. Side-on SN2 mechanisms for reactions of [CuH2](-) with methyl iodide and allyl iodide are favored on the basis of DFT calculations. Finally, the DFT calculated barriers for protonation of [CuH2](-) by methanol, 2,2,2-trifluoroethanol, and 1-butanethiol correlate with their gas-phase acidities, suggesting that reactivity is mainly controlled by the acidity of the substrate.

  12. Physics through the 1990s: Condensed-matter physics (United States)


    The volume presents the current status of condensed-matter physics from developments since the 1970s to opportunities in the 1990s. Topics include electronic structure, vibrational properties, critical phenomena and phase transitions, magnetism, semiconductors, defects and diffusion, surfaces and interfaces, low-temperature physics, liquid-state physics, polymers, nonlinear dynamics, instabilities, and chaos. Appendices cover the connections between condensed-matter physics and applications of national interest, new experimental techniques and materials, laser spectroscopy, and national facilities for condensed-matter physics research. The needs of the research community regarding support for individual researchers and for national facilities are presented, as are recommendations for improved government-academic-industrial relations.

  13. Turbulence and heat transfer in condensate in drying cylinders at high g-forces. Phase 1; Turbulens och vaermeoeverfoering i kondensat i torkcylindrar vid hoega g-krafter. Fas 1

    Energy Technology Data Exchange (ETDEWEB)

    Stenstroem, Stig; Ingvarsson, David [Lund Inst. of Tech. (Sweden). Dept. of Chemical Engineering


    Drying of paper is performed by bringing the paper into contact with a hot cylinder surface so that the water in the web is evaporated. The energy needed to heat the drying cylinder is supplied with condensing steam creating a condensate layer on the inside surface of the cylinder. For fast paper machines, the condensate layer will be close to stagnant, thus constituting a significant resistance for the heat transfer process from the steam to the paper. The traditional technique to improve the heat transfer has been to install turbulence bars on the inside surface of the cylinder but at machine speeds of up to 2000 m/min this technique is not sufficiently efficient. The goal in the project has been to study the condensate behaviour in drying cylinders at high centrifugal forces and explore different methods to improve the heat transfer in the condensate for both new and existing fast paper machines so that the capacity in the dryer section can be maintained at a high level. The results are of importance for the manufacturers of paper machines as well as the producing newsprint and printing paper companies. The project has been divided in the following parts: - Literature survey of techniques to increase the heat transfer in condensate and the removal of condensate with siphons. - Develop knowledge about the condensate behaviour in rotating cylinders at high g-forces with and without spoiler bars. This has been accomplished by designing a new cylinder where the condensate velocity relative to the cylinder could be measured at centrifugal forces corresponding to the levels today reached at fast paper machines. Such data have previously not been reported in the literature. - Present solutions for the design of the inside surface of the drying cylinder so that high heat transfer rates can be accomplished in fast paper machines. Solutions should be presented both for existing as well as new paper machines. The results in the project show that at centrifugal forces of

  14. Gas-Phase Reactions of Doubly Charged Lanthanide Cations with Alkanes and Alkenes. Trends in Metal(2+) Reactivity

    Energy Technology Data Exchange (ETDEWEB)

    Gibson, John K.; Marcalo, Joaquim; Santos, Marta; Pires de Matos, Antonio; Haire, Richard G.


    The gas-phase reactivity of doubly-charged lanthanide cations, Ln2+ (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), with alkanes (methane, ethane, propane, n-butane) and alkenes (ethene, propene, 1-butene) was studied by Fourier transform ion cyclotron resonance mass spectrometry. The reaction products consisted of different combinations of doubly-charged organometallic ions?adducts or species formed via metal-ion-induced hydrogen, dihydrogen, alkyl, or alkane eliminations from the hydrocarbons?and singly-charged ions that resulted from electron, hydride, or methide transfers from the hydrocarbons to the metal ions. The only lanthanide cations capable of activating the hydrocarbons to form doubly-charged organometallic ions were La2+, Ce2+, Gd2+, and Tb2+, which have ground-state or low-lying d1 electronic configurations. Lu2+, with an accessible d1 electronic configuration but a rather high electron affinity, reacted only through transfer channels. The remaining Ln2+ reacted via transfer channels or adduct formation. The different accessibilities of d1 electronic configurations and the range of electron affinities of the Ln2+ cations allowed for a detailed analysis of the trends for metal(2+) reactivity and the conditions for occurrence of bond activation, adduct formation, and electron, hydride, and methide transfers.

  15. Picosecond dynamics of reactions in the liquid phase: studies of iodine photodissociation and development of new laser techniques

    Energy Technology Data Exchange (ETDEWEB)

    Berg, M.A.


    Iodine photodissociation and recombination was studied as a model for processes common to chemical reaction in the liquid phase. Picosecond transient absorption measurements from 1000 to 295 nm were used to monitor the dynamics in a variety of solvents. Most of the atoms which undergo geminate recombination were found to do so in less than or equal to 15 ps, in agreement with the results of existing molecular dynamics simulations. Vibrational relaxation times vary from approx.15 ps near the middle of the ground state well to approx.150 ps for complete relaxation to v = 0. The prediction of strong resonant vibrational energy transfer to chlorinated methane solvents was not supported, but some evidence for this mechanism was found for alkane solvents. Current theory is unable to explain the large variation (65 to 2700 ps) of the excited A'-state lifetime in various solvents. The 10-Hz amplified, synchronously-pumped dye laser which was used in these studies is described and characterized. SERS (Stimulated Electronic Raman Scattering) and difference frequency mixing were used in the generation of the infrared and far-infrared, respectively. 54 refs., 38 figs., 3 tabs. (WRF)

  16. Aqueous two-phase system patterning of detection antibody solutions for cross-reaction-free multiplex ELISA (United States)

    Frampton, John P.; White, Joshua B.; Simon, Arlyne B.; Tsuei, Michael; Paczesny, Sophie; Takayama, Shuichi


    Accurate disease diagnosis, patient stratification and biomarker validation require the analysis of multiple biomarkers. This paper describes cross-reactivity-free multiplexing of enzyme-linked immunosorbent assays (ELISAs) using aqueous two-phase systems (ATPSs) to confine detection antibodies at specific locations in fully aqueous environments. Antibody cross-reactions are eliminated because the detection antibody solutions are co-localized only to corresponding surface-immobilized capture antibody spots. This multiplexing technique is validated using plasma samples from allogeneic bone marrow recipients. Patients with acute graft versus host disease (GVHD), a common and serious condition associated with allogeneic bone marrow transplantation, display higher mean concentrations for four multiplexed biomarkers (HGF, elafin, ST2 and TNFR1) relative to healthy donors and transplant patients without GVHD. The antibody co-localization capability of this technology is particularly useful when using inherently cross-reactive reagents such as polyclonal antibodies, although monoclonal antibody cross-reactivity can also be reduced. Because ATPS-ELISA adapts readily available antibody reagents, plate materials and detection instruments, it should be easily transferable into other research and clinical settings.

  17. A CFD study of wave influence on film steam condensation in the presence of non-condensable gas

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xianmao, E-mail: [Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084 (China); Chang, Huajian, E-mail: [Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084 (China); Corradini, Michael, E-mail: [Department of Engineering Physics, University of Wisconsin-Madison, 1500 Engineering Drive, Madison, WI 53706 (United States)


    Highlights: • A condensation model is incorporated in the ANSYS FLUENT. • Different turbulence models are evaluated for flows over wavy surfaces. • Wavy surfaces with and without moving velocities are used to model the wave. • Various wavy surfaces with different wave heights and wavelengths are selected. • Wave influence on film steam condensation is investigated. - Abstract: Steam condensation plays an important role in removing heat from the containment of a nuclear plant during postulated accidents. However, due to the presence of non-condensable gases such as air and hydrogen in the containment, the condensation rate can decrease dramatically. Under certain conditions, the condensate film on the cold containment walls can affect the overall heat transfer rate. The wavy interface of the condensate film is a factor and is usually believed to enhance the condensation rate, since the waves can both increase the interfacial area and disturb the non-condensable gas boundary layer. However, it is not clear how to properly account for this factor and what is its quantitative influence in experiments. In this work, a CFD approach is applied to study the wave effects on film condensation in the presence of non-condensable gas. Wavy surfaces with and without moving velocities are used to replace the wavy interface of the falling film. A condensation model is incorporated in the ANSYS FLUENT simulation and a realizable k–ε turbulence model is applied. Various wavy surfaces with different wave heights and wavelengths are selected to conduct numerical experiments with a wide range of gas velocities. The results show that the wave structure can enhance condensation rate up to ten percent mainly due to the alteration of local flow structures in the gas phase. The increments of the condensation rate due to the wavy interface can vary with different gas velocities. The investigation shows that a multiplication factor accounts for the wave effects on film

  18. Sonication effect on the reaction of 4-bromo-1-methylbenzene with sodium sulfide in liquid-liquid multi-site phase-transfer catalysis condition - kinetic study. (United States)

    Abimannan, Pachaiyappan; Selvaraj, Varathan; Rajendran, Venugopal


    The synthesis of di-p-tolylsulfane from the reaction of 4-bromo-1-methylbenzene (BMB) with sodium sulfide was carried out using a multi-site phase-transfer catalyst (MPTC) viz., 1,4-dihexyl-1,4-diazoniabicyclo[2.2.2]octanium dibromide and ultrasonic irradiation in a liquid-liquid reaction condition. The overall reaction rate is greatly enhanced when catalyzed by multi-site phase-transfer catalyst (MPTC) combined with sonication (40 kHz, 300 W) in a batch reactor than catalyzed by MPTC without sonication. Effects on the reaction due to various operating conditions, such as agitation speed, different ultrasound frequencies, different phase-transfer catalysts, different organic solvents, the amount of MPTC, temperature, amount of sodium sulfide, effect of sodium hydroxide, volume of n-hexane and the concentration of 4-bromo-1-methylbenzene. The reaction obeys a pseudo first-order rate law and a suitable mechanism was proposed based on the experimental observation. Copyright © 2014 Elsevier B.V. All rights reserved.

  19. Kinetics of the reaction of F atoms with O2 and UV spectrum of FO2 radicals in the gas phase at 295 K

    DEFF Research Database (Denmark)

    Ellermann, T.; Sehested, J.; Nielsen, O.J.


    The ultraviolet absorption spectrum of FO2 radicals and the kinetics of the reaction of F atoms with O2 have been studied in the gas phase at 295 K using pulse radiolysis combined with kinetic UV spectroscopy. At 230 nm, sigma(FO2) = (5.08 +/- 0.70) X 10(-18) cm2 molecule-1. The kinetics...

  20. Optimization of the surface modification process of cross-linked polythiol-coated chiral stationary phases synthesized by a two-step thiol-ene click reaction. (United States)

    Schmitt, Kristina; Lämmerhofer, Michael


    A new platform technology for the preparation of stable chiral stationary phases was successfully optimized. The chiral selector tert-butylcarbamoylquinine was firstly covalently connected to the polymer poly(3-mercaptopropyl)methylsiloxane by thiol-ene click reaction. Secondly, the quinine carbamate functionalized polysiloxane conjugate was coated onto the surface of vinyl modified silica particles and cross-linked via thiol-ene click reaction. The amount of polysiloxane, chiral selector, radical initiator, reaction solvent (chloroform and methanol), reaction time, and pore size of the supporting silica particles were varied and systematically optimized in terms of achievable plate numbers while maintaining simultaneously enantioselectivity. The optimization was based on elemental analysis data, chromatographic results, and H/u-curves (Van Deemter) of the resultant chiral stationary phases. The results suggest that better chromatographic efficiency (higher plate numbers) at equal enantioselectivity can be achieved with methanol (a poor solvent for the polysiloxane that is dispersed rather than dissolved) and a lower film thickness of quinine carbamate functionalized polysiloxane. In this study, chiral stationary phases based on 100 Å silica slightly outperformed 200 Å silica particles (each 5 μm). The optimized two step material exhibited significantly reduced mass transfer resistance compared to the one step material and equal performance as a brush-type chiral stationary phase. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.