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Sample records for copolymerization reactions experimental

  1. Chain Copolymerization Reactions: An Algorithm to Predict the Reaction Evolution with Conversion

    ERIC Educational Resources Information Center

    Gallardo, Alberto; Aguilar, Maria Rosa; Abraham, Gustavo A.; Roman, Julio San

    2004-01-01

    An algorithm is developed to study and understand the behavior of chain copolymerization reactions. When a binary copolymerization reaction follows the terminal model, Conversion is able to predict the evolution of different parameters, such as instantaneous and cumulative copolymer molar fractions, or molar fractions of any sequence with the…

  2. Development of group IV molecular catalysts for high temperature ethylene-α-olefin copolymerization reactions.

    PubMed

    Klosin, Jerzy; Fontaine, Philip P; Figueroa, Ruth

    2015-07-21

    This Account describes our research related to the development of molecular catalysts for solution phase olefin polymerization. Specifically, a series of constrained geometry and nonmetallocene (imino-amido-type) complexes were developed for high temperature olefin polymerization reactions. We have discovered many highly active catalysts that are capable of operating at temperatures above 120 °C and producing copolymers with a useful range of molecular weights (from medium to ultrahigh depending on precatalyst identity and polymerization conditions) and α-olefin incorporation capability. Constrained geometry catalysts (CGCs) exhibit very high activities and are capable of producing a variety of copolymers including ethylene-propylene and ethylene-1-octene copolymers at high reactor temperatures. Importantly, CGCs have much higher reactivity toward α-olefins than classical Ziegler-Natta catalysts, thus allowing for the production of copolymers with any desired level of comonomer. In search of catalysts with improved performance, we discovered 3-amino-substituted indenyl-based CGCs that exhibit the highest activity and produce copolymers with the highest molecular weight within this family of catalysts. Phenanthrenyl-based CGCs were found to be outstanding catalysts for the effective production of high styrene content ethylene-styrene copolymers under industrially relevant conditions. In contrast to CGC ligands, imino-amido-type ligands are bidentate and monoionic, leading to the use of trialkyl group IV precatalysts. The thermal instability of imino-amido complexes was addressed by the development of imino-enamido and amidoquinoline complexes, which are not only thermally very robust, but also produce copolymers with higher molecular weights, and exhibit improved α-olefin incorporation. Imido-amido and imino-enamido catalysts undergo facile chain transfer reactions with metal alkyls, as evidenced by a sharp decrease in polymer molecular weight when the

  3. Development of group IV molecular catalysts for high temperature ethylene-α-olefin copolymerization reactions.

    PubMed

    Klosin, Jerzy; Fontaine, Philip P; Figueroa, Ruth

    2015-07-21

    This Account describes our research related to the development of molecular catalysts for solution phase olefin polymerization. Specifically, a series of constrained geometry and nonmetallocene (imino-amido-type) complexes were developed for high temperature olefin polymerization reactions. We have discovered many highly active catalysts that are capable of operating at temperatures above 120 °C and producing copolymers with a useful range of molecular weights (from medium to ultrahigh depending on precatalyst identity and polymerization conditions) and α-olefin incorporation capability. Constrained geometry catalysts (CGCs) exhibit very high activities and are capable of producing a variety of copolymers including ethylene-propylene and ethylene-1-octene copolymers at high reactor temperatures. Importantly, CGCs have much higher reactivity toward α-olefins than classical Ziegler-Natta catalysts, thus allowing for the production of copolymers with any desired level of comonomer. In search of catalysts with improved performance, we discovered 3-amino-substituted indenyl-based CGCs that exhibit the highest activity and produce copolymers with the highest molecular weight within this family of catalysts. Phenanthrenyl-based CGCs were found to be outstanding catalysts for the effective production of high styrene content ethylene-styrene copolymers under industrially relevant conditions. In contrast to CGC ligands, imino-amido-type ligands are bidentate and monoionic, leading to the use of trialkyl group IV precatalysts. The thermal instability of imino-amido complexes was addressed by the development of imino-enamido and amidoquinoline complexes, which are not only thermally very robust, but also produce copolymers with higher molecular weights, and exhibit improved α-olefin incorporation. Imido-amido and imino-enamido catalysts undergo facile chain transfer reactions with metal alkyls, as evidenced by a sharp decrease in polymer molecular weight when the

  4. Mechanistic aspects of the copolymerization reaction of carbon dioxide and epoxides, using a chiral salen chromium chloride catalyst.

    PubMed

    Darensbourg, Donald J; Yarbrough, Jason C

    2002-06-01

    The air-stable, chiral (salen)Cr(III)Cl complex (3), where H(2)salen = N,N'-bis(3,5-di-tert-butyl-salicylidene)-1,2-cyclohexene diamine, has been shown to be an effective catalyst for the coupling of cyclohexene oxide and carbon dioxide to afford poly(cyclohexenylene carbonate), along with a small quantity of its trans-cyclic carbonate. The thus produced polycarbonate contained >99% carbonate linkages and had a M(n) value of 8900 g/mol with a polydispersity index of 1.2 as determined by gel permeation chromatography. The turnover number (TON) and turnover frequency (TOF) values of 683 g of polym/g of Cr and 28.5 g of polym/g of Cr/h, respectively for reactions carried out at 80 degrees C and 58.5 bar pressure increased by over 3-fold upon addition of 5 equiv of the Lewis base cocatalyst, N-methyl imidazole. Although this chiral catalyst is well documented for the asymmetric ring-opening (ARO) of epoxides, in this instance the copolymer produced was completely atactic as illustrated by (13)C NMR spectroscopy. Whereas the mechanism for the (salen)Cr(III)-catalyzed ARO of epoxides displays a squared dependence on [catalyst], which presumably is true for the initiation step of the copolymerization reaction, the rate of carbonate chain growth leading to copolymer or cyclic carbonate formation is linearly dependent on [catalyst]. This was demonstrated herein by way of in situ measurements at 80 degrees C and 58.5 bar pressure. Hence, an alternative mechanism for copolymer production is operative, which is suggested to involve a concerted attack of epoxide at the axial site of the chromium(III) complex where the growing polymer chain for epoxide ring-opening resides. Preliminary investigations of this (salen)Cr(III)-catalyzed system for the coupling of propylene oxide and carbon dioxide reveal that although cyclic carbonate is the main product provided at elevated temperatures, at ambient temperature polycarbonate formation is dominant. A common reaction pathway for

  5. Mechanistic studies of the copolymerization reaction of oxetane and carbon dioxide to provide aliphatic polycarbonates catalyzed by (Salen)CrX complexes.

    PubMed

    Darensbourg, Donald J; Moncada, Adriana I; Choi, Wonsook; Reibenspies, Joseph H

    2008-05-21

    Chromium salen derivatives in the presence of anionic initiators have been shown to be very effective catalytic systems for the selective coupling of oxetane and carbon dioxide to provide the corresponding polycarbonate with a minimal amount of ether linkages. Optimization of the chromium(III) system was achieved utilizing a salen ligand with tert-butyl groups in the 3,5-positions of the phenolate rings and a cyclohexylene backbone for the diimine along with an azide ion initiator. The mechanism for the coupling reaction of oxetane and carbon dioxide has been studied. Based on binding studies done by infrared spectroscopy, X-ray crystallography, kinetic data, end group analysis done by (1)H NMR, and infrared spectroscopy, a mechanism of the copolymerization reaction is proposed. The formation of the copolymer is shown to proceed in part by way of the intermediacy of trimethylene carbonate, which was observed as a minor product of the coupling reaction, and by the direct enchainment of oxetane and CO 2. The parity of the determined free energies of activation for these two processes, namely 101.9 kJ x mol (-1) for ring-opening polymerization of trimethylene carbonate and 107.6 kJ x mol (-1) for copolymerization of oxetane and carbon dioxide supports this conclusion.

  6. Experimental Demonstrations in Teaching Chemical Reactions.

    ERIC Educational Resources Information Center

    Hugerat, Muhamad; Basheer, Sobhi

    2001-01-01

    Presents demonstrations of chemical reactions by employing different features of various compounds that can be altered after a chemical change occurs. Experimental activities include para- and dia-magnetism in chemical reactions, aluminum reaction with base, reaction of acid with carbonates, use of electrochemical cells for demonstrating chemical…

  7. Experimental Study of Serpentinization Reactions

    NASA Technical Reports Server (NTRS)

    Cohen, B. A.; Brearley, A. J.; Ganguly, J.; Liermann, H.-P.; Keil, K.

    2004-01-01

    Current carbonaceous chondrite parent-body thermal models [1-3] produce scenarios that are inconsistent with constraints on aqueous alteration conditions based on meteorite mineralogical evidence, such as phase stability relationships within the meteorite matrix minerals [4] and isotope equilibration arguments [5, 6]. This discrepancy arises principally because of the thermal runaway effect produced by silicate hydration reactions (here loosely called serpentinization, as the principal products are serpentine minerals), which are so exothermic as to produce more than enough heat to melt more ice and provide a self-sustaining chain reaction. One possible way to dissipate the heat of reaction is to use a very small parent body [e.g., 2] or possibly a rubble pile model. Another possibility is to release this heat more slowly, which depends on the alteration reaction path and kinetics.

  8. EXFOR Library of Experimental Nuclear Reaction Data

    DOE Data Explorer

    The EXFOR library contains an extensive compilation of experimental nuclear reaction data up to 1 GeV. Neutron reactions have been compiled systematically since the discovery of the neutron, while charged particle(up to carbon) and photon reactions have been covered less extensively. Files contain nuclear reaction data such as cross sections, spectra, angular distributions, polarizations, etc, along with information on experimental technique, error analysis, and applied standards. Numerous search parameters include: target, beam, product, experimental method, and even author and publication names. The library contains data from more than 20,000 experiments. (Specialized Interface)

  9. Development of Novel Polymeric Prodrugs Synthesized by Mechanochemical Solid-State Copolymerization of Hydroxyethylcellulose and Vinyl Monomers.

    PubMed

    Doi, Naoki; Sasai, Yasushi; Yamauchi, Yukinori; Adachi, Tetsuo; Kuzuya, Masayuki; Kondo, Shin-ichi

    2015-01-01

    Novel polymeric prodrugs were synthesized by mechanochemical solid-state copolymerization of hydroxyethylcellulose and the methacryloyloxy derivative of 5-fluorouracil (5-FU). Copolymerization was about 94% complete after 4 h, and the polymeric prodrug was quantitatively obtained after 14 h of reaction. The number average molecular weight (Mn) and polydispersity (H) of the polymeric prodrug were 39000 g/mol and 6.20, respectively. Mechanical fracturing of the polymer in a stainless steel twin-shell blender improved these properties (Mn=16000 g/mol and H=1.94). 5-FU was sustainably released from the polymeric prodrugs, and the rate was not affected by the molecular weight or molecular weight distribution of the prodrug under the experimental conditions used. These results suggest that novel polymeric prodrugs composed of a polysaccharide and a synthetic polymer can be fabricated by mechanochemical solid-state copolymerization under anaerobic conditions.

  10. Development of Novel Polymeric Prodrugs Synthesized by Mechanochemical Solid-State Copolymerization of Hydroxyethylcellulose and Vinyl Monomers.

    PubMed

    Doi, Naoki; Sasai, Yasushi; Yamauchi, Yukinori; Adachi, Tetsuo; Kuzuya, Masayuki; Kondo, Shin-ichi

    2015-01-01

    Novel polymeric prodrugs were synthesized by mechanochemical solid-state copolymerization of hydroxyethylcellulose and the methacryloyloxy derivative of 5-fluorouracil (5-FU). Copolymerization was about 94% complete after 4 h, and the polymeric prodrug was quantitatively obtained after 14 h of reaction. The number average molecular weight (Mn) and polydispersity (H) of the polymeric prodrug were 39000 g/mol and 6.20, respectively. Mechanical fracturing of the polymer in a stainless steel twin-shell blender improved these properties (Mn=16000 g/mol and H=1.94). 5-FU was sustainably released from the polymeric prodrugs, and the rate was not affected by the molecular weight or molecular weight distribution of the prodrug under the experimental conditions used. These results suggest that novel polymeric prodrugs composed of a polysaccharide and a synthetic polymer can be fabricated by mechanochemical solid-state copolymerization under anaerobic conditions. PMID:26423117

  11. Immune reactions and allergy in experimental anisakiasis

    PubMed Central

    Lee, Haneul Nari

    2006-01-01

    The third-stage larvae (L3) of the parasitic nematode, Anisakis simplex, have been implicated in the induction of hyperimmune allergic reactions in orally infected humans. In this work, we have conducted a review of an investigation into immune reactions occurring in animals experimentally infected with A. simplex L3. The patterns of serum antibody productions in the experimental animals against excretory-secretory products (ESP) of A. simplex L3 contributed to our current knowledge regarding specific humoral immune reactions in humans. In our review, we were able to determine that L3 infection of experimental animals may constitute a good model system for further exploration of immune mechanisms and allergy in anisakiasis of humans. PMID:17170569

  12. Experimental nuclear reaction data collection EXFOR

    SciTech Connect

    Semkova, V.; Otuka, N.; Simakov, S. P.; Zerkin, V.

    2011-07-01

    The International Network of Nuclear Reaction Data Centres (NRDC) constitutes a worldwide cooperation of 14 nuclear data centres. The main activity of the NRDC Network is collection and compilation of experimental nuclear reaction cross section data and the related bibliographic information in the EXFOR and CINDA databases as well as dissemination of nuclear reaction data and associated documentation to users. The database contains information and numerical data from more than about 19000 experiments consisting of more than 140000 datasets. EXFOR is kept up to date by constantly adding newly published experimental information. Tools developed for data dissemination utilise modern database technologies with fast online capabilities over the Internet. Users are provided with sophisticated search options, a user-friendly retrieval interface for downloading data in different formats, and additional output options such as improved data plotting capabilities. The present status of the EXFOR database will be presented together with the latest development for data access and retrieval. (authors)

  13. Experimental studies of gas-aerosol reactions

    NASA Astrophysics Data System (ADS)

    Gupta, Anand

    1991-05-01

    The aqueous phase oxidation of SO2 by H2O2 is believed to the principle mechanism for atmospheric sulfate formation in cloud droplets. However, no studies in noncloud aerosol systems have been reported. The objective is to quantify the importance of the noncloud liquid phase reactions of SO2 by H2O2 in the atmosphere. Growth rates of submicron droplets exposed to SO2 and H2O2 were measured using the tandem differential mobility analyzer (TDMA) technique (Rader and McMurry, 1986). The technique uses differential mobility analyzers (DMA's) to generate monodisperse particles and to measure particle size after the reaction. To facilitate submicron monodisperse droplet production with the DMA, a low-ion-concentration charter capable of generating singly charged particles up to 1.0 microns was developed and experimentally evaluated. The experiments were performed using dry and deliquesced (NH4)2SO4 particles with SO2 and H2O2 concentrations from 0-860 ppb and 0-150 ppb, respectively. No growth was observed for dry particles. For droplets greater than or equal to 0.3 microns, the fractional diameter growth was independent of particle size and for droplets less than or equal to 0.2 microns, it decreased as particle size decreased. The observed decrease is due to NH3 evaporation. As ammonia evaporates, droplet pH decreases causing the oxidation rate to decrease, leading to a lower growth rate. To predict the size-dependent growth rates, a theoretical model was developed using solution thermodynamics, gas/particle equilibrium, and chemical kinetics. The experimental and theoretical results are in reasonable agreement. For dry (NH4)2SO4 particles exposed to SO2, H2O2, NH3, and H2O vapor, surface reaction-controlled growth was observed. Particle growth was very sensitive to particle composition. No growth was observed for Polystyrene latex particles, whereas (NH4)2SO4 particles doped with catalysts (Fe(2+), Fe(3+), Mn(2+) and Cu(2+)) in a molar ratio of 1:500 grew slower than

  14. Tuning the critical solution temperature of polymers by copolymerization

    SciTech Connect

    Schulz, Bernhard; Chudoba, Richard; Dzubiella, Joachim; Heyda, Jan

    2015-12-28

    We study statistical copolymerization effects on the upper critical solution temperature (CST) of generic homopolymers by means of coarse-grained Langevin dynamics computer simulations and mean-field theory. Our systematic investigation reveals that the CST can change monotonically or non-monotonically with copolymerization, as observed in experimental studies, depending on the degree of non-additivity of the monomer (A-B) cross-interactions. The simulation findings are confirmed and qualitatively explained by a combination of a two-component Flory-de Gennes model for polymer collapse and a simple thermodynamic expansion approach. Our findings provide some rationale behind the effects of copolymerization and may be helpful for tuning CST behavior of polymers in soft material design.

  15. Direct Copolymerization of CO2 and Diols.

    PubMed

    Tamura, Masazumi; Ito, Kazuki; Honda, Masayoshi; Nakagawa, Yoshinao; Sugimoto, Hiroshi; Tomishige, Keiichi

    2016-01-01

    Direct polymerization of CO2 and diols is promising as a simple and environmental-benign method in place of conventional processes using high-cost and/or hazardous reagents such as phosgene, carbon monoxide and epoxides, however, there are no reports on the direct method due to the inertness of CO2 and severe equilibrium limitation of the reaction. Herein, we firstly substantiate the direct copolymerization of CO2 and diols using CeO2 catalyst and 2-cyanopyridine promotor, providing the alternating cooligomers in high diol-based yield (up to 99%) and selectivity (up to >99%). This catalyst system is applicable to various diols including linear C4-C10 α,ω-diols to provide high yields of the corresponding cooligomers, which cannot be obtained by well-known methods such as copolymerization of CO2 and cyclic ethers and ring-opening polymerization of cyclic carbonates. This process provides us a facile synthesis method for versatile polycarbonates from various diols and CO2 owing to simplicity of diols modification. PMID:27075987

  16. Direct Copolymerization of CO2 and Diols

    PubMed Central

    Tamura, Masazumi; Ito, Kazuki; Honda, Masayoshi; Nakagawa, Yoshinao; Sugimoto, Hiroshi; Tomishige, Keiichi

    2016-01-01

    Direct polymerization of CO2 and diols is promising as a simple and environmental-benign method in place of conventional processes using high-cost and/or hazardous reagents such as phosgene, carbon monoxide and epoxides, however, there are no reports on the direct method due to the inertness of CO2 and severe equilibrium limitation of the reaction. Herein, we firstly substantiate the direct copolymerization of CO2 and diols using CeO2 catalyst and 2-cyanopyridine promotor, providing the alternating cooligomers in high diol-based yield (up to 99%) and selectivity (up to >99%). This catalyst system is applicable to various diols including linear C4-C10 α,ω-diols to provide high yields of the corresponding cooligomers, which cannot be obtained by well-known methods such as copolymerization of CO2 and cyclic ethers and ring-opening polymerization of cyclic carbonates. This process provides us a facile synthesis method for versatile polycarbonates from various diols and CO2 owing to simplicity of diols modification. PMID:27075987

  17. Porating anion-responsive copolymeric gels.

    PubMed

    England, Dustin; Yan, Feng; Texter, John

    2013-09-24

    A polymerizable ionic liquid surfactant, 1-(11-acryloyloxyundecyl)-3-methylimidiazolium bromide (ILBr), was copolymerized with methyl methacrylate (MMA) in aqueous microemulsions at 30% (ILBr w/w) and various water to MMA ratios. The ternary phase diagram of the ILBr/MMA/water system was constructed at 25 and 60 °C. Homopolymers and copolymers of ILBr and MMA were produced by thermally initiated chain radical microemulsion polymerization at various compositions in bicontinuous and reverse microemulsion subdomains. Microemulsion polymerization reaction products varied from being gel-like to solid, and these materials were analyzed by thermal and scanning electron microscopy methods. Microemulsion polymerized materials were insoluble in all solvents tested, consistent with light cross-linking. Ion exchange between Br(-) and PF6(-) in these copolymeric materials resulted in the formation of open-cell porous structures in some of these materials, as was confirmed by scanning electron microscopy (SEM). Several compositions illustrate the capture of prepolymerization nanoscale structure by thermally initiated polymerization, expanding the domain of compositions exhibiting this feat and yet to be demonstrated in any other system. Regular cylindrical pores in interpenetrating ILBr-co-MMA and PMMA networks are produced by anion exchange in the absence of templates. A percolating cluster/bicontinuous transition is "captured" by SEM after using anion exchange to visualize the mixed cluster/pore morphology. Some design principles for achieving this capture and for obtaining stimuli responsive solvogels are articulated, and the importance of producing solvogels in capturing the nanoscale is highlighted. PMID:23968242

  18. Direct Copolymerization of CO2 and Diols

    NASA Astrophysics Data System (ADS)

    Tamura, Masazumi; Ito, Kazuki; Honda, Masayoshi; Nakagawa, Yoshinao; Sugimoto, Hiroshi; Tomishige, Keiichi

    2016-04-01

    Direct polymerization of CO2 and diols is promising as a simple and environmental-benign method in place of conventional processes using high-cost and/or hazardous reagents such as phosgene, carbon monoxide and epoxides, however, there are no reports on the direct method due to the inertness of CO2 and severe equilibrium limitation of the reaction. Herein, we firstly substantiate the direct copolymerization of CO2 and diols using CeO2 catalyst and 2-cyanopyridine promotor, providing the alternating cooligomers in high diol-based yield (up to 99%) and selectivity (up to >99%). This catalyst system is applicable to various diols including linear C4-C10 α,ω-diols to provide high yields of the corresponding cooligomers, which cannot be obtained by well-known methods such as copolymerization of CO2 and cyclic ethers and ring-opening polymerization of cyclic carbonates. This process provides us a facile synthesis method for versatile polycarbonates from various diols and CO2 owing to simplicity of diols modification.

  19. Copolymerization of carbon dioxide and butadiene via a lactone intermediate.

    PubMed

    Nakano, Ryo; Ito, Shingo; Nozaki, Kyoko

    2014-04-01

    Although carbon dioxide has attracted broad interest as a renewable carbon feedstock, its use as a monomer in copolymerization with olefins has long been an elusive endeavour. A major obstacle for this process is that the propagation step involving carbon dioxide is endothermic; typically, attempted reactions between carbon dioxide and an olefin preferentially yield olefin homopolymerization. Here we report a strategy to circumvent the thermodynamic and kinetic barriers for copolymerizations of carbon dioxide and olefins by using a metastable lactone intermediate, 3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one, which is formed by the palladium-catalysed condensation of carbon dioxide and 1,3-butadiene. Subsequent free-radical polymerization of the lactone intermediate afforded polymers of high molecular weight with a carbon dioxide content of 33 mol% (29 wt%). Furthermore, the protocol was applied successfully to a one-pot copolymerization of carbon dioxide and 1,3-butadiene, and one-pot terpolymerizations of carbon dioxide, butadiene and another 1,3-diene. This copolymerization technique provides access to a new class of polymeric materials made from carbon dioxide.

  20. Characteristics of vestibulosensory reactions studied by experimental caloric test

    NASA Technical Reports Server (NTRS)

    Kapranov, V. Z.

    1980-01-01

    Vestibulo-sensory reactions were studied in 135 workers who were in contact with nitroethers, by the method of an experimental caloric test. The response vestibulo-sensory reactions were recorded by means of an electroencephalograph. The changes in the sensory reaction depended on the duration of the workers' contact with toxic agents. A study of illusion reactions by the labyrinth calorization widens diagnostic possibilities in the examination of functional condition of the vestibular analyser considerably.

  1. Experimental Study of Stellar Reactions at CNS

    SciTech Connect

    Kubono, S.; Yamaguchi, H.; Wakabayashi, Y.; Amadio, G.; Hayakawa, S.; He, J. J.; Saito, A.; Teranishi, T.; Nishimura, S.; Fukunishi, N.; Iwasa, N.; Inafuku, K.; Kato, S.; Tanaka, M. H.; Fuchi, Y.; Moon, J. Y.; Kwon, K.; Lee, C. S.; Khiem, Le Hong; Chen, A.

    2006-11-02

    After a brief review on low-energy RI beam production technology, nuclear astrophysics programs at CNS are presented including a scope of the field in the Wako campus. The CRIB project involves a total development of the whole facility to maximize the low-energy RI beam intensities, including the ion source, the AVF cyclotron and the low-energy RI beam separator CRIB, Some recent nuclear astrophysics experiments performed with the RI beams were discussed, including the measurement of the 14O({alpha},p)17F reaction, the key stellar reaction for the onset of the high-temperature rp-process. The first experiment performed with a newly installed high-resolution magnetic spectrograph PA of CNS was also presented. Collaboration possibilities for nuclear astrophysics in the RIKEN campus are also touched.

  2. Experimental Study of Stellar Reactions at CNS

    NASA Astrophysics Data System (ADS)

    Kubono, S.; Yamaguchi, H.; Wakabayashi, Y.; Amadio, G.; Hayakawa, S.; He, J. J.; Saito, A.; Teranishi, T.; Nishimura, S.; Fukunishi, N.; Iwasa, N.; Inafuku, K.; Kato, S.; Tanaka, M. H.; Fuchi, Y.; Moon, J. Y.; Kwon, K.; Lee, C. S.; Khiem, Le Hong; Chen, A.; Pearson, J.

    2006-11-01

    After a brief review on low-energy RI beam production technology, nuclear astrophysics programs at CNS are presented including a scope of the field in the Wako campus. The CRIB project involves a total development of the whole facility to maximize the low-energy RI beam intensities, including the ion source, the AVF cyclotron and the low-energy RI beam separator CRIB, Some recent nuclear astrophysics experiments performed with the RI beams were discussed, including the measurement of the 14O(α,p)17F reaction, the key stellar reaction for the onset of the high-temperature rp-process. The first experiment performed with a newly installed high-resolution magnetic spectrograph PA of CNS was also presented. Collaboration possibilities for nuclear astrophysics in the RIKEN campus are also touched.

  3. Experimental studies of reactions relevant for γ-process nucleosynthesis

    SciTech Connect

    Scholz, P.; Endres, J.; Hennig, A.; Mayer, J.; Netterdon, L.; Zilges, A.; Sauerwein, A.

    2014-05-09

    We report on our recent experimental studies of reactions relevant for the γ process nucleosynthesis. Applying the activation method using the Cologne Clover Counting Setup total cross sections of the reactions {sup 168}Yb(α,γ), {sup 168}Yb(α,n), and {sup 187}Re(α,n) could be obtained. Furthermore, the reaction {sup 89}Y(p,γ) was investigated via the in-beam technique with HPGe detectors at the high-efficiency g-ray spectrometer HORUS in Cologne in order to determine partial and total cross sections.

  4. Improving electrochromic properties via copolymerization

    NASA Astrophysics Data System (ADS)

    Tuba Taskin, Asli; Balan, Abidin; Arslan Udum, Yasemin; Toppare, Levent

    2010-06-01

    Copolymers of 5,8-di(1H-pyrrol-2-yl)-2,3-di(thiophen-2-yl)quinoxaline (PTQ) in the presence of 2, 2'-bis(3,4-ethylenedioxythiophene) (BiEDOT) and 4,7-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-2-dodecyl-2H-benzo[1,2,3] triazole (BEBT) were synthesized via the potentiodynamic method in a tetrabutylammonium perchlorate/dichloromethane (TBAP/DCM) (0.1 M) solvent-electrolyte couple. P(PTQ-co-BiEDOT) reveals an oxidation potential at + 0.45 V and a reduction potential at - 0.2 V (figure 1(a)), whereas the homopolymer, P(PTQ) has an oxidation potential of + 0.55 V and a reduction potential of + 0.1 V. Spectroelectrochemical behaviors and the switching ability of copolymers were investigated by ultraviolet-visible (UV-vis) spectroscopy and cyclic voltammetry. The spectroelectrochemical behaviors of the P(PTQ-co-BiEDOT) and P(PTQ-co-BEBT) in comparison to the homopolymer revealed solid evidence of copolymerization based upon the differences in the spectral signatures. P(PTQ-co-BEBT) reveals 80% optical contrast at 1450 nm whereas the homopolymer achieves only 66% at 1460 nm. Coloration efficiency of P(PTQ-co-BEBT) was found to be 132 cm2 C - 1 compared to 116 cm2 C - 1 of the homopolymer at 100% full switch in the visible region. Switching times of the polymers were evaluated by kinetic studies upon measuring the per cent transmittance (%T) at the maximum contrast point. P(PTQ-co-BEBT) switches between the two extreme states in 0.5 s compared to 1.2 s for the homopolymer.

  5. Theoretical consideration of bulk free-radical copolymerization with allowance for the preferential sorption of monomers into globular nanoreactors

    NASA Astrophysics Data System (ADS)

    Kuchanov, S. I.; Pogodin, S. G.

    2008-06-01

    The thermodynamics of a globular solution of binary copolymer in two-component solvent is theoretically considered. Classification of phase diagrams of such a solution is performed by their topological appearance. Based on the thermodynamic theory, binary bulk free-radical copolymerization under low conversions is examined in systems where macroradicals being in globular conformational state represent isolated nanoreactors. The theoretical results achieved permit an explanation of all qualitative peculiarities observed experimentally under copolymerization in such anomalous systems.

  6. Identifying Understudied Nuclear Reactions by Text-mining the EXFOR Experimental Nuclear Reaction Library

    NASA Astrophysics Data System (ADS)

    Hirdt, J. A.; Brown, D. A.

    2016-01-01

    The EXFOR library contains the largest collection of experimental nuclear reaction data available as well as the data's bibliographic information and experimental details. We text-mined the REACTION and MONITOR fields of the ENTRYs in the EXFOR library in order to identify understudied reactions and quantities. Using the results of the text-mining, we created an undirected graph from the EXFOR datasets with each graph node representing a single reaction and quantity and graph links representing the various types of connections between these reactions and quantities. This graph is an abstract representation of the connections in EXFOR, similar to graphs of social networks, authorship networks, etc. We use various graph theoretical tools to identify important yet understudied reactions and quantities in EXFOR. Although we identified a few cross sections relevant for shielding applications and isotope production, mostly we identified charged particle fluence monitor cross sections. As a side effect of this work, we learn that our abstract graph is typical of other real-world graphs.

  7. Reactivity ratios, and mechanistic insight for anionic ring-opening copolymerization of epoxides.

    PubMed

    Lee, Bongjae F; Wolffs, Martin; Delaney, Kris T; Sprafke, Johannes K; Leibfarth, Frank A; Hawker, Craig J; Lynd, Nathaniel A

    2012-05-01

    Reactivity ratios were evaluated for anionic ring-opening copolymerizations of ethylene oxide (EO) with either allyl glycidyl ether (AGE) or ethylene glycol vinyl glycidyl ether (EGVGE) using a benzyl alkoxide initiator. The chemical shift for the benzylic protons of the initiator, as measured by (1)H NMR spectroscopy, were observed to be sensitive to the sequence of the first two monomers added to the initiator during polymer growth. Using a simple kinetic model for initiation and the first propagation step, reactivity ratios for the copolymerization of AGE and EGVGE with EO could be determined by analysis of the (1)H NMR spectroscopy for the resulting copolymer. For the copolymerization between EO and AGE, the reactivity ratios were determined to be r(AGE) = 1.31 ± 0.26 and r(EO) = 0.54 ± 0.03, while for EO and EGVGE, the reactivity ratios were r(EGVGE) = 3.50 ± 0.90 and r(EO) = 0.32 ± 0.10. These ratios were consistent with the compositional drift observed in the copolymerization between EO and EGVGE, with EGVGE being consumed early in the copolymerization. These experimental results, combined with density functional calculations, allowed a mechanism for oxyanionic ring-opening polymerization that begins with coordination of the Lewis-basic epoxide to the cation to be proposed. The calculated transition-state energies agree qualitatively with the observed relative rates for polymerization. PMID:23226879

  8. Influence of diosgenin structure on the polymerization kinetics of acrylamide: An experimental and theoretical approach

    NASA Astrophysics Data System (ADS)

    Odio, Oscar F.; Martínez, Ariel; Martínez, Ricardo; Crespo-Otero, Rachel; Montero-Cabrera, Luis A.

    2011-01-01

    The acrylamide polymerization in presence of diosgenin has been investigated by experimental and theoretical methods. NMR spectroscopy shows the absence of copolymerization. Viscosimetric and dilatometric experiments support the occurrence of transfer reactions that retard the polymerization. The mechanism was studied at the MPWB1K/6-31G(d,p)//B3LYP/6-31G(d,p) level of theory. Transfer, homopropagation, copolymerization and reinitiation reactions were considered either in gas or solution phase. According to results, the retardation seems to be originated by the formation of an allylic radical in the ring B of diosgenin that reinitiates acrylamide polymerization at slow rate.

  9. Radiation initiated copolymerization of allyl alcohol with acrylonitrile

    NASA Astrophysics Data System (ADS)

    Şolpan, Dilek; Güven, Olgun

    1996-07-01

    Copolymerization of allyl alcohol (AA) with acrylonitrile (AN) initiated by γ-rays has been investigated to determine the respective reactivity ratios. Three different experimental techniques, namely Fourier Transform Infrared (FTIR), Ultraviolet (UV/vis) and elemental analysis (EA) have been used for the determination of copolymer compositions. Fineman-Ross (FR), Kelen-Tüdös (KT), Non-Linear Least Square (NLLS) Analysis and Q-e methods have been applied to the three sets of experimental data. It has been concluded that data obtained from elemental analysis as applied to the Non-Linear Least Square approach gave the most reliable reactivity ratios as 2.09 and 0.40 for acrylonitrile and allyl alcohol, respectively.

  10. Chain Transfer of Vegetable Oil Macromonomers in Acrylic Solution Copolymerization

    SciTech Connect

    Black, Micah; Messman, Jamie M; Rawlins, James

    2011-01-01

    Use of vegetable oil macromonomers (VOMMs) as comonomers in emulsion polymerization enables good film coalescence without the addition of solvents that constitute volatile organic compounds (VOCs). VOMMs are derived from renewable resources and offer the potential of post-application crosslinking via auto-oxidation. However, chain transfer reactions of VOMMs with initiator and/or polymer radicals during emulsion polymerization reduce the amount of allylic hydrogen atoms available for primary auto-oxidation during drying. Vegetable oils and derivatives were reacted in combination with butyl acrylate and methyl methacrylate via solution polymerization. The copolymerization was monitored using in situ infrared spectroscopy to determine the extent of chain transfer. 1H NMR spectroscopy was used to determine the loci of chain transfer and the molecular weight characteristics of the polymers were characterized by SEC. Solution polymerization was utilized to minimize temperature fluctuations and maintain polymer solubility during the initial characterization.

  11. Kinetics and thermodynamics of first-order Markov chain copolymerization

    SciTech Connect

    Gaspard, P.; Andrieux, D.

    2014-07-28

    We report a theoretical study of stochastic processes modeling the growth of first-order Markov copolymers, as well as the reversed reaction of depolymerization. These processes are ruled by kinetic equations describing both the attachment and detachment of monomers. Exact solutions are obtained for these kinetic equations in the steady regimes of multicomponent copolymerization and depolymerization. Thermodynamic equilibrium is identified as the state at which the growth velocity is vanishing on average and where detailed balance is satisfied. Away from equilibrium, the analytical expression of the thermodynamic entropy production is deduced in terms of the Shannon disorder per monomer in the copolymer sequence. The Mayo-Lewis equation is recovered in the fully irreversible growth regime. The theory also applies to Bernoullian chains in the case where the attachment and detachment rates only depend on the reacting monomer.

  12. Experimental Astrochemistry: Molecular Formation via Grain-Surface Reactions

    NASA Astrophysics Data System (ADS)

    Congiu, E.

    2007-03-01

    Central to this thesis is the chemistry occurring on dust grain surfaces leading to the formation of molecules in the ISM, and, in particular, the laboratory simulation of formation mechanisms and formation rates. Surface chemistry plays a crucial role in the ISM because it produces key species that are not formed in gas-phase reactions at an efficient rate. Among them, molecular hydrogen (H_2) is by far the most important. In this work (Chapter 3), I shall address the experimental investigation of H_2 formation on diverse samples of amorphous silicates. The experimental work was conducted in the Physics Department laboratories at Syracuse University, New York, as part of the most successful programme of experiments so far to study the processes involved in the formation of molecular hydrogen on a variety of dust analogue materials, also including poly-crystalline olivine, amorphous carbon, and ices. The experiments were carried out through mass spectrometry and TPD techniques and under conditions that come as close as technically feasible to the ones in the most relevant ISM environments, namely, under ultra high vacuum pressures (low 10e-10 torr) and at surface temperatures between 6 and 30 K. Experimental studies of H_2 formation on amorphous olivines are of major concern in grain-surface chemistry because amorphous silicates are believed, together with carbonaceous materials, to be the most realistic analogues of bare cosmic dust surfaces in diffuse clouds. In my doctorate work I carried out numerous experiments on a set of several samples of amorphous olivines of the type (Mg_x,Fe_1-x)_2SiO_4, namely, samples made up of diverse amounts of Mg and Fe. Besides, in Chapter 4, I shall address the project and the construction of a FT-RAIRS facility that is to integrate the existent research apparatus in the laboratory at Syracuse University. I shall first discuss the FT-IR spectroscopy, then I shall focus on a particular technique used in surface science called

  13. Spin-selective recombination reactions of radical pairs: Experimental test of validity of reaction operators

    SciTech Connect

    Maeda, Kiminori; Liddell, Paul; Gust, Devens; Hore, P. J.

    2013-12-21

    Spin-selective reactions of radical pairs are conventionally modelled using an approach that dates back to the 1970s [R. Haberkorn, Mol. Phys. 32, 1491 (1976)]. An alternative approach based on the theory of quantum measurements has recently been suggested [J. A. Jones and P. J. Hore, Chem. Phys. Lett. 488, 90 (2010)]. We present here the first experimental attempt to discriminate between the two models. Pulsed electron paramagnetic resonance spectroscopy has been used to investigate intramolecular electron transfer in the radical pair form of a carotenoid-porphyrin-fullerene molecular triad. The rate of spin-spin relaxation of the fullerene radical in the triad was found to be inconsistent with the quantum measurement description of the spin-selective kinetics, and in accord with the conventional model when combined with spin-dephasing caused by rotational modulation of the anisotropic g-tensor of the fullerene radical.

  14. Experimental Observation of Nuclear Reactions in Palladium and Uranium

    SciTech Connect

    J. Dufour; D. Murat; X. Dufour; J. Foos

    2001-11-12

    By submitting various metals (Pd, U) containing hydrogen (from 2000 to 700 000 atoms of hydrogen for 1 000 000 atoms of the host metal) to the combined action of electrical currents and magnetic fields, we have observed a sizeable exothermal effect (from 0.1 to 8 W for 500 mg of metal used). This effect is beyond experimental errors, the energy output being typically 130 to 250{percent} of the energy input and not of chemical origin (exothermal effect in the range of 7000 MJ/mol of metal in the case of palladium and of 60 MJ/mol in the case of uranium). New chemical species also appear in the processes metals. It has been shown by a QED calculation that resonances of long lifetime (s), nuclear dimensions (fm), and low energy of formation (eV) could exist. This concept seems to look like the 'shrunken hydrogen atoms' proposed by various authors. It is indeed very different in two ways (a) being a metastable state, it needs energy to be formed (a few eV) and reverts to normal hydrogen after a few seconds, liberating back its energy of formation (it is thus not the source of the energy observed); (b) its formation can be described as the electron spin/proton nuclear spin interaction becoming first order in the lattice environment (whereas it is third order in a normal hydrogen atom). Moreover, we consider that the hydrex cannot yield a neutron because this reaction is strongly endothermic. To explain our results, we put forward the following working hypothesis: In a metal lattice and under proper conditions, the formation of such resonances (metastable state) could be favored. We propose to call them HYDREX, and we assume that they are actually formed in cold fusion (CF) and low-energy nuclear reaction (LENR) experiments. Once formed, a number of HYDREX could gather around a nucleus of the lattice to form a cluster of nuclear size and of very long life time compared to nuclear time (10{sup -22} s). In this cluster, nuclear rearrangements could take place, yielding

  15. Copper mediated controlled radical copolymerization of styrene and 2-ethylhexyl acrylate and determination of their reactivity ratios.

    NASA Astrophysics Data System (ADS)

    Koiry, Bishnu; Singha, Nikhil

    2014-10-01

    Copolymerization is an important synthetic tool to prepare polymers with desirable combination of properties which are difficult to achieve from the different homopolymers concerned. This investigation reports the copolymerization of 2-ethylhexyl acrylate (EHA) and styrene using copper bromide (CuBr) as catalyst in combination with N,N,N’,N”,N”- pentamethyldiethylenetriamine (PMDETA) as ligand and 1-phenylethyl bromide (PEBr) as initiator. Linear kinetic plot and linear increase in molecular weights versus conversion indicate that copolymerization reactions were controlled. The copolymer composition was calculated using 1H NMR studies. The reactivity ratio of styrene and EHA (r1 and r2) were determined using the Finemann-Ross (FR), inverted Finemann-Ross (FR) and Kelen-Tudos (KT) methods. Thermal properties of the copolymers were also studied by using TGA and DSC analysis.

  16. Copper mediated controlled radical copolymerization of styrene and 2-ethylhexyl acrylate and determination of their reactivity ratios.

    PubMed

    Koiry, Bishnu P; Singha, Nikhil K

    2014-01-01

    Copolymerization is an important synthetic tool to prepare polymers with desirable combination of properties which are difficult to achieve from the different homopolymers concerned. This investigation reports the copolymerization of 2-ethylhexyl acrylate (EHA) and styrene using copper bromide (CuBr) as catalyst in combination with N,N,N',N″,N″- pentamethyldiethylenetriamine (PMDETA) as ligand and 1-phenylethyl bromide (PEBr) as initiator. Linear kinetic plot and linear increase in molecular weights vs. conversion indicate that copolymerization reactions were controlled. The copolymer composition was calculated using (1)H NMR studies. The reactivity ratio of styrene and EHA (r1 and r2) were determined using the Finemann-Ross (FR), inverted Finemann-Ross (IFR), and Kelen-Tudos (KT) methods. Thermal properties of the copolymers were also studied by using TGA and DSC analysis. PMID:25368866

  17. Fragmentation and Coagulation in Supramolecular (Co)polymerization Kinetics.

    PubMed

    Markvoort, Albert J; Eikelder, Huub M M Ten; Hilbers, Peter A J; de Greef, Tom F A

    2016-04-27

    The self-assembly of molecular building blocks into one-dimensional supramolecular architectures has opened up new frontiers in materials science. Due to the noncovalent interactions between the monomeric units, these architectures are intrinsically dynamic, and understanding their kinetic driving forces is key to rationally programming their morphology and function. To understand the self-assembly dynamics of supramolecular polymerizations (SP), kinetic models based on aggregate growth by sequential monomer association and dissociation have been analyzed. However, fragmentation and coagulation events can also play a role, as evident from studies on peptide self-assembly and the fact that aggregations can be sensitive to mechanical agitations. Here, we analyze how fragmentation and coagulation events influence SP kinetics by theoretical analysis of self-assembling systems of increasing complexity. Our analysis starts with single-component systems in which aggregates are able to grow via an isodesmic or cooperative nucleation-elongation mechanism. Subsequently, equilibration dynamics in cooperative two-component supramolecular copolymerizations are investigated. In the final part, we reveal how aggregate growth in the presence of competing, kinetically controlled pathways is influenced by fragmentation and coagulation reactions and reveal how seed-induced growth can give rise to block copolymers. Our analysis shows how fragmentation and coagulation reactions are able to modulate SP kinetics in ways that are highly system dependent. PMID:27163054

  18. Fragmentation and Coagulation in Supramolecular (Co)polymerization Kinetics

    PubMed Central

    2016-01-01

    The self-assembly of molecular building blocks into one-dimensional supramolecular architectures has opened up new frontiers in materials science. Due to the noncovalent interactions between the monomeric units, these architectures are intrinsically dynamic, and understanding their kinetic driving forces is key to rationally programming their morphology and function. To understand the self-assembly dynamics of supramolecular polymerizations (SP), kinetic models based on aggregate growth by sequential monomer association and dissociation have been analyzed. However, fragmentation and coagulation events can also play a role, as evident from studies on peptide self-assembly and the fact that aggregations can be sensitive to mechanical agitations. Here, we analyze how fragmentation and coagulation events influence SP kinetics by theoretical analysis of self-assembling systems of increasing complexity. Our analysis starts with single-component systems in which aggregates are able to grow via an isodesmic or cooperative nucleation–elongation mechanism. Subsequently, equilibration dynamics in cooperative two-component supramolecular copolymerizations are investigated. In the final part, we reveal how aggregate growth in the presence of competing, kinetically controlled pathways is influenced by fragmentation and coagulation reactions and reveal how seed-induced growth can give rise to block copolymers. Our analysis shows how fragmentation and coagulation reactions are able to modulate SP kinetics in ways that are highly system dependent. PMID:27163054

  19. Recent Direct Reaction Experimental Studies with Radioactive Tin Beams

    SciTech Connect

    Jones, K. L.; Ahn, S.; Allmond, J. M.; Ayres, A.; Bardayan, D. W.; Baugher, T.; Bazin, D.; Berryman, J. S.; Bey, A.; Bingham, C.; Cartegni, L.; Cerizza, G.; Chae, K. Y.; Cizewski, J. A.; Gade, A.; Galindo-Uribarri, A.; Garcia-Ruiz, R. F.; Grzywacz, R.; Howard, M. E.; Kozub, R. L.; Liang, J. F.; Manning, B.; Matoš, M.; McDaniel, S.; Miller, D.; Nesaraja, C. D.; O'Malley, P. D.; Padgett, S.; Padilla-Rodal, E.; Pain, S. D.; Pittman, S. T.; Radford, D. C.; Ratkiewicz, A.; Schmitt, K. T.; Shore, A.; Smith, M. S.; Stracener, D. W.; Stroberg, S. R.; Tostevin, J.; Varner, R. L.; Weisshaar, D.; Wimmer, K.; Winkler, R.

    2015-01-01

    Direct reaction techniques are powerful tools to study the single-particle nature of nuclei. Performing direct reactions on short-lived nuclei requires radioactive ion beams produced either via fragmentation or the Isotope Separation OnLine (ISOL) method. Some of the most interesting regions to study with direct reactions are close to the magic numbers where changes in shell structure can be tracked. These changes can impact the final abundances of explosive nucleosynthesis. The structure of the chain of tin isotopes is strongly influenced by the Z = 50 proton shell closure, as well as the neutron shell closures lying in the neutron-rich, N = 82, and neutron-deficient, N = 50, regions. Here, we present two examples of direct reactions on exotic tin isotopes. The first uses a one-neutron transfer reaction and a low-energy reaccelerated ISOL beam to study states in Sn-131 from across the N = 82 shell closure. The second example utilizes a one-neutron knockout reaction on fragmentation beams of neutron-deficient Sn-106,108Sn. In conclusion, In both cases, measurements of γ rays in coincidence with charged particles proved to be invaluable.

  20. Recent Direct Reaction Experimental Studies with Radioactive Tin Beams

    DOE PAGES

    Jones, K. L.; Ahn, S.; Allmond, J. M.; Ayres, A.; Bardayan, D. W.; Baugher, T.; Bazin, D.; Berryman, J. S.; Bey, A.; Bingham, C.; et al

    2015-01-01

    Direct reaction techniques are powerful tools to study the single-particle nature of nuclei. Performing direct reactions on short-lived nuclei requires radioactive ion beams produced either via fragmentation or the Isotope Separation OnLine (ISOL) method. Some of the most interesting regions to study with direct reactions are close to the magic numbers where changes in shell structure can be tracked. These changes can impact the final abundances of explosive nucleosynthesis. The structure of the chain of tin isotopes is strongly influenced by the Z = 50 proton shell closure, as well as the neutron shell closures lying in the neutron-rich, Nmore » = 82, and neutron-deficient, N = 50, regions. Here, we present two examples of direct reactions on exotic tin isotopes. The first uses a one-neutron transfer reaction and a low-energy reaccelerated ISOL beam to study states in Sn-131 from across the N = 82 shell closure. The second example utilizes a one-neutron knockout reaction on fragmentation beams of neutron-deficient Sn-106,108Sn. In conclusion, In both cases, measurements of γ rays in coincidence with charged particles proved to be invaluable.« less

  1. Improved homopolymer separation to enable the application of 1H NMR and HPLC for the determination of the reaction parameters of the graft copolymerization of acrylic acid onto starch.

    PubMed

    Witono, Judy R; Marsman, Jan Henk; Noordergraaf, Inge-Willem; Heeres, Hero J; Janssen, Leon P B M

    2013-04-01

    Graft copolymers of starch with acrylic acid are a promising green, bio based material with many potential applications. The grafting of acrylic acid onto cassava starch in an aqueous medium initiated by Fenton's reagent has been studied. Common grafting result parameters are add-on (yield) and graft efficiency (selectivity). However, the analysis of the reaction products and an accurate determination of these parameters stand or fall with a complete separation of the entangled but ungrafted homopolymer from the grafted product. Therefore, this separation is the core of the newly developed analytical procedure. An appropriate solvent has been selected with dedicated testing from the range methanol, ethanol, acetone, dioxane, 2-propanol, and 1-propanol. Acetone showed the best performance in many respects. It has a high dissolving power for the homopolymer, as well as the highest yield of precipitation for the starch derivatives and it is the most economical in use. After the successful separation, the precipitated graft copolymers could be analyzed quantitatively by nuclear magnetic resonance. The liquid with homopolymer and unreacted monomer was analyzed by high pressure liquid chromatography. Proof of grafting has been found by FTIR and TGA analyses. The mass balance calculation shows a systematic error which appears fairly consistent: 18.0±2.5 wt%. This was used as a correction factor in the calculation of the grafting parameters but more importantly, it means that the method we developed has a high level of repeatability, in the order of 97%. PMID:23435285

  2. Singlet Oxygen Reactions with Flavonoids. A Theoretical – Experimental Study

    PubMed Central

    Morales, Javier; Günther, Germán; Zanocco, Antonio L.; Lemp, Else

    2012-01-01

    Detection of singlet oxygen emission, λmax = 1270 nm, following laser excitation and steady-state methods were employed to measure the total reaction rate constant, kT, and the reactive reaction rate constant, kr, for the reaction between singlet oxygen and several flavonoids. Values of kT determined in deuterated water, ranging from 2.4×107 M−1s−1 to 13.4×107 M−1s−1, for rutin and morin, respectively, and the values measured for kr, ranging from 2.8×105 M−1s−1 to 65.7×105 M−1s−1 for kaempferol and morin, respectively, being epicatechin and catechin chemically unreactive. These results indicate that all the studied flavonoids are good quenchers of singlet oxygen and could be valuable antioxidants in systems under oxidative stress, in particular if a flavonoid-rich diet was previously consumed. Analysis of the dependence of rate constant values with molecular structure in terms of global descriptors and condensed Fukui functions, resulting from electronic structure calculations, supports the formation of a charge transfer exciplex in all studied reactions. The fraction of exciplex giving reaction products evolves through a hydroperoxide and/or an endoperoxide intermediate produced by singlet oxygen attack on the double bond of the ring C of the flavonoid. PMID:22802966

  3. Polynuclear aromatic hydrocarbons hydrogenation. 1: Experimental reaction pathways and kinetics

    SciTech Connect

    Korre, S.C.; Klein, M.T. . Dept. of Chemical Engineering); Quann, R.J. . Paulsboro Research Lab.)

    1995-01-01

    The relationship between molecular structure and hydrogenation reactivity in heavy oil hydroprocessing was sought via the elucidation of the controlling reaction pathways and kinetics of one-, two-, three-, and four-fused ring compounds. Hydrogenation reactions of o-xylene, tetralin, naphthalene, phenanthrene, anthracene, pyrene, and chrysene and their multicomponent mixtures were studied in cyclohexane solvent using a presulfided CoMo/Al[sub 2]O[sub 3] catalyst in a 1-liter batch autoclave at P[sub H[sub 2

  4. The Experimental Reduction of Stress Reaction by Cognitive Manipulation.

    ERIC Educational Resources Information Center

    Buck, John L.; And Others

    A cognitive appraisal of threat is believed to intervene between the appearance of a stressful stimulus and a stress reaction to the stimulus. The effect of a "rational" treatment on the appraisal of threat is investigated. Five groups of 13 college students each heard one of five treatment orientations before viewing slides showing the victims of…

  5. Direct reaction experimental studies with beams of radioactive tin ions

    SciTech Connect

    Jones, K. L. Ayres, A.; Bey, A.; Burcher, S.; Cartegni, L.; Cerizza, G.; Ahn, S.; Allmond, J. M.; Beene, J. R.; Galindo-Uribarri, A.; Liang, J. F.; Nesaraja, C. D.; Pain, S. D.; Radford, D. C.; Schmitt, K. T.; Smith, M. S.; Stracener, D. W.; Varner, R. L.; Bardayan, D. W.; Baugher, T.; and others

    2015-10-15

    The tin chain of isotopes provides a unique region in which to investigate the evolution of single-particle structure, spreading from N = 50 at {sup 100}Sn, through 10 stable isotopes and the N = 82 shell closure at {sup 132}Sn out into the r-process path. Direct reactions performed on radioactive ion beams are sensitive spectroscopic tools for studying exotic nuclei. Here we present one experiment knocking out neutrons from tin isotopes that are already neutron deficient and two reactions that add a neutron to neutron-rich {sup 130}Sn. Both techniques rely on selective particle identification and the measurement of γ rays in coincidence with charged ions. We present the goals of the two experiments and the particle identification for the channels of interest. The final results will be presented in future publications.

  6. Direct Reaction Experimental Studies with Beams of Radioactive Tin Ions

    SciTech Connect

    Jones, K. L.; Ahn, S.H.; Allmond, James M; Ayres, A.; Bardayan, Daniel W; Baugher, T.; Bazin, D.; Beene, James R; Berryman, J. S.; Bey, A.; Bingham, C. R.; Cartegni, L.; Chae, K. Y.; Gade, A.; Galindo-Uribarri, Alfredo {nmn}; Garcia-Ruiz, R.F.; Grzywacz, Robert Kazimierz; Howard, Meredith E; Kozub, R. L.; Liang, J Felix; Manning, Brett M; Matos, M.; McDaniel, S.; Miller, D.; Nesaraja, Caroline D; O'Malley, Patrick; Padgett, S; Padilla-Rodal, Elizabeth; Pain, Steven D; Pittman, S. T.; Radford, David C; Ratkiewicz, Andrew J; Schmitt, Kyle; Smith, Michael Scott; Stracener, Daniel W; Stroberg, S.; Tostevin, Jeffrey A; Varner Jr, Robert L; Weisshaar, D.; Wimmer, K.

    2015-01-01

    The tin chain of isotopes provides a unique region in which to investigate the evolution of single-particle structure, spreading from N = 50 at Sn-100, through 10 stable isotopes and the N = 82 shell closure at Sn-132 out into the r-process path. Direct reactions performed on radioactive ion beams are sensitive spectroscopic tools for studying exotic nuclei. Here we present one experiment knocking out neutrons from tin isotopes that are already neutron deficient and two reactions that add a neutron to neutron-rich Sn-130. Both techniques rely on selective particle identification and the measurement of gamma rays in coincidence with charged ions. We present the goals of the two experiments and the particle identification for the channels of interest. The final results will be presented in future publications.

  7. Acceleration and selective monomer addition during aqueous RAFT copolymerization of ionic monomers at 25 °C.

    PubMed

    Li, Guangxiang; Xu, Na; Yu, Qiuping; Lu, Xinhua; Chen, Hong; Cai, Yuanli

    2014-08-01

    An acceleration effect and selective monomer addition during RAFT copolymerization of the oppositely-charged ionic monomers in dilute aqueous solution at 25 °C are reported. The reaction is conducted using a non-ionic water-soluble polymer as a macromolecular chain transfer agent under visible light irradiation. A fast iterative polymerization can be induced, even in dilute solution, by the favorable ionic interactions and in situ self-assembly of zwitterionic growing chains. Selelctive monomer addition is achieved in the statistical copolymerization due to the ion-pairing of the oppositely-charged monomers, such as precisely the same reaction rates at a 1:1 of monomer ratio, otherwise a faster reaction of the minor monomer component over the major one. These behaviors open up an avenue towards the rapid synthesis of sequence-controlled zwitterionic polyelectrolytes that can satisfy the demands of emerging biological applications. PMID:24889131

  8. Histidine residues in the peptide D-Lys(6)-GnRH: potential for copolymerization in polymeric nanoparticles.

    PubMed

    Kafka, Alexandra P; Kleffmann, Torsten; Rades, Thomas; McDowell, Arlene

    2009-01-01

    Poly(ethylcyanoacrylate) (PECA) nanoparticles containing the bioactive d-Lys(6)-GnRH were manufactured by an in situ interfacial polymerization process using a w/o-microemulsion template containing the peptide in the dispersed aqueous pseudophase of the microemulsion. Polymeric nanoparticles were characterized using PCS, RP-HPLC (bulk level) and MALDI TOF mass spectrometry (molecular level). The peptide d-Lys(6)-GnRH was reactive with the alkylcyanoacrylate monomer, resulting in some of the peptide copolymerizing with the monomer. MALDI TOF/TOF (tandem) analysis revealed that the histidine residue in position 2 of d-Lys(6)-GnRH interacts covalently in the polymerization process. A reaction mechanism for this nucleophilic interference is suggested. The copolymerization reaction appeared to occur within seconds after the addition of the monomer to the microemulsion. The surface charge of resulting nanoparticles was less negative (-3 mV) compared with the zeta potential of empty nanoparticles (-27.5 mV). The copolymerization yielded high entrapment rates of 95 +/- 4% of peptide, but showed limited release ( approximately 11%) of free peptide over 5 days. A separate experiment demonstrated that the addition of d-Lys(6)-GnRH to preformed empty PECA nanoparticles (ex situ) also yielded fractions of copolymerized peptide suggesting a certain proportion of polymer remains available for copolymerization possibly through an unzipping depolymerization/repolymerization process. Therefore, the reactivity of histidine residues in bioactives needs to be considered whenever using the bioactive in situ or ex situ with polymeric PECA nanoparticles.

  9. Experimental evidence of reaction-induced fracturing during olivine carbonation

    NASA Astrophysics Data System (ADS)

    Zhu, Wenlu; Fusseis, Florian; Lisabeth, Harrison; Xing, Tiange; Xiao, Xianghui; De Andrade, Vincent; Karato, Shun-ichiro

    2016-09-01

    Mineral carbonation, a process that binds CO2 in the form of carbonates by silicate weathering, is widespread on the Earth's surface. Because of the abundance of silicate rocks and the permanence of the carbonated solids, sequestering CO2 via mineral carbonation has generated lots of interests. However, it is unclear how the fluid-rock reaction proceeds to completion in spite of an increasing solid volume. We conducted a mineral carbonation experiment in which a sintered olivine aggregate reacted with a sodium bicarbonate solution at reservoir conditions. Time-resolved synchrotron X-ray microtomographic images show cracks in polygonal patterns arising in the surface layers and propagating into the interior of the olivine aggregate. The nanotomography data reveal that the incipient cracks intersect at right angles. We infer that stretching due to nonuniform volume expansion generates polygonal cracking of the surfaces. Our data shed new lights on the processes that control hydration and carbonation of peridotite.

  10. Development of the Experimental Photo-Nuclear Reaction Database in Hokkaido University

    NASA Astrophysics Data System (ADS)

    Makinaga, A.

    2015-10-01

    Nuclear databases are important tools to apply nuclear phenomena to various fields of nuclear engineering. It is now recognized that the databases must be further developed for photo-nuclear reaction data for nuclear security, safety and nonproliferation applications. Hokkaido University Nuclear Reaction Data Centre (JCPRG) has contributed to the Experimental Nuclear Reaction Data Library (EXFOR) which is developed by the International Network of Nuclear Reaction Data Centres under coordination by IAEA. We report here on the recent compilation of the nuclear data files for the photonuclear reaction.

  11. Chemoselective Alternating Copolymerization of Limonene Dioxide and Carbon Dioxide: A New Highly Functional Aliphatic Epoxy Polycarbonate.

    PubMed

    Li, Chunliang; Sablong, Rafaël J; Koning, Cor E

    2016-09-12

    The alternating copolymerization of biorenewable limonene dioxide with carbon dioxide (CO2 ) catalyzed by a zinc β-diiminate complex is reported. The chemoselective reaction results in linear amorphous polycarbonates that carry pendent methyloxiranes and exhibit glass transition temperatures (Tg ) up to 135 °C. These polycarbonates can be efficiently modified by thiols or carboxylic acids in combination with lithium hydroxide or tetrabutylphosphonium bromide as catalysts, respectively, without destruction of the main chain. Moreover, polycarbonates bearing pendent cyclic carbonates can be quantitatively prepared by CO2 insertion catalyzed by lithium bromide.

  12. Chemoselective Alternating Copolymerization of Limonene Dioxide and Carbon Dioxide: A New Highly Functional Aliphatic Epoxy Polycarbonate.

    PubMed

    Li, Chunliang; Sablong, Rafaël J; Koning, Cor E

    2016-09-12

    The alternating copolymerization of biorenewable limonene dioxide with carbon dioxide (CO2 ) catalyzed by a zinc β-diiminate complex is reported. The chemoselective reaction results in linear amorphous polycarbonates that carry pendent methyloxiranes and exhibit glass transition temperatures (Tg ) up to 135 °C. These polycarbonates can be efficiently modified by thiols or carboxylic acids in combination with lithium hydroxide or tetrabutylphosphonium bromide as catalysts, respectively, without destruction of the main chain. Moreover, polycarbonates bearing pendent cyclic carbonates can be quantitatively prepared by CO2 insertion catalyzed by lithium bromide. PMID:27529815

  13. The phenyl + phenyl reaction as pathway to benzynes: An experimental and theoretical study

    NASA Astrophysics Data System (ADS)

    Dürrstein, Steffen H.; Olzmann, Matthias; Aguilera-Iparraguirre, Jorge; Barthel, Robert; Klopper, Wim

    2011-09-01

    Theoretical and experimental results shed light on the phenyl + phenyl reaction. Benzyne formation in the phenyl + phenyl reaction is important. Rate for benzyne formation is one order of magnitude below recombination rate. Coupled-cluster barrier heights differ significantly from CASPT2 results. Satisfactory agreement between B3LYP and coupled-cluster results.

  14. Extraction of palm tree cellulose and its functionalization via graft copolymerization.

    PubMed

    Al-Hoqbani, Abdulmajeed A; Abdel-Halim, E S; Al-Deyab, Salem S

    2014-09-01

    The work in this paper was planned with the aim of extracting the cellulosic component of palm tree waste and functionalizing this cellulose through graft copolymerization with acrylic acid. The cellulose extraction included hot alkali treatment with aqueous sodium hydroxide to remove the non-cellulosic binding materials. The alkali treatment was followed by an oxidative bleaching using peracid/hydrogen peroxide mixture with the aim of removing the rest of non-cellulosic materials to improve the fiber hydrophilicity and accessibility towards further grafting reaction. Optimum conditions for cellulose extraction are boiling in 5% (W/V) NaOH in a material to liquor ratio of 1:20 for 1 h then bleaching with 60 ml/l bleaching mixture at initial pH value of 6.5 for 30 min. The pH of the bleaching medium is turned to the alkaline range 11 and bleaching continues for extra 30 min. Graft copolymerization reaction was initiated by potassium bromate/thiourea dioxide redox system. Optimum conditions for grafting are 30 mmol of potassium bromate, 30 mmol of thiourea dioxide and 150 g of acrylic acid (each per 100 g of cellulose). The polymerization reaction was carried out for 120 min at 50°C using a material to liquor ratio of 1:20. PMID:25020080

  15. Synthesis of copolymerized porous organic frameworks with high gas storage capabilities at both high and low pressures.

    PubMed

    Pei, Cuiying; Ben, Teng; Li, Yanqiang; Qiu, Shilun

    2014-06-11

    A series of copolymerized porous organic frameworks (C-POFs) were synthesized with monomers of tetrakis(4-bromophenyl)methane and tris(4-bromophenyl)amine in different ratios by a Yamamoto-type Ullmann cross-coupling reaction. These C-POFs exhibit high physicochemical stability, large surface areas and excellent H2, CH4 and CO2 adsorption properties both at low and high pressures.

  16. Patient reactions to personalized medicine vignettes: An experimental design

    PubMed Central

    Butrick, Morgan; Roter, Debra; Kaphingst, Kimberly; Erby, Lori H.; Haywood, Carlton; Beach, Mary Catherine; Levy, Howard P.

    2011-01-01

    Purpose Translational investigation on personalized medicine is in its infancy. Exploratory studies reveal attitudinal barriers to “race-based medicine” and cautious optimism regarding genetically personalized medicine. This study describes patient responses to hypothetical conventional, race-based, or genetically personalized medicine prescriptions. Methods Three hundred eighty-seven participants (mean age = 47 years; 46% white) recruited from a Baltimore outpatient center were randomized to this vignette-based experimental study. They were asked to imagine a doctor diagnosing a condition and prescribing them one of three medications. The outcomes are emotional response to vignette, belief in vignette medication efficacy, experience of respect, trust in the vignette physician, and adherence intention. Results Race-based medicine vignettes were appraised more negatively than conventional vignettes across the board (Cohen’s d = −0.51−0.57−0.64, P < 0.001). Participants rated genetically personalized comparably with conventional medicine (− 0.14−0.15−0.17, P = 0.47), with the exception of reduced adherence intention to genetically personalized medicine (Cohen’s d = −0.38−0.41−0.44, P = 0.009). This relative reluctance to take genetically personalized medicine was pronounced for racial minorities (Cohen’s d =−0.38−0.31−0.25, P = 0.02) and was related to trust in the vignette physician (change in R2 = 0.23, P < 0.001). Conclusions This study demonstrates a relative reluctance to embrace personalized medicine technology, especially among racial minorities, and highlights enhancement of adherence through improved doctor-patient relationships. PMID:21270639

  17. Cross-checking of Large Evaluated and Experimental Nuclear Reaction Databases

    SciTech Connect

    Zeydina, O.; Koning, A.J.; Soppera, N.; Raffanel, D.; Bossant, M.; Dupont, E.; Beauzamy, B.

    2014-06-15

    Automated methods are presented for the verification of large experimental and evaluated nuclear reaction databases (e.g. EXFOR, JEFF, TENDL). These methods allow an assessment of the overall consistency of the data and detect aberrant values in both evaluated and experimental databases.

  18. Experimental studies in vortex pair motion coincident with a liquid reaction

    NASA Technical Reports Server (NTRS)

    Karagozian, A. R.; Suganuma, Y.; Strom, B. D.

    1988-01-01

    An experimental examination of the coincidence of a liquid reaction (acid/base) with the formation of a vortex pair structure is described in which emphasis is placed on the evolution of the strained diffusion layer and reacted core structures. Flow visualization of the reaction process is achieved via the technique of chemically sensitive LIF. The observed growth of reacted core structures associated with each vortex is compared with theoretically predicted behavior (Marble, 1983; Karagozian and Marble, 1986). Vortex pair separation is also compared with theoretical correlations, and the relevance of the analogy between a fast liquid reaction and a gaseous reaction is discussed.

  19. Catalysts for CO2/epoxide ring-opening copolymerization

    PubMed Central

    Trott, G.; Saini, P. K.; Williams, C. K.

    2016-01-01

    This article summarizes and reviews recent progress in the development of catalysts for the ring-opening copolymerization of carbon dioxide and epoxides. The copolymerization is an interesting method to add value to carbon dioxide, including from waste sources, and to reduce pollution associated with commodity polymer manufacture. The selection of the catalyst is of critical importance to control the composition, properties and applications of the resultant polymers. This review highlights and exemplifies some key recent findings and hypotheses, in particular using examples drawn from our own research. PMID:26755758

  20. Graft copolymerization onto polybutadiene: Cross-linking and thermal degradation of vinyl polymers and copolymers

    NASA Astrophysics Data System (ADS)

    Jiang, Dayue (David)

    This work consists of three parts. In Part I, the graft copolymerization of methyl methacrylate, methyl acrylate, methacylic acid and acrylic acid onto polybutadiene and its copolymers by benzoyl peroxide, BPO, or 2, 2'azobis(2-methylpropionitrile), AIBN, initiation were explored. The results show that these monomers can be grafted onto butadiene region of butadiene-containing polymers. The extent of both graft copolymerization and homopolymerization are dependent on the time and temperature of the reaction and the concentration of all of the reactants. One must specify the monomer, initiator and solvent for the efficient graft copolymerization. The methyl methacrylate adds directly to the radical sites which are formed on the backbone by the interaction of the polymer and the primary radical form the initiator, while for the other three monomers, the graft copolymerization occurs by addition of macro-radical to the double bonds. In Part II, the cross-linking of polybutadiene, butadiene-styrene copolymers, and polystyrene by irradiation, thermal and chemical processes, and Friedel-Crafts chemistry and the effect of cross-linking on the thermal stability were investigated. The proof of cross-linking of the polymer comes from the insolubility of the product after the cross-linking reaction and is characterized by gel content and swelling ratio. The results show that the thermal stability of the polymer can be improved by cross-linking. In Part III, the thermal degradation of three vinyl polymers, poly(vinylsulfonic acid) and its sodium salt and poly(vinylphosphonic acid) were studied by combination technique: TGA/FTIR. The results show that TGA/FTIR combined with analysis of residues provides an excellent opportunity to understand the degradation pathway of the compounds. The observation of foaming indicates that the char which is formed contains carbon as well as the inorganic salts which have been observed. The carbon is in a partially graphitized form. The salts

  1. Summary Report of the Workshop on The Experimental Nuclear Reaction Data Database

    SciTech Connect

    Semkova, V.; Pritychenko, B.

    2014-10-10

    The Workshop on the Experimental Nuclear Reaction Data Database (EXFOR) was held at IAEA Headquarters in Vienna from 6 to 10 October 2014. The workshop was organized to discuss various aspects of the EXFOR compilation process including compilation rules, different techniques for nuclear reaction data measurements, software developments, etc. A summary of the presentations and discussions that took place during the workshop is reported here.

  2. Armature reaction effects on a high temperature superconducting field winding of an synchronous machine: experimental results

    NASA Astrophysics Data System (ADS)

    Mijatovic, Nenad; Jensen, Bogi Bech

    2014-05-01

    This paper presents experimental results from the Superwind laboratory setup. Particular focus in the paper has been placed on describing and quantifying the influence of armature reaction on performance of the HTS filed winding. Presented experimental results have confirmed the HTS field winding sensitivity to both armature reaction intensity and angular position with respect to the HTS coils. Furthermore, the characterization of the HTS field winding has been correlated to the electromagnetic torque of the machine where the maximal Ic reduction of 21% has been observed for the maximum torque.

  3. Controlled graft copolymerization of lactic acid onto starch in a supercritical carbon dioxide medium.

    PubMed

    Salimi, Kouroush; Yilmaz, Mehmet; Rzayev, Zakir M O; Piskin, Erhan

    2014-12-19

    This work presents a new approach for the synthesis of a starch-g-poly L-lactic acid (St-g-PLA) copolymer via the graft copolymerization of LA onto starch using stannous 2-ethyl hexanoate (Sn(Oct)2) as a catalyst in a supercritical carbon dioxide (scCO2) medium. The effects of several process parameters, including the pressure, temperature, scCO2 flow rate and reaction time, on the polymerization yield and grafting degree were studied. Amorphous graft St-g-PLA copolymers with increased thermal stability and processability were produced with a high efficiency. The maximum grafting degree (i.e., 52% PLA) was achieved with the following reaction conditions: 6h, 100°C, 200 bar and a 1:3 (w/w) ratio of St/LA. It was concluded that these low cost biobased graft biopolymers are potential candidates for several environment-friendly applications.

  4. Controlled graft copolymerization of lactic acid onto starch in a supercritical carbon dioxide medium.

    PubMed

    Salimi, Kouroush; Yilmaz, Mehmet; Rzayev, Zakir M O; Piskin, Erhan

    2014-12-19

    This work presents a new approach for the synthesis of a starch-g-poly L-lactic acid (St-g-PLA) copolymer via the graft copolymerization of LA onto starch using stannous 2-ethyl hexanoate (Sn(Oct)2) as a catalyst in a supercritical carbon dioxide (scCO2) medium. The effects of several process parameters, including the pressure, temperature, scCO2 flow rate and reaction time, on the polymerization yield and grafting degree were studied. Amorphous graft St-g-PLA copolymers with increased thermal stability and processability were produced with a high efficiency. The maximum grafting degree (i.e., 52% PLA) was achieved with the following reaction conditions: 6h, 100°C, 200 bar and a 1:3 (w/w) ratio of St/LA. It was concluded that these low cost biobased graft biopolymers are potential candidates for several environment-friendly applications. PMID:25263875

  5. Evolution of composition, molar mass, and conductivity during the free radical copolymerization of polyelectrolytes.

    PubMed

    Alb, Alina M; Paril, Ahmet; Catalgil-Giz, Huceste; Giz, Ahmet; Reed, Wayne F

    2007-07-26

    Despite their importance in biological and technological contexts, copolymeric polyelectrolytes (or "copolyelectrolytes") continue to present challenges to theorists and experimentalists. The first results of a unified approach to the kinetics and mechanisms of copolyelectrolyte synthesis and the physical characteristics of the resulting polymers are presented. The free radical copolymerization of 4-vinylbenzenesulfonic acid sodium salt and acrylamide was monitored using automatic continuous online monitoring of polymerization reactions (ACOMP), from which the average bivariate composition and mass distributions were determined. Composition drift was related to the evolution of conductivity. In some cases bimodal populations of copolyelectrolyte and homopolymeric poly(acrylamide) resulted, i.e., blends of copolyelectrolyte and neutral homopolymer. The end-product scattering behavior depended on whether the end-product was bimodal or not, as demonstrated using automatic continuous mixing (ACM) in conjunction with light scattering and viscosity. Negative light-scattering third virial coefficients were found for bimodal end-products. This combined approach may allow connecting the synthesis kinetics to the resulting "trivariate" distribution of composition, molar mass, and linear charge density, which in turn controls the properties of end-product solutions, such as chain conformations, interparticle interactions, viscosity, interactions with colloids and other polymers, phase separation, etc. Unified results may allow testing and improvement of existing polyelectrolyte theories, development of new quantitative physicochemical models, provide advanced characterization methods, set the stage for studying more complex copolyelectrolytes, such as hydrophobically modified ones, and provide tools for ultimately controlling and tailoring the synthesis and properties of copolyelectrolytes.

  6. Experimental study to explore the 8Be-induced nuclear reaction via the Trojan horse method

    NASA Astrophysics Data System (ADS)

    Wen, Qun-Gang; Li, Cheng-Bo; Zhou, Shu-Hua; Irgaziev, Bakhadir; Fu, Yuan-Yong; Spitaleri, Claudio; La Cognata, Marco; Zhou, Jing; Meng, Qiu-Ying; Lamia, Livio; Lattuada, Marcello

    2016-03-01

    To explore a possible indirect method for 8Be induced astrophysical reactions, the 8Be=(8Be+n ) cluster structure has been studied via the Trojan horse method. For the first time a 8Be nucleus having an ultrashort lifetime is studied by the Trojan horse method and a 9Be nucleus in the ground state is used for this purpose. The 9Be nucleus is assumed to have a (8Be+n ) cluster structure and used as a Trojan horse nucleus. The 8Be nucleus acts as a participant, while the neutron is a spectator to the virtual 8Be+d →α +6Li reaction via the 3-body reaction 8Be+d →α +6Li+n . The experimental neutron momentum distribution inside 9Be has been reconstructed. The agreement between the experimental momentum distribution and the theoretical one indicates that a (8Be+n ) cluster structure inside 9Be is very likely. Therefore, the experimental study of 8Be induced reactions, for example, the measurement of the 8Be+α →12C reaction proceeding through the Hoyle state, is possible.

  7. Experimental studies of coherent structures in an advection-reaction-diffusion system.

    PubMed

    Gowen, Savannah; Solomon, Tom

    2015-08-01

    We present experimental studies of reaction front propagation in a single vortex flow with an imposed external wind. The fronts are produced by the excitable, ferroin-catalyzed Belousov-Zhabotinsky chemical reaction. The flow is generated using an electromagnetic forcing technique: an almost-radial electrical current interacts with a magnetic field from a magnet below the fluid layer to produce the vortex. The magnet is mounted on crossed translation stages allowing for movement of the vortex through the flow. Reaction fronts triggered in or in front of the moving vortex form persistent structures that are seen experimentally for time-independent (constant motion), time-periodic, and time-aperiodic flows. These results are examined with the use of burning invariant manifolds that act as one-way barriers to front motion in the flows. We also explore the usefulness of finite-time Lyapunov exponent fields as an instrument for analyzing front propagation behavior in a fluid flow. PMID:26328574

  8. Experimental Study of Estimating the Subgrade Reaction Modulus on Jointed Rock Foundations

    NASA Astrophysics Data System (ADS)

    Lee, Jaehwan; Jeong, Sangseom

    2016-06-01

    The subgrade reaction modulus for rock foundations under axial loading is investigated by model footing tests. This study focuses on quantifying a new subgrade reaction modulus by considering rock discontinuities. A series of model-scale footing tests are performed to investigate the effects of the unconfined compressive strength, discontinuity spacing and inclination of the rock joint. Based on the experimental results, it is observed that the subgrade reaction modulus of the rock with discontinuities decreases by up to approximately 60 % of intact rock. In addition, it is found that the modulus of subgrade reaction is proportional to the discontinuity spacing, and it decreases gradually within the range of 0°-30° and tends to increase within the range of 30°-90°.

  9. Experimental investigation of the 30S(α, p) thermonuclear reaction in x-ray bursts

    NASA Astrophysics Data System (ADS)

    Kahl, D.; Chen, A. A.; Kubono, S.; Yamaguchi, H.; Binh, D. N.; Chen, J.; Cherubini, S.; Duy, N. N.; Hashimoto, T.; Hayakawa, S.; Iwasa, N.; Jung, H. S.; Kato, S.; Kwon, Y. K.; Nishimura, S.; Ota, S.; Setoodehnia, K.; Teranishi, T.; Tokieda, H.; Yamada, T.; Yun, C. C.; Zhang, L. Y.

    2016-02-01

    We performed the first measurement of 30S+α resonant elastic scattering to experimentally examine the 30S(α, p) stellar reaction rate in type I x-ray bursts. These bursts are the most frequent thermonuclear explosions in the galaxy, resulting from thermonuclear runaway on the surface of accreting neutron star binaries. The 30S(α, p) reaction plays a critical role in burst models, yet very little is known about the compound nucleus 34Ar at these energies nor the reaction rate itself. We performed a measurement of alpha elastic scattering with a radioactive beam of 30S to experimentally probe the entrance channel. Utilizing a gaseous active target system and silicon detector array, we extracted the excitation function from 1.8 to 5.5 MeV near 160° in the center-of-mass frame. The experimental data were analyzed with an R-Matrix calculation, and we discovered several new resonances and extracted their quantum properties (resonance energy, width, spin, and parity). Finally, we calculated the narrow resonant thermonuclear reaction rate of 30S(α, p) for these new resonances.

  10. The dynamics of the D2 + OH --> HOD + D reaction: a combined theoretical and experimental study.

    PubMed

    Liu, Shu; Xiao, Chunlei; Wang, Tao; Chen, Jun; Yang, Tiangang; Xu, Xin; Zhang, Dong H; Yang, Xueming

    2012-01-01

    A combined theoretical and experimental study has been carried out to show the current status of comparison between experiment and theory on the title reaction. Differential cross sections and product relative translational energy distributions at collision energies of 0.25 and 0.34 eV, as well as the collision energy dependence of differential cross section in the backward direction have been measured by using crossed molecular beam experiment with D-atom Rydberg tagging technique. Theoretically, the time-dependent wave packet method has been employed to calculate state-to-state differential cross sections for the title reaction in full dimension. It is found that the experimental observations are in good accord with those of Davis and coworkers at the collision energy of 0.28 eV [Science, 290, 958 (2000)]. The overall agreement between theory and experiment on this benchmark four-atom reaction is good, but not perfect. Further studies, both theoretical and experimental, are called to bring a complete agreement between theory and experiment on the reaction.

  11. EXPERIMENTAL AND THEORETICAL STUDIES OF REACTIONS BETWEEN H ATOMS AND CARBANIONS OF INTERSTELLAR RELEVANCE

    SciTech Connect

    Yang Zhibo; Eichelberger, Brian; Carpenter, Marshall Y.; Martinez, Oscar; Bierbaum, Veronica M.; Snow, Theodore P. E-mail: BEichelberger@jbu.ed E-mail: Oscar.Martinez@colorado.ed E-mail: Theodore.Snow@colorado.ed

    2010-11-10

    The recent detection of molecular anions in the interstellar medium (ISM) has highlighted the need for laboratory studies of negative ion chemistry. Hydrogen atoms are the most abundant atomic species in the ISM, and the chemistry of H atoms with anions may contribute to molecular synthesis in interstellar clouds. This work is a combined experimental and computational study of a series of anions reacting with H atoms by associative detachment (A{sup -} + H {yields} AH + e {sup -}). The anions include deprotonated nitriles (CH{sub 2}CN{sup -}, CH{sub 3}CHCN{sup -}, and (CH{sub 3}){sub 2}CCN{sup -}), acetaldehyde (HC(O)CH{sub 2} {sup -}), acetone (CH{sub 3}C(O)CH{sub 2} {sup -}), ethyl acetate (CH{sub 3}CH{sub 2}OC(O)CH{sub 2} {sup -}), methanol (CH{sub 3}O{sup -}), and acetic acid (CH{sub 3}CO{sub 2} {sup -}). Experimental measurements of the reaction rate constants were made with the flowing afterglow-selected ion flow tube technique. Ab initio theoretical calculations were carried out to explore the reaction mechanism and investigate the factors influencing reaction efficiencies, which are largely proportional to reaction exothermicities. Other factors influencing reaction efficiencies include the charge density on the reactive site of the anion, the characteristics of the potential energy surfaces along the approach of the reactants, and angular momentum conservation of the anion-H atom collision.

  12. Reducing experimental variability in variance-based sensitivity analysis of biochemical reaction systems.

    PubMed

    Zhang, Hong-Xuan; Goutsias, John

    2011-03-21

    Sensitivity analysis is a valuable task for assessing the effects of biological variability on cellular behavior. Available techniques require knowledge of nominal parameter values, which cannot be determined accurately due to experimental uncertainty typical to problems of systems biology. As a consequence, the practical use of existing sensitivity analysis techniques may be seriously hampered by the effects of unpredictable experimental variability. To address this problem, we propose here a probabilistic approach to sensitivity analysis of biochemical reaction systems that explicitly models experimental variability and effectively reduces the impact of this type of uncertainty on the results. The proposed approach employs a recently introduced variance-based method to sensitivity analysis of biochemical reaction systems [Zhang et al., J. Chem. Phys. 134, 094101 (2009)] and leads to a technique that can be effectively used to accommodate appreciable levels of experimental variability. We discuss three numerical techniques for evaluating the sensitivity indices associated with the new method, which include Monte Carlo estimation, derivative approximation, and dimensionality reduction based on orthonormal Hermite approximation. By employing a computational model of the epidermal growth factor receptor signaling pathway, we demonstrate that the proposed technique can greatly reduce the effect of experimental variability on variance-based sensitivity analysis results. We expect that, in cases of appreciable experimental variability, the new method can lead to substantial improvements over existing sensitivity analysis techniques.

  13. Population-reaction model and microbial experimental ecosystems for understanding hierarchical dynamics of ecosystems.

    PubMed

    Hosoda, Kazufumi; Tsuda, Soichiro; Kadowaki, Kohmei; Nakamura, Yutaka; Nakano, Tadashi; Ishii, Kojiro

    2016-02-01

    Understanding ecosystem dynamics is crucial as contemporary human societies face ecosystem degradation. One of the challenges that needs to be recognized is the complex hierarchical dynamics. Conventional dynamic models in ecology often represent only the population level and have yet to include the dynamics of the sub-organism level, which makes an ecosystem a complex adaptive system that shows characteristic behaviors such as resilience and regime shifts. The neglect of the sub-organism level in the conventional dynamic models would be because integrating multiple hierarchical levels makes the models unnecessarily complex unless supporting experimental data are present. Now that large amounts of molecular and ecological data are increasingly accessible in microbial experimental ecosystems, it is worthwhile to tackle the questions of their complex hierarchical dynamics. Here, we propose an approach that combines microbial experimental ecosystems and a hierarchical dynamic model named population-reaction model. We present a simple microbial experimental ecosystem as an example and show how the system can be analyzed by a population-reaction model. We also show that population-reaction models can be applied to various ecological concepts, such as predator-prey interactions, climate change, evolution, and stability of diversity. Our approach will reveal a path to the general understanding of various ecosystems and organisms. PMID:26747638

  14. Experimental Study of the Cross Sections of {alpha}-Particle Induced Reactions on 209Bi

    SciTech Connect

    Hermanne, A.; Tarkanyi, F.; Takacs, S.; Szucs, Z.

    2005-05-24

    Alpha particle induced reactions for generation of 211At used in therapeutic nuclear medicine and possible contaminants were investigated with the stacked foil activation technique on natural bismuth targets up to E{alpha}=39 MeV. Excitation functions for the reactions 209Bi({alpha},2n)211At, 209Bi({alpha},3n)210At, 209Bi({alpha},x) 210Po obtained from direct alpha emission measurements and gamma spectra from decay products are compared with earlier literature values. Thick target yields have been deduced from the experimental cross sections.

  15. Decomposition reactions as general Poisson processes: Theory and an experimental example

    NASA Astrophysics Data System (ADS)

    Rydén, Tobias; Wernersson, Mikael

    1995-10-01

    The classical theory of decomposition reaction kinetics depends on a ``large scale'' assumption. In this paper we show how this assumption can be replaced by the assumption that the nucleation process is a space-time Poisson process. This framework is unifying in the sense that it includes many earlier formulas as special cases, and it naturally takes boundary effects into account. We consider the conversion of a sphere in detail, and fit the parameters of this model to gypsum decomposition experimental data. The so obtained model shows, for this particular reaction, that the boundary effects decrease with temperature.

  16. Experimental and Theoretical Investigations of Reaction-Coupled Flow and Transport in Porous Media

    NASA Astrophysics Data System (ADS)

    Kim, J.; Schwartz, F. W.

    2004-12-01

    In some systems, it is possible to observe complex patterns of coupling between fluid and flow and mass transport when reactions involving a solid phase are operative. For example, dissolution and precipitation reactions can change a porous medium's physical properties such as porosity and permeability. These changes influence fluid flow, which affect the concentration of dissolved solids, the composition of solid phases, and the rate and direction of advective transport. Both experimental and modeling studies were conducted to investigate the coupling between flow and transport due to effects of fluid density, dissolution/precipitation reactions, and heterogeneity in medium properties. The complex chemical system is created by pumping a dilute Fe(ClO4)3 solution through a medium created by mixing glass beads and crushed calcite. Fe3+ rapidly hydrolyzes to produce hydroxo complexes and H+. As pH increases through reaction with calcite, a poorly crystallized solid, ferric oxyhydroxide precipitates. Two-dimensional flow tank studies are use to verify a novel modeling approach. In the model, there is full coupling of flow and transport due to permeability changes from dissolution/precipitation reactions. Further, TOUGHREACT is used to study reaction-front dynamics, and how the aqueous phase concentrations depend upon this pattern of evolution. Both the experimental and theoretical results highlight the complexity of coupling in systems with heterogeneous reactions. The important implication of this study is that details of interactions between pore fluid and the porous medium need to be well characterized in order to predict the changing aqueous concentrations.

  17. Recent advances in photoinduced donor/acceptor copolymerization

    NASA Astrophysics Data System (ADS)

    Jönsson, S.; Viswanathan, K.; Hoyle, C. E.; Clark, S. C.; Miller, C.; Morel, F.; Decker, C.

    1999-05-01

    Photoinitiated free radical polymerization of donor (D)/acceptor (A) type monomers has gained considerable interest due to the possibility to efficiently photopolymerize non-acrylate based systems. Furthermore, this photoinduced alternating copolymerization can be accomplished without the presence of a conventional free radical generating photoinitiator. In the past, we have shown that the structural influences in the direct photolysis of N-Alkyl and N-Arylmaleimides as well as their corresponding ground state charge transfer complexes (CTC) with suitable donors have carefully been investigated. For certain combinations of A and D type monomers, a direct photolysis of the ground state complex or the excitation of the acceptor, followed by the formation of an exciplex, has been shown to initiate the copolymerization. Herein, we show that the main route of initiation is based on inter or intra molecular H-abstraction from an excited state maleimide, whereby no exciplex formation takes place. H-abstraction will predominantly take place in systems where easily abstractable hydrogens are present. Our laser flash photolysis investigation, ESR [1] (A. Hiroshi, I. Takasi, T. Nosi, Macromol. Chem. 190 (1989) 2821) and phosphorescence emissions [2,3] (K.S. Chen, T. Foster, J.K.S. Wan, J. Phys. Chem. 84 (1980) 2473; C.J. Seliskar, S.P. McGlynn, J. Chem. Phys. 55 (1971) 4337) studies show that triplet excited states of N-alkyl substituted maleimides (RMI), which are well known strong precursors for direct H-abstractions from aliphatic ethers and secondary alcohols, are formed upon excitation. Rates of copolymerization and degrees of conversion for copolymerization of maleimide/vinyl ether pairs in air and nitrogen have been measured as a function of hydrogen abstractability of the excited triplet state MI as well as the influence of concentration and hydrogen donating effect of the hydrogen donor.

  18. CAMELOT: A machine learning approach for coarse-grained simulations of aggregation of block-copolymeric protein sequences

    SciTech Connect

    Ruff, Kiersten M.; Harmon, Tyler S.; Pappu, Rohit V.

    2015-12-28

    We report the development and deployment of a coarse-graining method that is well suited for computer simulations of aggregation and phase separation of protein sequences with block-copolymeric architectures. Our algorithm, named CAMELOT for Coarse-grained simulations Aided by MachinE Learning Optimization and Training, leverages information from converged all atom simulations that is used to determine a suitable resolution and parameterize the coarse-grained model. To parameterize a system-specific coarse-grained model, we use a combination of Boltzmann inversion, non-linear regression, and a Gaussian process Bayesian optimization approach. The accuracy of the coarse-grained model is demonstrated through direct comparisons to results from all atom simulations. We demonstrate the utility of our coarse-graining approach using the block-copolymeric sequence from the exon 1 encoded sequence of the huntingtin protein. This sequence comprises of 17 residues from the N-terminal end of huntingtin (N17) followed by a polyglutamine (polyQ) tract. Simulations based on the CAMELOT approach are used to show that the adsorption and unfolding of the wild type N17 and its sequence variants on the surface of polyQ tracts engender a patchy colloid like architecture that promotes the formation of linear aggregates. These results provide a plausible explanation for experimental observations, which show that N17 accelerates the formation of linear aggregates in block-copolymeric N17-polyQ sequences. The CAMELOT approach is versatile and is generalizable for simulating the aggregation and phase behavior of a range of block-copolymeric protein sequences.

  19. CAMELOT: A machine learning approach for coarse-grained simulations of aggregation of block-copolymeric protein sequences

    NASA Astrophysics Data System (ADS)

    Ruff, Kiersten M.; Harmon, Tyler S.; Pappu, Rohit V.

    2015-12-01

    We report the development and deployment of a coarse-graining method that is well suited for computer simulations of aggregation and phase separation of protein sequences with block-copolymeric architectures. Our algorithm, named CAMELOT for Coarse-grained simulations Aided by MachinE Learning Optimization and Training, leverages information from converged all atom simulations that is used to determine a suitable resolution and parameterize the coarse-grained model. To parameterize a system-specific coarse-grained model, we use a combination of Boltzmann inversion, non-linear regression, and a Gaussian process Bayesian optimization approach. The accuracy of the coarse-grained model is demonstrated through direct comparisons to results from all atom simulations. We demonstrate the utility of our coarse-graining approach using the block-copolymeric sequence from the exon 1 encoded sequence of the huntingtin protein. This sequence comprises of 17 residues from the N-terminal end of huntingtin (N17) followed by a polyglutamine (polyQ) tract. Simulations based on the CAMELOT approach are used to show that the adsorption and unfolding of the wild type N17 and its sequence variants on the surface of polyQ tracts engender a patchy colloid like architecture that promotes the formation of linear aggregates. These results provide a plausible explanation for experimental observations, which show that N17 accelerates the formation of linear aggregates in block-copolymeric N17-polyQ sequences. The CAMELOT approach is versatile and is generalizable for simulating the aggregation and phase behavior of a range of block-copolymeric protein sequences.

  20. Experimental and theoretical data on ion-molecule-reactions relevant for plasma modelling

    SciTech Connect

    Hansel, A.; Praxmarer, C.; Lindinger, W.

    1995-12-31

    Despite the fact that the rate coefficients of hundreds of ion-molecule-reactions have been published in the literature, much more data are required for the purpose of plasma modelling. Many ion molecule reactions have rate coefficients, k, as large as the collisional limiting value, k{sub c}, i.e. the rate coefficients k{sub c} at which ion-neutral collision complexes are formed are close to the actual rate coefficients observed. In the case of the interaction of an ion with a non polar molecule, k{sub c}, is determined by the Langevin limiting value k{sub L} being typically 10{sup -9} cm{sup 3} s{sup -1}. However, when ions react with polar molecules k{sub c} is predicted by the average dipole orientation (ADO) theory. These classical theories yield accurate rate coefficients at thermal and elevated temperatures for practically all proton transfer as well as for many charge transfer and hydrogen abstraction reactions. The agreement between experimental and calculated values is usually better than {plus_minus}20% and in the case of proton transfer reactions the agreement seems to be even better as recent investigations have shown. Even the interaction of the permanent ion dipole with non polar and polar neutrals can be taken into account to predict reaction rate coefficients as has been shown very recently in reactions of the highly polar ion ArH{sub 3}{sup +} with various neutrals.

  1. Formation of orthopyroxenite by reaction between peridotite and hydrous basaltic melt: an experimental study

    NASA Astrophysics Data System (ADS)

    Wang, Chunguang; Liang, Yan; Dygert, Nick; Xu, Wenliang

    2016-09-01

    The consequences of hydrous basaltic melts and peridotite interaction were examined experimentally in Au-Pd, Pt, and graphite capsules using the reaction couple method. Reactions between a hydrous basaltic andesite (4 wt% H2O) and dunite or lherzolite in an Au-Pd capsule at 1 GPa and 1200 °C produce a melt-bearing orthopyroxenite-dunite sequence. Reactions between a hydrous ferro-basalt and lherzolite in Pt or Au-Pd capsules at 0.8-2 GPa and 1250-1385 °C produce a melt-bearing orthopyroxenite-harzburgite sequence. Reactions between the ferro-basalt and lherzolite in graphite capsules (not designed to retain water) result in a melt-bearing dunite-harzburgite sequence at 1 GPa and a melt-bearing harzburgite-lherzolite sequence at 2 GPa. The orthopyroxenite from the hydrous reaction experiments has a high porosity, and it is separated by a sharp lithological interface from the dunite or harzburgite. Orthopyroxenes in the orthopyroxenite are large in size with resorbed olivine inclusions. Formation of the high-porosity orthopyroxenite in the hydrous melt-rock reaction experiments is determined by the liquidus phase relation of the interface reacting melt and reaction kinetics. Reaction between orthopyroxene-saturated hydrous melt and olivine at melt-rock interface produces orthopyroxenite. Water infiltration induces hydrous melting of the lherzolite, producing a dunite or an orthopyroxene-depleted harzburgite. Efficient diffusive exchange between the partial melt and the hydrous reacting melt promotes orthopyroxene-oversaturation around the melt-rock interfacial region. The simplified experiments reveal end-member processes for understanding the formation of orthopyroxenite in the upper mantle. The presence of orthopyroxenites in mantle samples is a strong indication of hydrous melt and peridotite interaction.

  2. Reactions to Ingroup and Outgroup Deviants: An Experimental Group Paradigm for Black Sheep Effect

    PubMed Central

    2015-01-01

    In the classic black sheep effect (BSE) an ingroup deviant member is usually evaluated more negatively than the corresponding outgroup deviant. This effect is usually obtained by using scenarios and asking people to imagine the situation as vividly as possible. The present study proposes a new method to investigate the BSE by considering the behavioral and physiological reactions to unfair behavior (aggressive game behavior) in a realistic experimental group-setting. The study involved 52 university students in a minimal group setting who performed a modified version of the competitive reaction time (CRT) task adapted to be played in groups of four people. The classic BSE was replicated for evaluation but not for the behavioral reactions (retaliate to aggression) to deviants. More interestingly, a negative relationship emerged in the ingroup deviant condition between the level of behavioral derogation and the systolic blood pressure level. PMID:25946148

  3. Experimental study of the astrophysical γ -process reaction 124Xe(α ,γ )128Ba

    NASA Astrophysics Data System (ADS)

    Halász, Z.; Somorjai, E.; Gyürky, Gy.; Elekes, Z.; Fülöp, Zs.; Szücs, T.; Kiss, G. G.; Szegedi, N. T.; Rauscher, T.; Görres, J.; Wiescher, M.

    2016-10-01

    Background: The synthesis of heavy, proton rich isotopes in the astrophysical γ process proceeds through photodisintegration reactions. For the improved understanding of the process, the rates of the involved nuclear reactions must be known. The reaction 128Ba(γ ,α )124Xe was found to affect the abundance of the p nucleus 124Xe in previous rate variation studies. Purpose: Since the stellar rate for this reaction cannot be determined by a measurement directly, the aim of the present work was to measure the cross section of the inverse 124Xe(α ,γ )128Ba reaction and to compare the results with statistical model predictions used in astrophysical networks. Modified nuclear input can then be used to provide an improved stellar reaction rate. Of great importance is the fact that data below the (α ,n ) threshold was obtained. Studying simultaneously the 124Xe(α ,n )127Ba reaction channel at higher energy allowed to further identify the source of a discrepancy between data and prediction. Method: The 124Xe(α ,γ )128Ba and 124Xe(α ,n )127Ba cross sections were measured with the activation method using a thin window 124Xe gas cell and an α beam from a cyclotron accelerator. The studied energy range was between Eα=11 and 15 MeV close above the astrophysically relevant energy range. Results: The obtained cross sections are compared with Hauser-Feshbach statistical model calculations. The experimental cross sections are smaller than standard predictions previously used in astrophysical calculations. As a dominating source of the difference, the theoretical α width was identified. The experimental data suggest an α width lower by at least a factor of 0.125 in the astrophysically important energy range. Conclusions: An upper limit for the 128Ba(γ ,α )124Xe stellar rate was inferred from our measurement. The impact of this rate and lower rates was studied in two different models for core-collapse supernova explosions of 25 M⊙ stars. A significant contribution to

  4. Block Copolymerization of Lactide and an Epoxide Facilitated by a Redox Switchable Iron-Based Catalyst.

    PubMed

    Biernesser, Ashley B; Delle Chiaie, Kayla R; Curley, Julia B; Byers, Jeffery A

    2016-04-18

    A cationic iron(III) complex was active for the polymerization of various epoxides, whereas the analogous neutral iron(II) complex was inactive. Cyclohexene oxide polymerization could be "switched off" upon in situ reduction of the iron(III) catalyst and "switched on" upon in situ oxidation, which is orthogonal to what was observed previously for lactide polymerization. Conducting copolymerization reactions in the presence of both monomers resulted in block copolymers whose identity can be controlled by the oxidation state of the catalyst: selective lactide polymerization was observed in the iron(II) oxidation state and selective epoxide polymerization was observed in the iron(III) oxidation state. Evidence for the formation of block copolymers was obtained from solubility differences, GPC, and DOSY-NMR studies. PMID:26991820

  5. Structural and behavioral characteristics of radiolytically synthesized polyacrylic acid-polyacrylonitrile copolymeric hydrogels

    NASA Astrophysics Data System (ADS)

    Bera, Anuradha; Misra, R. K.; Singh, Shailendra K.

    2013-10-01

    Copolymeric hydrogels of polyacrylic acid (PAA) - polyacrylonitrile (PAN) was radiolytically synthesized from their respective monomers with trimethyloltrimethacrylate (TMPTMA) as the crosslinker wherein both polymerization and crosslinking could be achieved in a single step reaction using 60Co γ-radiation under varying doses and dose rates. The formation of the hydrogels was confirmed by their FT-IR analysis, while their thermal degradation patterns were investigated through thermogravimetric analysis in both the dry and swelled state. The water sorption studies showed rapid swelling behavior of these hydrogels, where swelling (%EWC) was found to be strongly dependent on the ratio of the two monomers in the hydrogels and the swelling kinetics dependent on the dose rates of hydrogel synthesis. These radiolytically synthesized hydrogels responded to electrical stimulus both in terms of the bending speed as well as bending angle under an applied voltage. The nature of the deformation was reversible and can be controlled through switching the voltage on and off.

  6. Block Copolymerization of Lactide and an Epoxide Facilitated by a Redox Switchable Iron-Based Catalyst.

    PubMed

    Biernesser, Ashley B; Delle Chiaie, Kayla R; Curley, Julia B; Byers, Jeffery A

    2016-04-18

    A cationic iron(III) complex was active for the polymerization of various epoxides, whereas the analogous neutral iron(II) complex was inactive. Cyclohexene oxide polymerization could be "switched off" upon in situ reduction of the iron(III) catalyst and "switched on" upon in situ oxidation, which is orthogonal to what was observed previously for lactide polymerization. Conducting copolymerization reactions in the presence of both monomers resulted in block copolymers whose identity can be controlled by the oxidation state of the catalyst: selective lactide polymerization was observed in the iron(II) oxidation state and selective epoxide polymerization was observed in the iron(III) oxidation state. Evidence for the formation of block copolymers was obtained from solubility differences, GPC, and DOSY-NMR studies.

  7. cine-Substitution reactions of metallabenzenes: an experimental and computational study.

    PubMed

    Wang, Tongdao; Zhang, Hong; Han, Feifei; Long, Lipeng; Lin, Zhenyang; Xia, Haiping

    2013-08-12

    Alkali-resistant osmabenzene [(SCN)2(PPh3)2Os{CHC(PPh3)CHCICH}] (2) can undergo nucleophilic aromatic substitution with MeOH or EtOH to give cine-substitution products [(SCN)2(PPh3)2Os{CHC(PPh3)CHCHCR}] (R=OMe (3), OEt(4)) in the presence of strong alkali. However, the reactions of compound 2 with various amines, such as n-butylamine and aniline, afford five-membered ring species, [(SCN)2(PPh3)2Os{CH=C(PPh3)CH=C(CH=NHR')}] (R'=nBu(8), Ph(9)), in addition to the desired cine-substitution products, [(SCN)2(PPh3)2Os{CHC(PPh3)CHCHC(NHR')}] (R'=nBu(6), Ph(7)), under similar reaction conditions. The mechanisms of these reactions have been investigated in detail with the aid of isotopic labeling experiments and density functional theory (DFT) calculations. The results reveal that the cine-substitution reactions occur through nucleophilic addition, dissociation of the leaving group, protonation, and deprotonation steps, which resemble the classical "addition-of-nucleophile, ring-opening, ring-closure" (ANRORC) mechanism. DFT calculations suggest that, in the reaction with MeOH, the formation of a five-membered metallacycle species is both kinetically and thermodynamically less favorable, which is consistent with the experimental results that only the cine-substitution product is observed. For the analogous reaction with n-butylamine, the pathway for the formation of the cine-substitution product is kinetically less favorable than the pathway for the formation of a five-membered ring species, but is much more thermodynamically favorable, again consistent with the experimental conversion of compound 8 into compound 6, which is observed in an in situ NMR experiment with an isolated pure sample of 8.

  8. cine-Substitution reactions of metallabenzenes: an experimental and computational study.

    PubMed

    Wang, Tongdao; Zhang, Hong; Han, Feifei; Long, Lipeng; Lin, Zhenyang; Xia, Haiping

    2013-08-12

    Alkali-resistant osmabenzene [(SCN)2(PPh3)2Os{CHC(PPh3)CHCICH}] (2) can undergo nucleophilic aromatic substitution with MeOH or EtOH to give cine-substitution products [(SCN)2(PPh3)2Os{CHC(PPh3)CHCHCR}] (R=OMe (3), OEt(4)) in the presence of strong alkali. However, the reactions of compound 2 with various amines, such as n-butylamine and aniline, afford five-membered ring species, [(SCN)2(PPh3)2Os{CH=C(PPh3)CH=C(CH=NHR')}] (R'=nBu(8), Ph(9)), in addition to the desired cine-substitution products, [(SCN)2(PPh3)2Os{CHC(PPh3)CHCHC(NHR')}] (R'=nBu(6), Ph(7)), under similar reaction conditions. The mechanisms of these reactions have been investigated in detail with the aid of isotopic labeling experiments and density functional theory (DFT) calculations. The results reveal that the cine-substitution reactions occur through nucleophilic addition, dissociation of the leaving group, protonation, and deprotonation steps, which resemble the classical "addition-of-nucleophile, ring-opening, ring-closure" (ANRORC) mechanism. DFT calculations suggest that, in the reaction with MeOH, the formation of a five-membered metallacycle species is both kinetically and thermodynamically less favorable, which is consistent with the experimental results that only the cine-substitution product is observed. For the analogous reaction with n-butylamine, the pathway for the formation of the cine-substitution product is kinetically less favorable than the pathway for the formation of a five-membered ring species, but is much more thermodynamically favorable, again consistent with the experimental conversion of compound 8 into compound 6, which is observed in an in situ NMR experiment with an isolated pure sample of 8. PMID:23843260

  9. Experimental study of the reaction of methane with petroleum hydrocarbons in geological conditions

    SciTech Connect

    Gold, T.; Gordon, B.E.; Streett, W.; Bilson, E.; Patnaik, P.

    1986-11-01

    In order to assess the possible role of methane in petroleum formation, they studied the reaction of methane with liquid hydrocarbons representing the three main classes of compounds dominant in crude oil. The experimental reaction conditions simulated those of a geological setting for petroleum formations, at 1000 atm and 150-250/sup 0/C in the presence of montmorillonite, a natural clay catalyst. Since they expected very slow reaction rates and thus low yields, we used /sup 14/C labeled methane to trace the reaction products. They report here the detection of ethylbenzene and ethyltoluene formed by the interaction of methane with benzene and toluene, respectively. Instead of methylation of benzene, predominantly C/sub 2/ addition occurred, although very small amounts of products corresponding to C/sub 1/ addition were also detected. They propose that catalytic dissociation of methane occurred, forming ethylene which participated in a Friedel-Crafts type alkylation process of the aromatic ring on the catalyst surface. In addition to ring alkylation, side reactions such as polymerization of unsaturates (ethylene, acetylene) appeared to have occurred on the catalyst surface. The nature of these polymers is yet to be determined.

  10. Experimental study of the reaction of methane with petroleum hydrocarbons in geological conditions

    NASA Astrophysics Data System (ADS)

    Gold, Thomas; Gordon, Benjamin E.; Streett, William; Bilson, Elizabeth; Patnaik, Pradyot

    1986-11-01

    In order to assess the possible role of methane in petroleum formation, we studied the reaction of methane with liquid hydrocarbons representing the three main classes of compounds dominant in crude oil. The experimental reaction conditions simulated those of a geological setting for petroleum formations, at 1000 atm and 150-250°C in the presence of montmorillonite, a natural clay catalyst. Since we expected very slow reaction rates and thus low yields, we used 14C labeled methane to trace the reaction products. We report here the detection of ethylbenzene and ethyltoluene formed by the interaction of methane with benzene and toluene, respectively. Instead of methylation of benzene, predominantly C 2 addition occurred, although very small amounts of products corresponding to C 1 addition were also detected. We propose that catalytic dissociation of methane occurred, forming ethylene which participated in a Friedel-Crafts type alkylation process of the aromatic ring on the catalyst surface. In addition to ring alkylation, side reactions such as polymerization of unsaturates (ethylene, acetylene) appeared to have occurred on the catalyst surface. The nature of these polymers is yet to be determined.

  11. Chemical morphogenesis: recent experimental advances in reaction-diffusion system design and control.

    PubMed

    Szalai, István; Cuiñas, Daniel; Takács, Nándor; Horváth, Judit; De Kepper, Patrick

    2012-08-01

    In his seminal 1952 paper, Alan Turing predicted that diffusion could spontaneously drive an initially uniform solution of reacting chemicals to develop stable spatially periodic concentration patterns. It took nearly 40 years before the first two unquestionable experimental demonstrations of such reaction-diffusion patterns could be made in isothermal single phase reaction systems. The number of these examples stagnated for nearly 20 years. We recently proposed a design method that made their number increase to six in less than 3 years. In this report, we formally justify our original semi-empirical method and support the approach with numerical simulations based on a simple but realistic kinetic model. To retain a number of basic properties of real spatial reactors but keep calculations to a minimal complexity, we introduce a new way to collapse the confined spatial direction of these reactors. Contrary to similar reduced descriptions, we take into account the effect of the geometric size in the confinement direction and the influence of the differences in the diffusion coefficient on exchange rates of species with their feed environment. We experimentally support the method by the observation of stationary patterns in red-ox reactions not based on oxihalogen chemistry. Emphasis is also brought on how one of these new systems can process different initial conditions and memorize them in the form of localized patterns of different geometries.

  12. Chemical morphogenesis: recent experimental advances in reaction-diffusion system design and control.

    PubMed

    Szalai, István; Cuiñas, Daniel; Takács, Nándor; Horváth, Judit; De Kepper, Patrick

    2012-08-01

    In his seminal 1952 paper, Alan Turing predicted that diffusion could spontaneously drive an initially uniform solution of reacting chemicals to develop stable spatially periodic concentration patterns. It took nearly 40 years before the first two unquestionable experimental demonstrations of such reaction-diffusion patterns could be made in isothermal single phase reaction systems. The number of these examples stagnated for nearly 20 years. We recently proposed a design method that made their number increase to six in less than 3 years. In this report, we formally justify our original semi-empirical method and support the approach with numerical simulations based on a simple but realistic kinetic model. To retain a number of basic properties of real spatial reactors but keep calculations to a minimal complexity, we introduce a new way to collapse the confined spatial direction of these reactors. Contrary to similar reduced descriptions, we take into account the effect of the geometric size in the confinement direction and the influence of the differences in the diffusion coefficient on exchange rates of species with their feed environment. We experimentally support the method by the observation of stationary patterns in red-ox reactions not based on oxihalogen chemistry. Emphasis is also brought on how one of these new systems can process different initial conditions and memorize them in the form of localized patterns of different geometries. PMID:23919126

  13. Experimental deformation of a mafic rock - interplay between fracturing, reaction and viscous deformation

    NASA Astrophysics Data System (ADS)

    Marti, Sina; Stünitz, Holger; Heilbronner, Renée; Plümper, Oliver; Drury, Martyn

    2016-04-01

    Deformation experiments were performed on natural Maryland Diabase (˜ 55% Plg, 42% Px, 3% accessories, 0.18 wt.-% H2O added) in a Griggs-type deformation apparatus in order to explore the brittle-viscous transition and the interplay between deformation and mineral reactions. Shear experiments at strain rates of ˜ 2e-5 /s are performed, at T=600, 700 and 800°C and confining pressures Pc=1.0 and 1.5 GPa. Deformation localizes in all experiments. Below 700°C, the microstructure is dominated by brittle deformation with a foliation formed by cataclastic flow and high strain accommodated along 3-5 major ultracataclasite shear bands. At 700°C, the bulk of the material still exhibits abundant microfractures, however, deformation localizes into an anastomosing network of shear bands (SB) formed from a fine-grained (<< 1 μm) mixture of newly formed Plg and Amph. These reaction products occur almost exclusively along syn-kinematic structures such as fractures and SB. Experiments at 800°C show extensive mineral reactions, with the main reaction products Amph+Plg (+Zo). Deformation is localized in broad C' and C SB formed by a fine-grained (0.1 - 0.8 μm) mixture of Plg+Amph (+Zo). The onset of mineral reactions in the 700°C experiments shows that reaction kinetics and diffusional mass transport are fast enough to keep up with the short experimental timescales. While in the 700°C experiments brittle processes kinematically contribute to deformation, fracturing is largely absent at 800°C. Diffusive mass transfer dominates. The very small grain size within SB favours a grain size sensitive deformation mechanism. Due to the presence of water (and relatively high supported stresses), dissolution-precipitation creep is interpreted to be the dominant strain accommodating mechanism. From the change of Amph coronas around Px clasts with strain, we can determine that Amph is re-dissolved at high stress sites while growing in low stress sites, showing the ability of Amph to

  14. Experimental Investigation of (p,n) reactions relevant to the astrophysical νp process

    NASA Astrophysics Data System (ADS)

    Perdikakis, G.; Almus, R. M.; Avetisyan, R.; Bataglia, A. A.; Bucher, B. M.; Casarella, C. R.; Fröhlich, C.; Lipschutz, S.; Long, A. M.; Lyons, S.; Marley, S. T.; Ostdiek, K. M.; Redpath, T. H.; Smith, K. I.; Smith, M. K.; Spyrou, A.; Stech, E. J.; Tan, W.; Talwar, R.; Wiescher, M.; Zegers, R. G. T.

    2013-10-01

    A recently discovered nucleosynthesis process, the νp process is thought to take place in core-collapse supernovae and could explain some of the observed abundance trends. The underlying nuclear physics and its role is not yet known due to a lack of experimental information. Aiming to study relevant reaction rates, the (n,p) reactions on 61Cu and 59Ni have been studied through their time-inverse reactions 61Ni(p,n) and 59Co(p,n). Protons with energies between 2.2 and 4 MeV from the FN Tandem of the University of Notre Dame were used to extract excitation functions in 100 keV steps covering the energy range of relevance. Neutrons from the (p,n) reactions with energies between 130 keV and 1 MeV where detected using a subset of the LENDA neutron array. Preliminary results from this investigation will be presented and the impact to nucleosynthesis will be discussed.

  15. Experimental Approach to High-Temperature Stellar Reactions with Low-Energy RI Beams

    NASA Astrophysics Data System (ADS)

    Kubono, S.; Yamaguchi, H.; Amadio, G.; Hayakawa, S.; Wakabayashi, Y.; Kurihara, Y.; He, J. J.; Saito, A.; Fujikawa, H.; Khiem, Le Hong; Niikura, M.; Teranishi, T.; Nishimura, S.; Kato, S.; Lee, C. S.; Kwon, Y. K.; Hahn, I. S.; Kim, A.

    2008-04-01

    The experimental efforts for the stellar reactions under high-temperature and high densities have been made as the major program using the RI beams from the CNS low-energy in-flight RI beam separator (CRIB) of University of Tokyo, in order to understand the evolution of the universe as well as various stellar phenomena. Specifically, two subjects of hydrogen burning are discussed here. One is a reaction study of the pp-chain and the second is of the explosive hydrogen burning, the rp-process. Some s-wave resonances have been identified by the thick target method in the crucial reaction processes in the hydrogen burning. The resonant scattering with the thick target method also succeeded in identifying inelastic resonant scattering, giving proton widths for the first excited state of the target nucleus. This provides very efficiently the reaction rate estimate for the process under high-temperature equilibrium condition. Possibilities of the CRIB facility in near future are also briefly discussed.

  16. A comprehensive collection of experimentally validated primers for Polymerase Chain Reaction quantitation of murine transcript abundance

    PubMed Central

    Spandidos, Athanasia; Wang, Xiaowei; Wang, Huajun; Dragnev, Stefan; Thurber, Tara; Seed, Brian

    2008-01-01

    Background Quantitative polymerase chain reaction (QPCR) is a widely applied analytical method for the accurate determination of transcript abundance. Primers for QPCR have been designed on a genomic scale but non-specific amplification of non-target genes has frequently been a problem. Although several online databases have been created for the storage and retrieval of experimentally validated primers, only a few thousand primer pairs are currently present in existing databases and the primers are not designed for use under a common PCR thermal profile. Results We previously reported the implementation of an algorithm to predict PCR primers for most known human and mouse genes. We now report the use of that resource to identify 17483 pairs of primers that have been experimentally verified to amplify unique sequences corresponding to distinct murine transcripts. The primer pairs have been validated by gel electrophoresis, DNA sequence analysis and thermal denaturation profile. In addition to the validation studies, we have determined the uniformity of amplification using the primers and the technical reproducibility of the QPCR reaction using the popular and inexpensive SYBR Green I detection method. Conclusion We have identified an experimentally validated collection of murine primer pairs for PCR and QPCR which can be used under a common PCR thermal profile, allowing the evaluation of transcript abundance of a large number of genes in parallel. This feature is increasingly attractive for confirming and/or making more precise data trends observed from experiments performed with DNA microarrays. PMID:19108745

  17. Single particle refuse-derived fuel devolatilization: Experimental measurements of reaction products

    SciTech Connect

    Lai, Weichuan; Krieger-Brockett, B. . Dept. of Chemical Engineering)

    1993-11-01

    The authors present experimentally measured devolatilization product yields from single particles of refuse-derived fuel (RDF), a more uniform, transportable municipal solid waste. Disposal costs and environmental concerns have stimulated interest in thermochemical conversion of this material to chemicals and fuels. The composition, reaction conditions, and particle properties were systematically varied over the range found in practice to develop quantitative measures that rank the process controllables' influence on altering the product slate. Specialized regression methods and experimental designs enhanced the accuracy in view of the feed heterogeneity and offer a general method to extract real effects from experimental and sample noise''. The results have been verified successfully using actual commercial RDF and fabricated compositions that surpass those normally found in municipal waste to anticipate the influence of trends in recycling. The results show that the reaction conditions have a greater influence on altering fuel utilization and the relative yields of char, condensibles, and gases than does the composition over the range found in MSW and RDF.

  18. A new compilation of experimental nuclear data for total reaction cross sections

    NASA Astrophysics Data System (ADS)

    Lantz, Mattias; Sihver, L.

    The nucleon-nucleus and nucleus-nucleus total reaction cross sections are of importance in many different fields, both for a better theoretical understanding as well as for a number of applications, including space radiation dosimetry. We have performed a comprehensive literature study in order to find all available experimental data on total reaction cross sections, σR , and interaction cross sections, σI , for neutrons, protons, and all stable and exotic heavy ions. Excluded from the data base are measurements where the cross sections have been derived through model-dependent calculations from other kinds of measurements. The objective of the study is to identify where more measurements are needed in view of different applications, and to make the data easily available for model developers and experimentalists. We will present some examples from the study, which is in the stage of quality control of all the gathered data.

  19. An experimental and computational study of the ions formed by the reaction of cyclopentanone with O-

    NASA Astrophysics Data System (ADS)

    Hoenigman, Rebecca L.; Kato, Shuji; Borden, Weston Thatcher; Bierbaum, Veronica M.

    2005-03-01

    The structures and reactivities of the ions formed by the reaction of cyclopentanone with O- have been studied using flowing afterglow-selected ion flow tube (FA-SIFT) experiments in conjunction with density functional theory (DFT) calculations. Three C5H6O- isomers were found to be generated - cyclopentanone-2,5-diyl radical anion (4-), 2-carbenacyclopentanone radical anion (5-), and cyclopentanone-2,4-diyl radical anion (6-). The large amount of signal loss observed in this reaction is attributed to formation of 2-cyclopentenone radical anion (10-), in which the electron is predicted to be unbound. DFT calculations predict 4- to be the most stable of the bound C5H6O- ions, and FA-SIFT experiments confirm 4- is the major ion formed in this reaction. Bracketing experiments found the proton affinity (PA) of 4- to be 362 +/- 5 kcal/mol and the electron binding energy (EBE) to be ca. 0.5 eV. Although the PA of this species predicted by DFT calculations (363.2 kcal/mol) is consistent with the experimental value, both DFT and ab initio calculations predict an EBE of ca. 1.6 eV for this radical anion. The apparent conflict between the calculated and experimental EBE is resolved by proposing that, in the gas phase bracketing experiments, the electron transfer process leads adiabatically, not to cyclopentanone-2,5-diyl (4), but, by a retro-Nazarov reaction, to the more stable 1,4-pentadien-3-one (18). DFT calculations show that the difference between the computed and measured EBEs of 4- can be accounted for by the calculated difference between the energies of 18 and 4.

  20. Fuel-rich, catalytic reaction experimental results. [fuel development for high-speed civil transport aircraft

    NASA Technical Reports Server (NTRS)

    Rollbuhler, Jim

    1991-01-01

    Future aeropropulsion gas turbine combustion requirements call for operating at very high inlet temperatures, pressures, and large temperature rises. At the same time, the combustion process is to have minimum pollution effects on the environment. Aircraft gas turbine engines utilize liquid hydrocarbon fuels which are difficult to uniformly atomize and mix with combustion air. An approach for minimizing fuel related problems is to transform the liquid fuel into gaseous form prior to the completion of the combustion process. Experimentally obtained results are presented for vaporizing and partially oxidizing a liquid hydrocarbon fuel into burnable gaseous components. The presented experimental data show that 1200 to 1300 K reaction product gas, rich in hydrogen, carbon monoxide, and light-end hydrocarbons, is formed when flowing 0.3 to 0.6 fuel to air mixes through a catalyst reactor. The reaction temperatures are kept low enough that nitrogen oxides and carbon particles (soot) do not form. Results are reported for tests using different catalyst types and configurations, mass flowrates, input temperatures, and fuel to air ratios.

  1. Cordierite formation during the experimental reaction of plagioclase with Mg-rich aqueous solutions

    NASA Astrophysics Data System (ADS)

    Hövelmann, J.; Austrheim, H.; Putnis, A.

    2014-09-01

    The reaction between plagioclase (labradorite and oligoclase) and Mg-rich aqueous solutions was studied experimentally at hydrothermal conditions (600-700 °C, 2 kbar). During the experiments, plagioclase grains were readily converted to cordierite and quartz within 4 days. The cordierite crystals had well-developed polyhedral shapes, but showed skeletal internal morphologies suggesting that the initial growth occurred fast under high-driving-force conditions. In pure MgCl2 solutions (0.5-5 M), plagioclase dissolution and cordierite precipitation were spatially uncoupled indicating that Al was to some extent mobile in the fluid. Cordierite crystals formed at 700 °C showed orthorhombic symmetry, whereas those formed at 600 °C dominantly persisted in the metastable hexagonal form suggesting a strong increase in Al, Si ordering speed between 600 and 700 °C. The thermodynamic evolution of the fluid-solid system ultimately resulted in stabilization of Ca-rich plagioclase as demonstrated by partial anorthitization of unreacted plagioclase grains. Cordierite was also observed to form when Mg was added to a potentially albitizing Na-silicate-bearing solution. In that case, cordierite precipitation appeared to be more closely coupled to plagioclase dissolution, and secondary alteration of remnant plagioclase grains did not occur most likely due to armoring of the plagioclase by the cordierite overgrowth. The fast reaction rates observed in our experimental study have potential implications for Mg-metasomatism as a rock-forming process.

  2. Graft copolymerization of acrylic acid onto polyamide fibers

    NASA Astrophysics Data System (ADS)

    Makhlouf, Chahira; Marais, Stéphane; Roudesli, Sadok

    2007-04-01

    The grafting of acrylic acid (AA) monomer (CH 2dbnd CH sbnd COOH) on polyamide 6.6 monofilaments (PA 6.6) using benzoyl peroxide (BPO) as initiator was carried out in order to enhance the hydrophilic nature of fibers. The grafting rate depends on the AA concentration, the BPO concentration, the time and the temperature of reaction. The best conditions for optimum rate of grafting were obtained with a AA concentration of 0.5 M, a BPO concentration of 0.03 M, a reaction temperature of T = 85 °C and a reaction time of 120 mn. The fiber surface has been investigated by many experimental techniques of characterization such as Fourier transform infrared spectroscopy (FTIR), calorimetric analysis (DSC), scanning electron microscopy (SEM), and contact angle measurements. The effect of grafting of acrylic acid onto PA 6.6 fibers on their moisture and mechanical resistances was analyzed from water sorption and elongation at break measurements. The analysis of the experimental data shows clearly the efficiency of the grafting reaction used, leading to a significant increase of the hydrophilic character of the PA 6.6 surface.

  3. Experimental verification of a computational technique for determining ground reactions in human bipedal stance.

    PubMed

    Audu, Musa L; Kirsch, Robert F; Triolo, Ronald J

    2007-01-01

    We have developed a three-dimensional (3D) biomechanical model of human standing that enables us to study the mechanisms of posture and balance simultaneously in various directions in space. Since the two feet are on the ground, the system defines a kinematically closed-chain which has redundancy problems that cannot be resolved using the laws of mechanics alone. We have developed a computational (optimization) technique that avoids the problems with the closed-chain formulation thus giving users of such models the ability to make predictions of joint moments, and potentially, muscle activations using more sophisticated musculoskeletal models. This paper describes the experimental verification of the computational technique that is used to estimate the ground reaction vector acting on an unconstrained foot while the other foot is attached to the ground, thus allowing human bipedal standing to be analyzed as an open-chain system. The computational approach was verified in terms of its ability to predict lower extremity joint moments derived from inverse dynamic simulations performed on data acquired from four able-bodied volunteers standing in various postures on force platforms. Sensitivity analyses performed with model simulations indicated which ground reaction force (GRF) and center of pressure (COP) components were most critical for providing better estimates of the joint moments. Overall, the joint moments predicted by the optimization approach are strongly correlated with the joint moments computed using the experimentally measured GRF and COP (0.78 < or = r(2) < or = 0.99,median,0.96) with a best-fit that was not statistically different from a straight line with unity slope (experimental=computational results) for postures of the four subjects examined. These results indicate that this model-based technique can be relied upon to predict reasonable and consistent estimates of the joint moments using the predicted GRF and COP for most standing postures.

  4. Alternating copolymerization of propylene oxide with biorenewable terpene-based cyclic anhydrides: a sustainable route to aliphatic polyesters with high glass transition temperatures.

    PubMed

    Van Zee, Nathan J; Coates, Geoffrey W

    2015-02-23

    The alternating copolymerization of propylene oxide with terpene-based cyclic anhydrides catalyzed by chromium, cobalt, and aluminum salen complexes is reported. The use of the Diels-Alder adduct of α-terpinene and maleic anhydride as the cyclic anhydride comonomer results in amorphous polyesters that exhibit glass transition temperatures (Tg ) of up to 109 °C. The polymerization conditions and choice of catalyst have a dramatic impact on the molecular weight distribution, the relative stereochemistry of the diester units along the polymer chain, and ultimately the Tg of the resulting polymer. The aluminum salen complex exhibits exceptional selectivity for copolymerization without transesterification or epimerization side reactions. The resulting polyesters are highly alternating and have high molecular weights and narrow polydispersities.

  5. Copolymerization as a Strategy to Combine Epoxidized Linseed Oil and Furfuryl Alcohol: The Design of a Fully Bio-Based Thermoset.

    PubMed

    Pin, Jean-Mathieu; Guigo, Nathanaël; Vincent, Luc; Sbirrazzuoli, Nicolas; Mija, Alice

    2015-12-21

    Epoxidized linseed oil and furfuryl alcohol are bio-sourced monomers known for their high-potential applications in materials science. In this work, we propose the association of these monomers through copolymerization reactions with the target to design fully bio-based thermosets. Herein, investigations on cationic polymerization reactivity have been explored using differential scanning calorimetry. The obtained structures have been confirmed by IR spectroscopy and 2 D NMR spectroscopy, which revealed the principal chain connections. In spite of the multiple capabilities of chemical connections, which include copolymerization and cross-linking, the obtained networks are homogeneous as confirmed by dynamic mechanical analysis and SEM. Furthermore, the copolymer demonstrates a semiductile behavior if subjected to tensile measurements (tensile strain at break ≈40 %), which is a significant advance in terms of its applications as a furanic bio-based thermoset material. PMID:26663869

  6. Experimental Measurements of the Chemical Reaction Zone of TATB and HMX based explosives

    NASA Astrophysics Data System (ADS)

    Bouyer, Viviane; Héebert, Philippe; Doucet, Michel; Sollier, Arnaud; Decaris, Lionel; Terzulli, Louis-Pierre

    2011-06-01

    In order to have an insight into the chemical reaction zone of explosives, experimental measurement of the detonation wave profile of solid explosives using laser velocimetry techniques are performed. The experiments consist in initiating a detonation wave in a cylinder of explosive using an explosive wire detonator and an explosive booster and measuring the particle velocity of an explosive-window interface or free surface velocity of an accelerated foil. Two explosives (TATB based and TATB-HMX based) have been studied through several configurations where the cylinder diameter and window or plate material could vary. Particle velocity profiles have been measured by VISAR and Heterodyne Velocimetry (HV). The results on the behavior of the explosives have been analyzed and compared with those of Photon Doppler Velocimetry of expanding species experiments. These experiments also enabled to carry on the comparison of the efficiency of VISAR and HV in such applications.

  7. Experimental measurements of the chemical reaction zone of TATB and HMX based explosives

    NASA Astrophysics Data System (ADS)

    Bouyer, Viviane; Hebert, Philippe; Doucet, Michel; Decaris, Lionel; Terzulli, Louis-Pierre

    2012-03-01

    In order to have an insight into the chemical reaction zone of high explosives (HE), experimental measurements of the detonation wave profile of solid explosives using laser velocimetry techniques have been performed. The experiments consisted in initiating a detonation wave in a cylinder of explosive using an explosive wire detonator associated with an explosive booster and in measuring the particle velocity of an explosive-window interface. A TATB based HE and a TATBHMX based HE have been studied through several configurations where the cylinder geometry and the window material could vary. Particle velocity profiles were measured by VISAR and Heterodyne Velocimetry (HV). The results on the behavior of the explosives have been analyzed and compared with those of Photon Doppler Velocimetry of expanding species experiments. These experiments also enabled to carry on the comparison of the efficiency of VISAR and HV in such applications.

  8. Experimental cross-sections for proton-induced nuclear reactions on natMo

    NASA Astrophysics Data System (ADS)

    Červenák, Jaroslav; Lebeda, Ondřej

    2016-08-01

    In the framework of the Co-ordinated Research Project of the IAEA, we measured in detail cross-sections of the nuclear reactions natMo(p,x)93gTc, 93mTc, 93m+gTc, 94gTc, 94mTc, 95gTc, 95mTc, 96m+gTc, 97mTc, 99mTc, 90Mo, 93mMo, 99Mo, 88gNb, 88mNb, 89gNb, 89mNb, 90m+gNb, 90m+gNbcum, 91mNb, 92mNb, 95gNb, 95mNb, 95m+gNb, 96Nb, 97m+gNb, 88m+gZrcum and 89m+gZrcum in the energy range of 6.9-35.8 MeV. The data for formation of 97mTc, 88gNb, 88mNb and 89mNb are reported for the first time. The obtained results were compared to the prediction of the nuclear reaction model code TALYS adopted from the TENDL-2015 library and to the previously published cross-sections. The thick target yields for all the radionuclides were calculated from the measured data. We suggest recommended cross-sections and thick target yields for the 100Mo(p,2n)99mTc, 100Mo(p,x)99Mo and natMo(p,x)96m+gTc nuclear reactions deduced from the selected experimental data.

  9. Generation of Hydrogen and Methane during Experimental Low-Temperature Reaction of Ultramafic Rocks with Water

    NASA Astrophysics Data System (ADS)

    McCollom, Thomas M.; Donaldson, Christopher

    2016-06-01

    Serpentinization of ultramafic rocks is widely recognized as a source of molecular hydrogen (H2) and methane (CH4) to support microbial activity, but the extent and rates of formation of these compounds in low-temperature, near-surface environments are poorly understood. Laboratory experiments were conducted to examine the production of H2 and CH4 during low-temperature reaction of water with ultramafic rocks and minerals. Experiments were performed by heating olivine or harzburgite with aqueous solutions at 90°C for up to 213 days in glass bottles sealed with butyl rubber stoppers. Although H2 and CH4 increased steadily throughout the experiments, the levels were very similar to those found in mineral-free controls, indicating that the rubber stoppers were the predominant source of these compounds. Levels of H2 above background were observed only during the first few days of reaction of harzburgite when CO2 was added to the headspace, with no detectable production of H2 or CH4 above background during further heating of the harzburgite or in experiments with other mineral reactants. Consequently, our results indicate that production of H2 and CH4 during low-temperature alteration of ultramafic rocks may be much more limited than some recent experimental studies have suggested. We also found no evidence to support a recent report suggesting that spinels in ultramafic rocks may stimulate H2 production. While secondary silicates were observed to precipitate during the experiments, formation of these deposits was dominated by Si released by dissolution of the glass bottles, and reaction of the primary silicate minerals appeared to be very limited. While use of glass bottles and rubber stoppers has become commonplace in experiments intended to study processes that occur during serpentinization of ultramafic rocks at low temperatures, the high levels of H2, CH4, and SiO2 released during heating indicate that these reactor materials are unsuitable for this purpose.

  10. Modification of flax fibres by radiation induced emulsion graft copolymerization of glycidyl methacrylate

    NASA Astrophysics Data System (ADS)

    Moawia, Rihab Musaad; Nasef, Mohamed Mahmoud; Mohamed, Nor Hasimah; Ripin, Adnan

    2016-05-01

    Flax fibres were modified by radiation induced graft copolymerization of glycidyl methacrylate (GMA) by pre-irradiation method in an emulsion medium. The effect of reaction parameters on the degree of grafting (DOG) such as concentration of bleaching agent, absorbed dose, monomer concentration, temperature and reaction time were investigated. The DOG was found to be dependent on the investigated parameters. The incorporation of poly(GMA) grafts in the bleached flax fibres was confirmed by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The structural and mechanical changes were evaluated by X-ray diffraction (XRD) and mechanical tester, respectively. The results revealed that reacting bleached flax fibres irradiated with 20 kGy with 5% GMA emulsion containing 0.5% polyoxyethylene-sorbitan monolaurate (Tween 20) surfactant at 40 °C for 1 h led to a maximum DOG of 148%. The grafted fibres showed sufficient mechanical strength and hydrophobicity which make them promising precursors for development of adsorbents after appropriate chemical treatments.

  11. Hyperbranched PEG by random copolymerization of ethylene oxide and glycidol.

    PubMed

    Wilms, Daniel; Schömer, Martina; Wurm, Frederik; Hermanns, M Iris; Kirkpatrick, C James; Frey, Holger

    2010-10-18

    The synthesis of hyperbranched poly(ethylene glycol) (hbPEG) in one step was realized by random copolymerization of ethylene oxide and glycidol, leading to a biocompatible, amorphous material with multiple hydroxyl functionalities. A series of copolymers with moderate polydispersity ($\\overline {M} _{{\\rm w}} /\\overline {M} _{{\\rm n}} $ < 1.8) was obtained with varying glycidol content (3-40 mol-%) and molecular weights up to 49 800 g mol(-1) . The randomly branched structure of the copolymers was confirmed by (1) H and (13) C NMR spectroscopy and thermal analysis (differential scanning calorimetry). MTS assay demonstrated low cell toxicity of the hyperbranched PEG, comparable to the highly established linear PEG.

  12. Cationic resins prepared by radiation-induced graft copolymerization

    NASA Astrophysics Data System (ADS)

    Siyam, T.; Youssef, H. A.

    1999-07-01

    Poly(acrylamide-acrylic acid) resin P(PAM-AA) was prepared by gamma radiation-initiated grafting copolymerization of acrylic acid (AA) on polyacrylamide (PAM) by addition of Mohr's salt as an inhibitor for homopolymerization. The polymerization was studied at different absorbed doses, polymor/monomer ratios and the monomer concentrations. The grafting percentage increases by increasing the dose and the monomer concentration and decreases by increasing polymer/monomer ratio. There is no significant change in the swelling degree of the obtained resin. It was found that the capacity of the resins towards Cu 2+ increases with increasing the monomer concentration and decreases by increasing the polymer/monomer ratio. The capacity of the resin was found to be constant at all doses.

  13. Experimental and Guided Theoretical Investigation of Complex Reaction Mechanisms in a Prins Reaction of Glyoxylic Acid and Isobutene

    ERIC Educational Resources Information Center

    Angelici, Gaetano; Nicolet, Stefan; Uda, Narasimha R.; Creus, Marc

    2014-01-01

    A laboratory experiment was designed for undergraduate students, in which the outcome of an easy single-step organic synthesis with well-defined conditions was not elucidated until the end of the exercise. In class, students predict and discuss the possible products using their knowledge of reaction mechanisms. In the laboratory, they learn how to…

  14. Experimental Cross Sections for Reactions of Heavy Ions and 208Pb, 209Bi, 238U, and 248Cm Targets

    SciTech Connect

    Patin, Joshua B.

    2002-05-24

    The study of the reactions between heavy ions and {sup 208}Pb, {sup 209}Bi, {sup 238}U, and {sup 248} Cm targets was performed to look at the differences between the cross sections of hot and cold fusion reactions. Experimental cross sections were compared with predictions from statistical computer codes to evaluate the effectiveness of the computer code in predicting production cross sections. Hot fusion reactions were studied with the MG system, catcher foil techniques and the Berkeley Gas-filled Separator (BGS). 3n- and 4n-exit channel production cross sections were obtained for the {sup 238}U({sup 18}O,xn){sup 256-x}Fm, {sup 238}U({sup 22}Ne,xn){sup 260-x}No, and {sup 248}Cm({sup 15}N,xn){sup 263-x}Lr reactions and are similar to previous experimental results. The experimental cross sections were accurately modeled by the predictions of the HIVAP code using the Reisdorf and Schaedel parameters and are consistent with the existing systematics of 4n exit channel reaction products. Cold fusion reactions were examined using the BGS. The {sup 208}Pb({sup 48}Ca,xn){sup 256-x}No, {sup 208}Pb({sup 50}Ti,xn){sup 258-x}Rf, {sup 208}Pb({sup 51}V,xn){sup 259-x}Db, {sup 209}Bi({sup 50}Ti,xn){sup 259-x}Db, and {sup 209}Bi({sup 51}V,xn){sup 260-x}Sg reactions were studied. The experimental production cross sections are in agreement with the results observed in previous experiments. It was necessary to slightly alter the Reisdorf and Schaedel parameters for use in the HIVAP code in order to more accurately model the experimental data. The cold fusion experimental results are in agreement with current 1n- and 2n-exit channel systematics.

  15. Experimental and Theoretical Study of Reactions of OH Radicals with Hexenols: An Evaluation of the Relative Importance of the H-Abstraction Reaction Channel.

    PubMed

    Gai, Yanbo; Lin, Xiaoxiao; Ma, Qiao; Hu, Changjin; Gu, Xuejun; Zhao, Weixiong; Fang, Bo; Zhang, Weijun; Long, Bo; Long, Zhengwen

    2015-09-01

    C6 hexenols are one of the most significant groups of volatile organic compounds with biogenic emissions. The lack of corresponding kinetic parameters and product information on their oxidation reactions will result in incomplete atmospheric chemical mechanisms and models. In this paper, experimental and theoretical studies are reported for the reactions of OH radicals with a series of C6 hexenols, (Z)-2-hexen-1-ol, (Z)-3-hexen-1-ol, (Z)-4-hexen-1-ol, (E)-2-hexen-1-ol, (E)-3-hexen-1-ol, and (E)-4-hexen-1-ol, at 298 K and 1.01 × 10(5) Pa. The corresponding rate constants were 8.53 ± 1.36, 10.1 ± 1.6, 7.86 ± 1.30, 8.08 ± 1.33, 9.10 ± 1.50, and 7.14 ± 1.20 (in units of 10(-11) cm(3) molecule(-1) s(-1)), respectively, measured by gas chromatography with a flame ionization detector (GC-FID), using a relative technique. Theoretical calculations concerning the OH-addition and H-abstraction reaction channels were also performed for these reactions to further understand the reaction mechanism and the relative importance of the H-abstraction reaction. By contrast to previously reported results, the H-abstraction channel is a non-negligible reaction channel for reactions of OH radicals with these hexenols. The rate constants of the H-abstraction channel are comparable with those for the OH-addition channel and contribute >20% for most of the studied alcohols, even >50% for (E)-3-hexen-1-ol. Thus, H-abstraction channels may have an important role in the reactions of these alcohols with OH radicals and must be considered in certain atmospheric chemical mechanisms and models. PMID:26274814

  16. Towards a More Complete and Accurate Experimental Nuclear Reaction Data Library (EXFOR). International Collaboration Between Nuclear Reaction Data Centres (NRDC)

    SciTech Connect

    Otuka, N.; Pritychenko, B.; Otuka, N.; Dupont, E.; Semkova, V.; Pritychenko, B.; Blokhin, A. I.; Aikawa, M.; Babykina, S.; Bossant, M.; Chen, G.; Dunaeva, S.; Forrest, R. A.; Fukahori, T.; Furutachi, N.; Ganesan, S.; Ge, Z.; Gritzay, O. O.; Herman, M.; Hlavac, S.; Kato, K.; Lalremruata, B.; Lee, Y. O.; Makinaga, A.; Matsumoto, K.; Mikhaylyukova, M.; Pikulina, G.; Pronyaev, V. G.; Saxena, A.; Schwerer, O.; Simakov, S. P.; Soppera, N.; Suzuki, R.; Takacs, S.; Tao, X.; Taova, S.; Tarkanyi, F.; Varlamov, V. V.; Wang, J.; Yang, S. C.; Zerkin, V.; Zhuang, Y.

    2014-06-01

    The International Network of Nuclear Reaction Data Centres (NRDC) coordinated by the IAEA Nuclear Data Section (NDS) successfully collaborates in the maintenance and development of the EXFOR library. Likewise, as the scope of published data expands (e.g. to higher energy, to heavier projectile) to meet the needs of research and applications, it has become a challenging task to maintain both the completeness and accuracy of the EXFOR library. Evolution of the library highlighting recent developments is described.

  17. Towards a More Complete and Accurate Experimental Nuclear Reaction Data Library (EXFOR): International Collaboration Between Nuclear Reaction Data Centres (NRDC)

    SciTech Connect

    Otuka, N.; Dupont, E.; Semkova, V.; Pritychenko, B.; Blokhin, A.I.; Aikawa, M.; Babykina, S.; Bossant, M.; Chen, G.; Dunaeva, S.; Forrest, R.A.; Fukahori, T.; Furutachi, N.; Ganesan, S.; Ge, Z.; Gritzay, O.O.; Herman, M.; Hlavač, S.; and others

    2014-06-15

    The International Network of Nuclear Reaction Data Centres (NRDC) coordinated by the IAEA Nuclear Data Section (NDS) successfully collaborates in the maintenance and development of the EXFOR library. As the scope of published data expands (e.g. to higher energy, to heavier projectile) to meet the needs of research and applications, it has become a challenging task to maintain both the completeness and accuracy of the EXFOR library. Evolution of the library highlighting recent developments is described.

  18. Growth of polyphenyls via ion-molecule reactions: an experimental and theoretical mechanistic study.

    PubMed

    Aysina, Julia; Maranzana, Andrea; Tonachini, Glauco; Tosi, Paolo; Ascenzi, Daniela

    2013-05-28

    The reactivity of biphenylium cations C12H9(+) with benzene C6H6 is investigated in a joint experimental and theoretical approach. Experiments are performed by using a triple quadruple mass spectrometer equipped with an atmospheric pressure chemical ion source to generate C12H9(+) via dissociative ionization of various isomers of the neutral precursor hydroxybiphenyl (C12H10O). C-C coupling reactions leading to hydrocarbon growth are observed. The most abundant ionic products are C18H15(+), C18H13(+), C17H12(+), and C8H7(+). The dependence of product ion yields on the kinetic energy of reagent ions, as well as further experiments performed using partial isotopic labelling of reagents, support the idea that the reaction proceeds via a long lived association product, presumably the covalently bound protonated terphenyl C18H15(+). Its formation is found to be exothermic and barrierless and, therefore, might occur under the low pressure and temperature conditions typical of planetary atmospheres and the interstellar medium. Theoretical calculations have focussed on the channel leading to C8H7(+) plus C10H8, identifying, as the most probable fragments, the phenylethen-1-ylium cation and naphthalene, thus suggesting that the pathway leading to them might be of particular interest for the synthesis of polycyclic aromatic hydrocarbons. Both experiments and theory agree in finding this channel exoergic but hampered by small barriers of 2.7 and 3.7 kcal mol(-1) on the singlet potential energy surface. PMID:23742478

  19. Growth of polyphenyls via ion-molecule reactions: An experimental and theoretical mechanistic study

    SciTech Connect

    Aysina, Julia; Tosi, Paolo; Ascenzi, Daniela; Maranzana, Andrea; Tonachini, Glauco

    2013-05-28

    The reactivity of biphenylium cations C{sub 12}H{sub 9}{sup +} with benzene C{sub 6}H{sub 6} is investigated in a joint experimental and theoretical approach. Experiments are performed by using a triple quadruple mass spectrometer equipped with an atmospheric pressure chemical ion source to generate C{sub 12}H{sub 9}{sup +} via dissociative ionization of various isomers of the neutral precursor hydroxybiphenyl (C{sub 12}H{sub 10}O). C-C coupling reactions leading to hydrocarbon growth are observed. The most abundant ionic products are C{sub 18}H{sub 15}{sup +}, C{sub 18}H{sub 13}{sup +}, C{sub 17}H{sub 12}{sup +}, and C{sub 8}H{sub 7}{sup +}. The dependence of product ion yields on the kinetic energy of reagent ions, as well as further experiments performed using partial isotopic labelling of reagents, support the idea that the reaction proceeds via a long lived association product, presumably the covalently bound protonated terphenyl C{sub 18}H{sub 15}{sup +}. Its formation is found to be exothermic and barrierless and, therefore, might occur under the low pressure and temperature conditions typical of planetary atmospheres and the interstellar medium. Theoretical calculations have focussed on the channel leading to C{sub 8}H{sub 7}{sup +} plus C{sub 10}H{sub 8}, identifying, as the most probable fragments, the phenylethen-1-ylium cation and naphthalene, thus suggesting that the pathway leading to them might be of particular interest for the synthesis of polycyclic aromatic hydrocarbons. Both experiments and theory agree in finding this channel exoergic but hampered by small barriers of 2.7 and 3.7 kcal mol{sup -1} on the singlet potential energy surface.

  20. Melt-Peridotite Reaction Mechanism of North China Craton Destruction: Experimental Constrains

    NASA Astrophysics Data System (ADS)

    Wang, C.; Jin, Z.; Gao, S.; Zhang, J.; Zheng, S.

    2009-12-01

    Although the geoscientsts in the world have reached an agreement about the Mesozoic thinning of North China Craton, the dynamics of this process is still under debate, especially the thinning mechanism. There are two popular thinning mechanisms were proposed for the North China Craton, one is the delamination model and the other is thermo-mechanical erosion model. The delamination model has aroused great interests since Gao et al. use it to explain the formation of Xilonggou high Mg# andesite from Liaoxi region of Liaoning Province. These Lavas, which possessed an adakitic signature with high Mg#, were believed to origin by the interaction between silica rich and yttrium delepted melt, which are formed by partile melting of low crust eclogite, and asthenospheric peridotite. The discovery of zoned mantle olivine and pyroxene xenocrysts, especially zoned mantle peridotitic xenoliths in Mesozoic basaltic rocks from eastern North China, indicates that peridotite-melt reaction was widespread in Mesozoic lithospheric mantle beneath the southeastern North China craton. Such interaction could be an important mechanism for the compositional transformation and rapid enrichment of the lithospheric mantle. We conducted a series of experiments at a pressure of 2.0 GPa and temperatures of 1250-1400 °C using Bixiling eclogite and Damaping peridotite as starting materials to study the mechanism of melt-peridotite reaction. Our results show that olivine and orthopyroxene were dissolved in the reacting melts between eclogite and peridotite, resulting in clinopyroxene precipitation along the interface of melts and lherzolite. The experimental run products, possessing a lherzolite-pyroxenite-garnet pyroxenite sequence, are identical to the composite mantle xenoliths in the Neogene Hannuoba basalt of the North China craton. The later is considered as strong evidence of the maffic lower continental crust recycling into the mantle during the Mesozoic Era. The reacting melts have a high

  1. Cycloaddition Reaction of Vinylphenylfurans and Dimethyl Acetylenedicarboxylate to [8 + 2] Isomers via Tandem [4 + 2]/Diradical Alkene-Alkene Coupling/[1,3]-H Shift Reactions: Experimental Exploration and DFT Understanding of Reaction Mechanisms.

    PubMed

    Chen, Kai; Wu, Feng; Ye, Lijuan; Tian, Zi-You; Yu, Zhi-Xiang; Zhu, Shifa

    2016-09-16

    An experimental test of designed [8 + 2] reaction of vinylphenylfuran and dimethyl acetylenedicarboxylate (DMAD) has been carried out, showing that the reaction gave unexpected addition products under different conditions. When the reaction was conducted under thermal conditions in toluene, expoxyphenanthrene, which was named as a [8 + 2] isomer, was generated. The scope of this reaction has been investigated in the present study. In addition, experiments and DFT calculations have been conducted to investigate how the reaction between vinylphenylfuran and DMAD took place. Surprisingly, the reaction did not involve the expected [8 + 2] intermediate, o-quinodimethane. Instead, the reaction starts from intermolecular Diels-Alder reactions between DMAD and the furan moiety of vinylphenylfuran, followed by unexpected intramolecular alkene-alkene coupling. This step generates a diradical species, which then undergoes [1,3]-H shift to give the experimentally observed expoxyphenanthrene. DFT calculations revealed that, the [8 + 2] cycloadduct cannot be obtained because the [1,5]-H shift process from the [1,5]-vinyl shift intermediate is disfavored kinetically compared to the [1,3]-H shift to the [8 + 2] isomer.

  2. Cycloaddition Reaction of Vinylphenylfurans and Dimethyl Acetylenedicarboxylate to [8 + 2] Isomers via Tandem [4 + 2]/Diradical Alkene-Alkene Coupling/[1,3]-H Shift Reactions: Experimental Exploration and DFT Understanding of Reaction Mechanisms.

    PubMed

    Chen, Kai; Wu, Feng; Ye, Lijuan; Tian, Zi-You; Yu, Zhi-Xiang; Zhu, Shifa

    2016-09-16

    An experimental test of designed [8 + 2] reaction of vinylphenylfuran and dimethyl acetylenedicarboxylate (DMAD) has been carried out, showing that the reaction gave unexpected addition products under different conditions. When the reaction was conducted under thermal conditions in toluene, expoxyphenanthrene, which was named as a [8 + 2] isomer, was generated. The scope of this reaction has been investigated in the present study. In addition, experiments and DFT calculations have been conducted to investigate how the reaction between vinylphenylfuran and DMAD took place. Surprisingly, the reaction did not involve the expected [8 + 2] intermediate, o-quinodimethane. Instead, the reaction starts from intermolecular Diels-Alder reactions between DMAD and the furan moiety of vinylphenylfuran, followed by unexpected intramolecular alkene-alkene coupling. This step generates a diradical species, which then undergoes [1,3]-H shift to give the experimentally observed expoxyphenanthrene. DFT calculations revealed that, the [8 + 2] cycloadduct cannot be obtained because the [1,5]-H shift process from the [1,5]-vinyl shift intermediate is disfavored kinetically compared to the [1,3]-H shift to the [8 + 2] isomer. PMID:27541179

  3. An experimental study of the organic molecules produced in cometary and interstellar ice analogs by thermal formaldehyde reactions

    NASA Technical Reports Server (NTRS)

    Schutte, W. A.; Allamandola, L. J.; Sandford, S. A.

    1993-01-01

    Results of an experimental study tracing thermal formaldehyde reactions in astrophysically relevant ices in dense molecular clouds are reported. The formaldehyde chemistry during warm-up of ices containing H2CO and one or more of the molecules H2O, CH3OH, CO, O2, and NH3 were monitored using IR spectroscopy. Conversion of H2CO into residues was observed to start at about 40 K for NH3:H2CO ices and at about 80 K in H2O-rich ices. A total of five different organic products of these reactions were distinguished: POM and reaction products of H2CO and H2O, CH3OH, and NH3. Given the measured reaction paths and efficiencies, it is estimated that on the order of 1 percent of the organics found in the coma of Comet P/Halley could have been produced by thermal formaldehyde reactions taking place in the nucleus.

  4. Experimental Correlation of Substrate Position with Reaction Outcome in the Aliphatic Halogenase, SyrB2

    PubMed Central

    Martinie, Ryan J.; Livada, Jovan; Chang, Wei-chen; Green, Michael T.; Krebs, Carsten; Bollinger, J. Martin; Silakov, Alexey

    2015-01-01

    The iron(II)- and 2-(oxo)glutarate-dependent (Fe/2OG) oxygenases catalyze an array of challenging transformations, but how individual members of the enzyme family direct different outcomes is poorly understood. The Fe/2OG halogenase, SyrB2, chlorinates C4 of its native substrate, L-threonine appended to the carrier protein, SyrB1, but hydroxylates C5 of L-norvaline and, to a lesser extent, C4 of L-aminobutyric acid when SyrB1 presents these non-native amino acids. To test the hypothesis that positioning of the targeted carbon dictates the outcome, we defined the positions of these three substrates by measuring hyperfine couplings between substrate deuterium atoms and the stable, EPR-active iron-nitrosyl adduct, a surrogate for reaction intermediates. The Fe-2H distances and N-Fe-2H angles, which vary from 4.2 Å and 85° for threonine to 3.4 Å and 65° for norvaline, rationalize the trends in reactivity. This experimental correlation of position to outcome should aid in judging from structural data on other Fe/2OG enzymes whether they suppress hydroxylation or form hydroxylated intermediates on the pathways to other outcomes. PMID:25965587

  5. Diffusion and defect reactions between donors, C, and vacancies in Ge. I. Experimental results

    NASA Astrophysics Data System (ADS)

    Brotzmann, S.; Bracht, H.; Hansen, J. Lundsgaard; Larsen, A. Nylandsted; Simoen, E.; Haller, E. E.; Christensen, J. S.; Werner, P.

    2008-06-01

    The diffusion of self-atoms and n -type dopants such as phosphorus, arsenic, and antimony in germanium was studied by means of isotopically controlled multilayer structures doped with carbon. The diffusion profiles reveal an aggregation of the dopants within the carbon-doped layers and a retarded penetration depth compared to dopant diffusion in high-purity natural Ge. Dopant aggregation and diffusion retardation are strongest for Sb and similar for P and As. In addition, the shape of the dopant profiles changes for dopant concentrations in the range of 1020cm-3 mainly due to the formation of dopant-vacancy complexes, which is more significant at high concentrations. Accurate modeling of the simultaneous self-diffusion and dopant diffusion is achieved on the basis of the vacancy mechanism and additional reactions that take into account the formation of neutral carbon-vacancy-dopant and neutral dopant-vacancy complexes. The stability of these complexes is compared to theoretical calculations published recently and to additional calculations presented in Part II. The overall consistency between the experimental and theoretical results supports the stabilization of donor-vacancy complexes in Ge by the presence of carbon and the dopant deactivation via the formation of dopant-vacancy and carbon-vacancy-dopant complexes.

  6. Experimental and Estimated Rate Constants for the Reactions of Hydroxyl Radicals with Several Halocarbons

    NASA Technical Reports Server (NTRS)

    DeMore, W.B.

    1996-01-01

    Relative rate experiments are used to measure rate constants and temperature dependencies of the reactions of OH with CH3F (41), CH2FCl (31), CH2BrCl (30B1), CH2Br2 (3OB2), CHBr3 (2OB3), CF2BrCHFCl (123aBl(alpha)), and CF2ClCHCl2 (122). Rate constants for additional compounds of these types are estimated using an empirical rate constant estimation method which is based on measured rate constants for a wide range of halocarbons. The experimental data are combined with the estimated and previously reported rate constants to illustrate the effects of F, Cl, and Br substitution on OH rate constants for a series of 19 halomethanes and 25 haloethanes. Application of the estimation technique is further illustrated for some higher hydrofluorocarbons (HFCs), including CHF2CF2CF2CF2H (338pcc), CF3CHFCHFCF2CF3 (43-10mee), CF3CH2CH2CF3 (356ffa), CF3CH2CF2CH2CF3 (458mfcf), CF3CH2CHF2 (245fa), and CF3CH2CF2CH3 (365mfc). The predictions are compared with literature data for these compounds.

  7. Experimental and Theoretical Study of Thermodynamics of the Reaction of Titania and Water at High Temperatures

    NASA Technical Reports Server (NTRS)

    Nguyen, Quynhgiao N.; Myers, Dwight L.; Jacobson, Nathan S.; Opila, Elizabeth J.

    2014-01-01

    The transpiration method was used to determine the volatility of titanium dioxide (TiO2) in water vapor-containing environments at temperatures between 1473 and 1673 K. Water contents ranged from 0 to 76 mole % in oxygen or argon carrier gases for 20 to 250 hr exposure times. Results indicate that oxygen is not a key contributor to volatilization and the primary reaction for volatilization in this temperature range is: TiO2(s) + H2O(g) = TiO(OH)2(g). Data were analyzed with both the second and third law methods to extract an enthalpy and entropy of formation. The geometry and vibrational frequencies of TiO(OH)2(g) were computed using B3LYP density functional theory, and the enthalpy of formation was computed using the coupled-cluster singles and doubles method with a perturbative correction for connected triple substitutions [CCSD(T)]. Thermal functions are calculated using both a structure with bent and linear hydroxyl groups. Calculated second and third heats show closer agreement with the linear hydroxyl group, suggesting more experimental and computational spectroscopic and structural work is needed on this system.

  8. Radiation induced graft copolymerization of methyl methacrylate onto chrome-tanned pig skins

    NASA Astrophysics Data System (ADS)

    Pietrucha, K.; Pȩkala, W.; Kroh, J.

    Graft copolymerization of methyl methacrylate (MMA) onto chrome-tanned pig skins was carried out by the irradiation with 60Co ?-rays. The grafted polymethyl methacrylate (PMMA) chains were isolated by acid hydrolysis of the collagen backbone in order to characterize the graft copolymers. Proof of grafting was obtained through the detection of amino acid endgroups in the isolated grafts by reaction with ninhydrin. The grafting yield of MMA in aqueous emulsion was found to be higher than that for pure MMA and MMA in acetone. The degree of grafting increases with increasing monomer concentration in emulsion and reaches maximum at radiation dose ca 15 kGy. The yield of grafting is very high - ca 90% of monomer converts into copolymer and only 10% is converted into homopolymer. The present paper reports the physical properties of chrome-tanned pig skins after graft polymerization with MMA in emulsion. Modified leathers are more resistant against water absorption and abrasion in comparison with unmodified ones. They have more uniform structure over the whole surface, greater thickness and stiffness. The results reported seem to indicate that MMA may be used in the production of shoe upper and sole leathers. The mechanism of some of the processes occuring during radiation grafting of MMA in water emulsion on tanned leathers has been also suggested and discussed.

  9. Comparison of experimental and theoretical reaction rail currents, rail voltages, and airgap fields for the linear induction motor research vehicle

    NASA Technical Reports Server (NTRS)

    Elliott, D. G.

    1977-01-01

    Measurements of reaction rail currents, reaction rail voltages, and airgap magnetic fields in tests of the Linear Induction Motor Research Vehicle (LIMRV) were compared with theoretical calculations from the mesh/matrix theory. It was found that the rail currents and magnetic fields predicted by the theory are within 20 percent of the measured currents and fields at most motor locations in most of the runs, but differ by as much as a factor of two in some cases. The most consistent difference is a higher experimental than theoretical magnetic field near the entrance of the motor and a lower experimental than theoretical magnetic field near the exit. The observed differences between the theoretical and experimental magnetic fields and currents do not account for the differences of as much as 26 percent between the theoretical and experimental thrusts.

  10. Experimental study on controls on fluid chemistry and permeability evolution during serpentinization reactions

    NASA Astrophysics Data System (ADS)

    Farough, A.; Moore, D. E.; Lockner, D. A.; Lowell, R. P.

    2013-12-01

    Serpentinization plays a key role in hydrothermal processes and structural deformation at slow and ultraslow mid-ocean ridges, where it is commonly associated with the formation of oceanic core complexes and detachment faults. Many details of how serpentinization reactions progress at small scales and the links between the reactions and changes in permeability and stresses are poorly understood. To advance our understanding of the evolution of permeability and fluid chemistry accompanying serpentinization reactions and provide a framework for developing more realistic models at a larger scale, we performed a series of high-temperature permeability experiments on fractured solid ultramafic rock samples that reasonably simulate serpentinization in natural settings. Experimental conditions were 260°C, 50 MPa confining pressure, and 20×2 MPa pore pressure. Ultramafic rock types containing different proportions of olivine and pyroxene were tested, to investigate the effect of mineral assemblage on fluid-rock interaction and permeability. Samples were cylindrical cores of 18 mm diameter and 23 mm length that were split axially to form a well-mated tensile fracture, jacketed in a 0.5 mm thick teflon liner and inserted into a 0.4 mm thick annealed silver jacket. A 7.5 mm thick layer of the same rock, crushed and sieved (0.18-1.0 mm size range) was placed on the inlet side of the sample to produce a coarse-grained gouge. The gouge layer provided a heated fluid reservoir with which the deionized water, used as pore fluid, could equilibrate before entering the fracture. Routinely, about 1 cm3 of water was pumped through the sample each day and collected (without dropping sample pore pressure) for chemical analysis. Pore fluid flow was in one direction and the pore pressure change and flow rate were recorded to determine permeability. In most samples, the initial fracture permeability at 260°C was between 10-15 and 10-18 m2, and decreased by about 3 orders of magnitude in

  11. Semen characteristics and reaction time of Yankasa rams experimentally infected with Trypanosoma evansi infection.

    PubMed

    Ogundele, Francis Abidemi; Okubanjo, Oluyinka Oluseyi; Ajanusi, Olagunju Joseph; Fadason, Samuel Tanko

    2016-08-01

    Trypanosomosis is a serious, often fatal disease of domestic animals and humans, and a major constraint to livestock productivity and agricultural development in areas of Africa, Latin America, the Middle East, and Asia. It is caused by hemoflagelate protozoan of the genus Trypanosoma. Several species of Trypanosoma such as Trypanosoma congolense, Trypanosoma vivax, Trypanosoma brucei, and Trypanosoma evansi are known to infect domestic animals. Trypanosoma evansi is one of the most widespread pathogenic trypanosomes in the world causing disease known as "Surra" in animals. The effects of experimental T evansi infection on some aspects of reproduction in Yankasa rams were investigated over a 108-day period. Rams in the infected group A (n = 7) were each inoculated with 1 × 10(6) trypanosomes in 1 mL of donor blood via the jugular vein, whereas the control group B (n = 5) were administered 1 mL of normal saline. Semen volume, gross motility, live and/or dead sperm ratio, sperm morphologic abnormalities, and concentration as well as reaction time of infected and control rams were evaluated on a weekly basis. The results showed a nonsignificant (P > 0.05) decrease in semen volume and a significant (P < 0.05) decrease in concentration compared to the control rams. Reaction time showed considerable significant (P < 0.05) increase from preinfection values 26.7 ± 4.54 to 94.7 ± 7.54 seconds compared to control 32.9 ± 2.64 to 33.4 ± 4.78 seconds. Furthermore, semen gross motility for infected rams differed significantly (P < 0.05) from those of the control. There was a significant surge (P < 0.05) in the total sperm morphologic abnormalities in the infected rams to 90.75 ± 2.73% by week 20 (14 weeks after infection), compared to preinfection value of 20.9 ± 0.52%. The outcome of this study suggests that infection with T evansi in Yankasa rams has far reaching severe effects on their reproductive performance.

  12. Semen characteristics and reaction time of Yankasa rams experimentally infected with Trypanosoma evansi infection.

    PubMed

    Ogundele, Francis Abidemi; Okubanjo, Oluyinka Oluseyi; Ajanusi, Olagunju Joseph; Fadason, Samuel Tanko

    2016-08-01

    Trypanosomosis is a serious, often fatal disease of domestic animals and humans, and a major constraint to livestock productivity and agricultural development in areas of Africa, Latin America, the Middle East, and Asia. It is caused by hemoflagelate protozoan of the genus Trypanosoma. Several species of Trypanosoma such as Trypanosoma congolense, Trypanosoma vivax, Trypanosoma brucei, and Trypanosoma evansi are known to infect domestic animals. Trypanosoma evansi is one of the most widespread pathogenic trypanosomes in the world causing disease known as "Surra" in animals. The effects of experimental T evansi infection on some aspects of reproduction in Yankasa rams were investigated over a 108-day period. Rams in the infected group A (n = 7) were each inoculated with 1 × 10(6) trypanosomes in 1 mL of donor blood via the jugular vein, whereas the control group B (n = 5) were administered 1 mL of normal saline. Semen volume, gross motility, live and/or dead sperm ratio, sperm morphologic abnormalities, and concentration as well as reaction time of infected and control rams were evaluated on a weekly basis. The results showed a nonsignificant (P > 0.05) decrease in semen volume and a significant (P < 0.05) decrease in concentration compared to the control rams. Reaction time showed considerable significant (P < 0.05) increase from preinfection values 26.7 ± 4.54 to 94.7 ± 7.54 seconds compared to control 32.9 ± 2.64 to 33.4 ± 4.78 seconds. Furthermore, semen gross motility for infected rams differed significantly (P < 0.05) from those of the control. There was a significant surge (P < 0.05) in the total sperm morphologic abnormalities in the infected rams to 90.75 ± 2.73% by week 20 (14 weeks after infection), compared to preinfection value of 20.9 ± 0.52%. The outcome of this study suggests that infection with T evansi in Yankasa rams has far reaching severe effects on their reproductive performance. PMID:27188633

  13. Synthesis of α(1→4)-linked non-natural mannoglucans by α-glucan phosphorylase-catalyzed enzymatic copolymerization.

    PubMed

    Baba, Ryotaro; Yamamoto, Kazuya; Kadokawa, Jun-Ichi

    2016-10-20

    α-Glucan phosphorylase catalyzes enzymatic polymerization of α-d-glucose 1-phosphate (Glc-1-P) as a monomer from a maltooligosaccharide primer to produce α(1→4)-glucan, i.e., amylose, with liberating inorganic phosphate (Pi). Because of quite weak specificity for the recognition of substrates by thermostable α-glucan phosphorylase (from Aquifex aeolicus VF5), in this study, we investigated the enzymatic copolymerization of Glc-1-P with its analogue monomer, α-d-mannose 1-phosphate (Man-1-P) under the conditions for removal of Pi as the precipitate with ammonium and magnesium in ammonia buffer containing Mg(2+) ion to produce α(1→4)-linked non-natural mannoglucans composed of Glc/Man units. The reaction was conducted in different feed ratios using the maltotriose primer at 40°C for 7days. The MALDI-TOF mass and (1)H NMR spectra of the products fully supported the mannoglucan structures.

  14. Temperature trends for reaction rates, hydrogen generation, and partitioning of iron during experimental serpentinization of olivine

    NASA Astrophysics Data System (ADS)

    McCollom, Thomas M.; Klein, Frieder; Robbins, Mark; Moskowitz, Bruce; Berquó, Thelma S.; Jöns, Niels; Bach, Wolfgang; Templeton, Alexis

    2016-05-01

    A series of laboratory experiments were conducted to examine how partitioning of Fe among solid reaction products and rates of H2 generation vary as a function of temperature during serpentinization of olivine. Individual experiments were conducted at temperatures ranging from 200 to 320 °C, with reaction times spanning a few days to over a year. The extent of reaction ranged from <1% to ∼23%. Inferred rates for serpentinization of olivine during the experiments were 50-80 times slower than older studies had reported but are consistent with more recent results, indicating that serpentinization may proceed more slowly than previously thought. Reaction products were dominated by chrysotile, brucite, and magnetite, with minor amounts of magnesite, dolomite, and iowaite. The chrysotile contained only small amounts of Fe (XFe = 0.03-0.05, with ∼25% present as ferric Fe in octahedral sites), and displayed little variation in composition with reaction temperature. Conversely, the Fe contents of brucite (XFe = 0.01-0.09) increased steadily with decreasing reaction temperature. Analysis of the reaction products indicated that the stoichiometry of the serpentinization reactions varied with temperature, but remained constant with increasing reaction progress at a given temperature. The observed distribution of Fe among the reaction products does not appear to be entirely consistent with existing equilibrium models of Fe partitioning during serpentinization, suggesting improved models that include kinetic factors or multiple reaction steps need to be developed. Rates of H2 generation increased steeply from 200 to 300 °C, but dropped off at higher temperatures. This trend in H2 generation rates is attributable to a combination of the overall rate of serpentinization reactions and increased partitioning of Fe into brucite rather than magnetite at lower temperatures. The results suggest that millimolal concentration of H2 could be attained in moderately hot hydrothermal

  15. Population of high spin states in very heavy ion transfer reactions. The experimental evidence

    SciTech Connect

    Guidry, M.W.

    1985-01-01

    Transfer reactions have been studied for some time with light heavy ions such as oxygen. Although states of spin I approx.10 h are sometimes populated in such reactions, it is assumed that collective excitation is small, and the transferred particles are responsible for the angular momentum transfer. In this paper we will discuss a qualitatively different kind of transfer reaction using very heavy ions (A greater than or equal to 40). In these reactions the collective excitation in both the entrance and exit channels is strong, and there may be appreciable angular momentum transfer associated with inelastic excitation. 12 refs., 13 figs.

  16. Palladium(II)-catalyzed copolymerization of styrenes with carbon monoxide: mechanism of chain propagation and chain transfer.

    PubMed

    Rix, Francis C; Rachita, Michael J; Wagner, Mark I; Brookhart, Maurice; Milani, Barbara; Barborak, James C

    2009-11-01

    A mechanistic interpretation of the [(1,10-phenanthroline)Pd(CH(3))(CH(3)CN)](+)[BArF](-) (1a) and [(2,2'-bipyridine)Pd(CH(3))(CH(3)CN)](+)[BArF](-) (1b) (BArF = 3,5-(CF(3))(2)-C(6)H(3)) catalyzed perfectly alternating copolymerization of styrenes with CO is reported. The copolymerization in CH(2)Cl(2) or chlorobenzene has been found to be first order in styrene and inverse first order in CO concentrations. The microscopic steps involved in the catalytic cycle have been studied via low temperature NMR techniques. Palladium alkyl chelate complex [(2,2'-bipyridine)Pd(CHArCH(2)C(O)CH(3)](+)[BArF](-) (5b sigma) and [(2,2'-bipyridine)Pd(eta(3)-CH(CH(2)C(O)CH(3))Ar)](+)[BArF](-) (5b pi), existing in equilibrium, were prepared. Treatment of 5b sigma,pi with (13)CO followed by 4-tert-butylstyrene at -78 degrees C allowed for (13)C NMR monitoring of the alternating chain growth of a series of palladium acyl carbonyl complexes. The acyl carbonyl species, representing the catalyst resting state, is in equilibrium with a palladium acyl styrene complex. The equilibrium constant, K(4), measured between [(phen)Pd(CO)(C(O)CH(3)](+)[BArF](-) (3a) and [(phen)Pd(C(O)CH(3))-(C(6)H(5)C=CH(2))](+)[BArF](-) (8a), was determined to be 2.84 +/- 2.8 x 10(-7) at -66 degrees C. The barrier to migratory insertion in 8a was determined (DeltaG(double dagger) (-66 degrees C) = 15.6 +/- 0.1 kcal mol(-1)). From the experimentally determined kinetic and thermodynamic data for the copolymerization of styrene with CO a mechanistic model has been constructed. The ability of this model to predict catalyst turnover frequency (TOF) was used as a test of its validity. A series of para-substituted styrenes, p-XC(6)H(4)CH=CH(2) (X = -OCH(3), -CH(3), -H, -Cl), were copolymerized with CO. A Hammett treatment of TOF for the series showed that electron-donating groups increase the rate of copolymerization (rho p = -0.8). The ratio of chain transfer to chain propagation was found to increase with styrene

  17. Clickable degradable aliphatic polyesters via copolymerization with alkyne epoxy esters: synthesis and postfunctionalization with organic dyes.

    PubMed

    Teske, Nele S; Voigt, Julia; Shastri, V Prasad

    2014-07-23

    Degradable aliphatic polyesters are the cornerstones of nanoparticle (NP)-based therapeutics. In this paradigm, covalent modification of the NP with cell-targeting motifs and dyes can aid in guiding the NP to its destination and gaining visual confirmation. Therefore, strategies to impart chemistries along the polymer backbone that are amenable to easy modification, such as 1,3-dipolar cycloaddition of an azide to an alkyne (the "click reaction"), could be significant. Here we present a simple and efficient way to introduce alkyne groups at high density in aliphatic polyesters without compromising their crystallinity via the copolymerization of cyclic lactones with propargyl 3-methylpentenoate oxide (PMPO). Copolymers of lactic acid and ε-caprolactone with PMPO were synthesized with up to 9 mol % alkyne content, and accessibility of the alkyne groups to the click reaction was demonstrated using several dyes commonly employed in fluorescence microscopy and imaging (Cy3, ATTO-740, and coumarin 343). In order to establish the suitability of these copolymers as nanocarriers, copolymers were formulated into NPs, and cytocompatibility, cellular uptake, and visualization studies undertaken in HeLa cells. Dye-modified NPs exhibited no quenching, remained stable in solution for at least 10 days, showed no cytotoxicity, and were readily taken up by HeLa cells. Furthermore, in addition to enabling the incorporation of multiple fluorophores within the same NP through blending of individual dye-modified copolymers, dye-modified polyesters offer advantages over physical entrapment of dye, including improved signal to noise ratio and localization of the fluorescence signal within cells, and possess the necessary prerequisites for drug delivery and imaging.

  18. Experimental probe for the production of 97Ru from the 7Li+93Nb reaction: A study of precompound emissions

    NASA Astrophysics Data System (ADS)

    Kumar, Deepak; Maiti, Moumita; Lahiri, Susanta

    2016-10-01

    Background: Interaction of weakly bound heavy ions with an intermediate or heavy target is not yet understood completely due to the scarcity of experimental data. In order to develop a clear understanding of breakup fusion or preequilibrium emission even in the low energy range, 3-10 MeV/nucleon, more experimental investigations are necessary. Purpose: We aim to study the reaction mechanisms involved in the weakly bound heavy-ion induced reaction 7Li+93Nb at low energies by measuring the production cross sections of the residual radionuclides. Method: Natural niobium (93Nb) foil, backed by an aluminum (Al) catcher, arranged in a stack was bombarded by 7Li ions of 20-45 MeV energy. Activity of the residues produced in each 93Nb target was measured by off line γ -ray spectrometry after the end of bombardment (EOB) and cross sections were calculated. Experimental cross sections were compared with those computed using compound and precompound models. Results: In general, measured excitation functions of all residues produced in the 7Li+93Nb reaction showed good agreement with the model calculations based on the Hauser-Feshbach formalism and the exciton model for compound and precompound processes, respectively. Significant preequilibrium emission of neutrons was observed at the relatively high energy tail of the excitation function of 97Ru. Conclusions: Preequilibrium processes played an important role in the enhancement of the cross section in the x n reaction channel over the compound reaction mechanism at higher energies for the 7Li+93Nb reaction. Additionally, indirect evidence of incomplete or breakup fusion was also perceived.

  19. Rate coefficients for the reaction of OH radicals with cis-3-hexene: an experimental and theoretical study.

    PubMed

    Barbosa, Thaís da Silva; Peirone, Silvina; Barrera, Javier A; Abrate, Juan P A; Lane, Silvia I; Arbilla, Graciela; Bauerfeldt, Glauco Favilla

    2015-04-14

    The kinetics of the cis-3-hexene + OH reaction were investigated by an experimental relative rate method and at the density functional theory level. The experimental set-up consisted of a 200 L Teflon bag, operated at atmospheric pressure and 298 K. OH radicals were produced by the photolysis of H2O2 at 254 nm. Relative rate coefficients were determined by comparing the decays of the cis-3-hexene and reference compounds (cyclohexene, 2-buten-1-ol and allyl ether). The mean second-order rate coefficient value found was (6.27 ± 0.66) × 10(-11) cm(3) molecule(-1) s(-1), the uncertainty being estimated by propagation of errors. Theoretical calculations for the addition reaction of OH to cis-3-hexene have also been performed, at the BHandHLYP/aug-cc-pVDZ level, in order to investigate the reaction mechanism, to clarify the experimental observations and to model the reaction kinetics. Different conformations of the reactants, pre-barrier complexes and saddle points were considered in our calculations. The individual rate coefficients, calculated for each conformer of the reactant, at 298 K, using a microcanonical variational transition state method, are 4.19 × 10(-11) and 1.23 × 10(-10) cm(3) molecule(-1) s(-1). The global rate coefficient was estimated from the Boltzmann distribution of the conformers to be 8.10 × 10(-11) cm(3) molecule(-1) s(-1), which is in agreement with the experimental value. Rate coefficients calculated over the temperature range from 200-500 K are also given. Our results suggest that the complex mechanism, explicitly considering different conformations for the stationary points, must be taken into account for a proper description of the reaction kinetics.

  20. Experimental study of exclusive $^2$H$(e,e^\\prime p)n$ reaction mechanisms at high $Q^2$

    SciTech Connect

    Kim Egiyan; Gegham Asryan; Nerses Gevorgyan; Keith Griffioen; Jean Laget; Sebastian Kuhn; Gary Adams; Moscov Amaryan; Pawel Ambrozewicz; Marco Anghinolfi; Gerard Audit; Harutyun AVAKIAN; Harutyun Avakian; Hovhannes Baghdasaryan; Nathan Baillie; Jacques Ball; Nathan Baltzell; Steve Barrow; Vitaly Baturin; Marco Battaglieri; Ivan Bedlinski; Ivan Bedlinskiy; Mehmet Bektasoglu; Matthew Bellis; Nawal Benmouna; Barry Berman; Angela Biselli; Lukasz Blaszczyk; Sylvain Bouchigny; Sergey Boyarinov; Robert Bradford; Derek Branford; William Briscoe; William Brooks; Stephen Bueltmann; Volker Burkert; Cornel Butuceanu; John Calarco; Sharon Careccia; Daniel Carman; Antoine Cazes; Shifeng Chen; Philip Cole; Patrick Collins; Philip Coltharp; Dieter Cords; Pietro Corvisiero; Donald Crabb; Volker Crede; John Cummings; Natalya Dashyan; Rita De Masi; Raffaella De Vita; Enzo De Sanctis; Pavel Degtiarenko; Haluk Denizli; Lawrence Dennis; Alexandre Deur; Kahanawita Dharmawardane; Richard Dickson; Chaden Djalali; Gail Dodge; Joseph Donnelly; David Doughty; Michael Dugger; Steven Dytman; Oleksandr Dzyubak; Hovanes Egiyan; Lamiaa Elfassi; Latifa Elouadrhiri; Paul Eugenio; Renee Fatemi; Gleb Fedotov; Gerald Feldman; Robert Feuerbach; Robert Fersch; Michel Garcon; Gagik Gavalian; Gerard Gilfoyle; Kevin Giovanetti; Francois-Xavier Girod; John Goetz; Atilla Gonenc; Christopher Gordon; Ralf Gothe; Michel Guidal; Matthieu Guillo; Hayko Guler; Lei Guo; Vardan Gyurjyan; Cynthia Hadjidakis; Kawtar Hafidi; Hayk Hakobyan; Rafael Hakobyan; Charles Hanretty; John Hardie; F. Hersman; Kenneth Hicks; Ishaq Hleiqawi; Maurik Holtrop; Charles Hyde-Wright; Yordanka Ilieva; David Ireland; Boris Ishkhanov; Eugeny Isupov; Mark Ito; David Jenkins; Hyon-Suk Jo; Kyungseon Joo; Henry Juengst; Narbe Kalantarians; James Kellie; Mahbubul Khandaker; Wooyoung Kim; Andreas Klein; Franz Klein; Alexei Klimenko; Mikhail Kossov; Zebulun Krahn; Laird Kramer; V. Kubarovsky; Joachim Kuhn; Sergey Kuleshov; Jeff Lachniet; Jorn Langheinrich; David Lawrence; Ji Li; Kenneth Livingston; Haiyun Lu; Marion MacCormick; Claude Marchand; Nikolai Markov; Paul Mattione; Simeon McAleer; Bryan McKinnon; John McNabb; Bernhard Mecking; Surik Mehrabyan; Joseph Melone; Mac Mestayer; Curtis Meyer; Tsutomu Mibe; Konstantin Mikhaylov; Ralph Minehart; Marco Mirazita; Rory Miskimen; Viktor Mokeev; Kei Moriya; Steven Morrow; Maryam Moteabbed; James Mueller; Edwin Munevar Espitia; Gordon Mutchler; Pawel Nadel-Turonski; Rakhsha Nasseripour; Silvia Niccolai; Gabriel Niculescu; Maria-Ioana Niculescu; Bogdan Niczyporuk; Megh Niroula; Rustam Niyazov; Mina Nozar; Grant O'Rielly; Mikhail Osipenko; Alexander Ostrovidov; Kijun Park; Evgueni Pasyuk; Craig Paterson; Sergio Pereira; Joshua Pierce; Nikolay Pivnyuk; Dinko Pocanic; Oleg Pogorelko; Sergey Pozdnyakov; Barry Preedom; John Price; Yelena Prok; Dan Protopopescu; Brian Raue; Gregory Riccardi; Giovanni Ricco; Marco Ripani; Barry Ritchie; Federico Ronchetti; Guenther Rosner; Patrizia Rossi; Franck Sabatie; Julian Salamanca; Carlos Salgado; Joseph Santoro; Vladimir Sapunenko; Reinhard Schumacher; Vladimir Serov; Youri Sharabian; Nikolay Shvedunov; Alexander Skabelin; Elton Smith; Lee Smith; Daniel Sober; Daria Sokhan; Aleksey Stavinskiy; Samuel Stepanyan; Stepan Stepanyan; Burnham Stokes; Paul Stoler; Steffen Strauch; Mauro Taiuti; David Tedeschi; Ulrike Thoma; Avtandil Tkabladze; Svyatoslav Tkachenko; Luminita Todor; Clarisse Tur; Maurizio Ungaro; Michael Vineyard; Alexander Vlassov; Daniel Watts; Lawrence Weinstein; Dennis Weygand; M. Williams; Elliott Wolin; Michael Wood; Amrit Yegneswaran; Lorenzo Zana; Jixie Zhang; Bo Zhao; Zhiwen Zhao

    2007-06-01

    The reaction {sup 2}H(e,e{prime} p)n has been studied with full kinematic coverage for photon virtuality 1.75 < 5.5 {approx} GeV{sup 2}. Comparisons of experimental data with theory indicate that for very low values of neutron recoil momentum (p{sub n} < 100 MeV/c) the neutron is primarily a spectator and the reaction can be described by the plane-wave impulse approximation. For 100 < 750 MeV/c proton-neutron rescattering dominates the cross section, while {Delta} production followed by the N{Delta} {yields} NN transition is the primary contribution at higher momenta.

  1. An experimental study of enstatite formation reaction between forsterite and Si-rich gas

    NASA Astrophysics Data System (ADS)

    Imae, Naoya; Tsuchiyama, Akira; Kitamura, Masao

    1993-07-01

    Experiments on the reaction between forsterite and Si-rich gas were carried out in a vacuum furnace, using a newly designed double-capsule technique. A thin layer of enstatite was formed on the surface of the forsterite by the reaction. The thickness of the enstatite layer changes in proportion to the square root of time (parabolic rate law), indicating that the rate is controlled by diffusion in the enstatite layer. The activation energy and the logarithm of the preexponential term of the parabolic rate constant were obtained at 505 +/- 188 kJ/mol and 3.6 +/- 5.6 sq cm/s, respectively. It is difficult to definitely determine the mechanism of the reaction from these values, but consideration of strain generation due to the volume change during the reaction may suggest that the counterdiffusion of Si and Mg takes place along the grain boundary in the enstatite layer. The degree of the reaction of forsterite with Si-rich residual gas in the primordial solar nebula is discussed based upon the measured reaction rate, and it is suggested that very little enstatite was formed by this reaction in the cooling nebula if the grain size of the forsterite crystals was controlled by homogeneous nucleation theory.

  2. Experimental study of the 13C+12C fusion reaction at deep sub-barrier energies

    NASA Astrophysics Data System (ADS)

    Tudor, D.; Chilug, A. I.; Straticiuc, M.; Trache, L.; Chesneanu, D.; Toma, S.; Ghita, D. G.; Burducea, I.; Margineanu, R.; Pantelica, A.; Gomoiu, C.; Zhang, N. T.; Tang, X.; Li, Y. J.

    2016-04-01

    Heavy-ion fusion reactions between light nuclei such as carbon and oxygen isotopes have been studied because of their significance for a wide variety of stellar burning scenarios. One important stellar reaction is 12C+12C, but it is difficult to measure it in the Gamow window because of very low cross sections and several resonances occurring. Hints can be obtained from the study of 13C+12C reaction. We have measured this process by an activation method for energies down to Ecm=2.5 MeV using 13C beams from the Bucharest 3 MV tandetron and gamma-ray deactivation measurements in our low and ultralow background laboratories, the latter located in a salt mine about 100 km north of Bucharest. Results obtained so far are shown and discussed in connection with the possibility to go even further down in energy and with the interpretation of the reaction mechanism at such deep sub-barrier energies.

  3. Mononuclear nonheme iron(IV)-oxo and manganese(IV)-oxo complexes in oxidation reactions: experimental results prove theoretical prediction.

    PubMed

    Chen, Junying; Cho, Kyung-Bin; Lee, Yong-Min; Kwon, Yoon Hye; Nam, Wonwoo

    2015-08-25

    Reactivities of mononuclear nonheme iron(IV)-oxo and manganese(IV)-oxo complexes bearing a pentadentate N4Py ligand, [M(IV)O(N4Py)](2+) (M = Fe and Mn), are compared in hydrogen atom transfer (HAT) and oxygen atom transfer (OAT) reactions; theoretical and experimental results show that Fe(IV)O is more reactive than Mn(IV)O. The latter is shown to react through excited state reactivity (ESR).

  4. Experimental Observation of Nuclear Reactions in Palladium and Uranium - Possible Explanation by Hydrex Mode

    SciTech Connect

    Dufour, J.; Murat, D.; Dufour, X.; Foos, J

    2001-07-15

    Experiments with uranium are presented that show a highly exothermal reaction, which can only be of nuclear origin. One striking point of these results is that they clearly show that what is being observed is not some kind of fusion reaction of the deuterium present (only exceedingly small amounts of it are present). This is a strong indication that hydrogen can trigger nuclear reactions that seem to involve the nuclei of the lattice (which would yield a fission-like pattern of products). Confronted with a situation where some experiments in the field yield a fusion-like pattern of products (CF experiments) and others a fissionlike one (LENR experiments), one can reasonably wonder whether one is not observing two aspects of the same phenomenon. Thus, it is proposed to describe CF and LENR reactions as essentially the same phenomenon based on the possible existence of a still hypothetical proton/electron resonance, which would catalyze fissionlike reactions with a neutron sink. Finally, a series of experiments is proposed to assess this hypothesis.

  5. Fusion reactions and experimental approaches to the synthesis of superheavy nuclei

    SciTech Connect

    Yeremin, A. V.; Utyonkov, V. K.; Oganessian, Yu. Ts.

    1998-02-15

    The question whether the asymmetric actinide based heavy ion reactions could be used for the synthesis of heavy (Z{>=}106) nuclides is essential from the point of view of the study of limitation on fusion, it is also important in such reactions new nuclides close to the magic number N=162 can be produced. Thus as the problem of a hindrance to fusion still remains unsolved the high excitation energy of the compound nucleus looks to be an obvious obstacle to using these reactions. Using the gas-filled recoil separator and electrostatic recoil separator VAS-SILISSA installed at the beam lines of the U-400 heavy ion cyclotron of the FLNR JINR we investigated the fusion reactions leading to 102, 103, 104, 105 and heaviest isotopes of the 106, 108 and 110 elements. The analysis of the measured cross-sections did not reveal any evidence of a hindrance to fusion at the ion bombarding energy close to the Coulomb barrier. {sup 48}Ca+{sup 232}Th{yields}{sup 280}110*, {sup 48}Ca+{sup 238}U{yields}{sup 286}112*, {sup 48}Ca+{sup 244}Pu{yields}{sup 292}114* appear to be the best reactions from the point of view of their cross-sections.

  6. Experimental setup and procedure for the measurement of the 7Be(n,α)α reaction at n_TOF

    NASA Astrophysics Data System (ADS)

    Cosentino, L.; Musumarra, A.; Barbagallo, M.; Pappalardo, A.; Colonna, N.; Damone, L.; Piscopo, M.; Finocchiaro, P.; Maugeri, E.; Heinitz, S.; Schumann, D.; Dressler, R.; Kivel, N.; Aberle, O.; Andrzejewski, J.; Audouin, L.; Ayranov, M.; Bacak, M.; Barros, S.; Balibrea-Correa, J.; Bécares, V.; Bečvář, F.; Beinrucker, C.; Berthoumieux, E.; Billowes, J.; Bosnar, D.; Brugger, M.; Caamaño, M.; Calviani, M.; Calviño, F.; Cano-Ott, D.; Cardella, R.; Casanovas, A.; Castelluccio, D. M.; Cerutti, F.; Chen, Y. H.; Chiaveri, E.; Cortés, G.; Cortés-Giraldo, M. A.; Diakaki, M.; Domingo-Pardo, C.; Dupont, E.; Duran, I.; Fernandez-Dominguez, B.; Ferrari, A.; Ferreira, P.; Furman, W.; Ganesan, S.; García-Rios, A.; Gawlik, A.; Gheorghe, I.; Glodariu, T.; Göbel, K.; Gonc̗alves, I. F.; González-Romero, E.; Griesmayer, E.; Guerrero, C.; Gunsing, F.; Harada, H.; Heftrich, T.; Heyse, J.; Jenkins, D. G.; Jericha, E.; Käppeler, F.; Katabuchi, T.; Kavrigin, P.; Kimura, A.; Kokkoris, M.; Krtička, M.; Leal-Cidoncha, E.; Lerendegui, J.; Lederer, C.; Leeb, H.; Meo, S. Lo; Lonsdale, S.; Losito, R.; Macina, D.; Marganiec, J.; Martínez, T.; Massimi, C.; Mastinu, P.; Mastromarco, M.; Matteucci, F.; Mazzone, A.; Mendoza, E.; Mengoni, A.; Milazzo, P. M.; Mingrone, F.; Mirea, M.; Montesano, S.; Nolte, R.; Oprea, A.; Patronis, N.; Pavlik, A.; Perkowski, J.; Praena, J.; Quesada, J.; Rajeev, K.; Rauscher, T.; Reifarth, R.; Riego-Perez, A.; Rout, P.; Rubbia, C.; Ryan, J.; Sabate-Gilarte, M.; Saxena, A.; Schillebeeckx, P.; Schmidt, S.; Sedyshev, P.; Smith, A. G.; Stamatopoulos, A.; Tagliente, G.; Tain, J. L.; Tarifeño-Saldivia, A.; Tassan-Got, L.; Tsinganis, A.; Valenta, S.; Vannini, G.; Variale, V.; Vaz, P.; Ventura, A.; Vlachoudis, V.; Vlastou, R.; Vollaire, J.; Wallner, A.; Warren, S.; Weigand, M.; Weiß, C.; Wolf, C.; Woods, P. J.; Wright, T.; Z̆ugec, P.

    2016-09-01

    The newly built second experimental area EAR2 of the n_TOF spallation neutron source at CERN allows to perform (n, charged particles) experiments on short-lived highly radioactive targets. This paper describes a detection apparatus and the experimental procedure for the determination of the cross-section of the 7Be(n,α)α reaction, which represents one of the focal points toward the solution of the cosmological Lithium abundance problem, and whose only measurement, at thermal energy, dates back to 1963. The apparently unsurmountable experimental difficulties stemming from the huge 7Be γ-activity, along with the lack of a suitable neutron beam facility, had so far prevented further measurements. The detection system is subject to considerable radiation damage, but is capable of disentangling the rare reaction signals from the very high background. This newly developed setup could likely be useful also to study other challenging reactions requiring the detectors to be installed directly in the neutron beam.

  7. An experimental study of tissue reaction to hyaluronic acid (Restylane) and polymethylmethacrylate (Metacrill) in the mouse.

    PubMed

    Rosa, Simone C; Macedo, Jefferson L S; Magalhães, Albino V

    2012-10-01

    The aging skin is a challenge for medical science. Plastic surgeons and dermatologists are called every day to solve problems like filling wrinkles or folds. The material used must be biocompatible because abnormal reactions may cause catastrophic results. This study analyzes the biological behavior of polymethylmethacrylate (Metacrill) and hyaluronic acid (Restylane), using a histopathologic study in mice. A prospective study was performed using 40 mice for each substance: polymethylmethacrylate or hyaluronic acid was injected into the right ear, the left ear been used as a control. Histopathologic analyses of the right ear, liver, and kidney were performed at intervals during the study and revealed the development of a granulomatous reaction with fibrosis and absorption of spheres and signs of liver and kidney sistematization for polymethylmethacrylate. A discrete cellular reaction, with less formation of fibrosis, and no giant cells were seen in the mice injected with hyaluronic acid.

  8. Mechanism for the uncatalyzed cyclic acetone-peroxide formation reaction: an experimental and computational study.

    PubMed

    Espinosa-Fuentes, Eduardo A; Pacheco-Londoño, Leonardo C; Hidalgo-Santiago, Migdalia; Moreno, Martha; Vivas-Reyes, Ricardo; Hernández-Rivera, Samuel P

    2013-10-17

    In this study, a mechanism for the uncatalyzed reaction between acetone and hydrogen peroxide is postulated. The reaction leads to the formation of the important homemade explosives collectively known as cyclic acetone peroxides (CAP). The proposed mechanistic scheme is based on Raman, GC-MS, and nuclear magnetic resonance measurements, and it is supported by ab initio density functional theory (DFT) calculations. The results demonstrate that the proposed mechanism for the uncatalyzed formation reaction of CAP occurs in three steps: monomer formation, polymerization of the 2-hydroperoxipropan-2-ol monomer, and cyclization. The temporal decay of the intensities of important assigned-bands is in excellent agreement with the proposed mechanism. Previous reports also confirm that the polymerization step is favored in comparison to other possible pathways.

  9. Experimental and computational investigation on the gas phase reaction of p-cymene with Cl atoms.

    PubMed

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

    2015-01-29

    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.

  10. Experimental study of the reactions of limonene with OH and OD radicals: kinetics and products.

    PubMed

    Braure, Tristan; Bedjanian, Yuri; Romanias, Manolis N; Morin, Julien; Riffault, Véronique; Tomas, Alexandre; Coddeville, Patrice

    2014-10-01

    The kinetics of the reactions of limonene with OH and OD radicals has been studied using a low-pressure flow tube reactor coupled with a quadrupole mass spectrometer: OH + C10H16 → products (1), OD + C10H16 → products (2). The rate constants of the title reactions were determined using four different approaches: either monitoring the kinetics of OH (OD) radicals or limonene consumption in excess of limonene or of the radicals, respectively (absolute method), and by the relative rate method using either the reaction OH (OD) + Br2 or OH (OD) + DMDS (dimethyl disulfide) as the reference one and following HOBr (DOBr) formation or DMDS and limonene consumption, respectively. As a result of the absolute and relative measurements, the overall rate coefficients, k1 = (3.0 ± 0.5) × 10(-11) exp((515 ± 50)/T) and k2 = (2.5 ± 0.6) × 10(-11) exp((575 ± 60)/T) cm(3) molecule(-1) s(-1), were determined at a pressure of 1 Torr of helium over the temperature ranges 220-360 and 233-353 K, respectively. k1 was found to be pressure independent over the range 0.5-5 Torr. There are two possible pathways for the reaction between OH (OD) and limonene: addition of the radical to one of the limonene double bonds (reactions 1a and 2a ) and abstraction of a hydrogen atom (reactions 1b and 2b ), resulting in the formation of H2O (HOD). Measurements of the HOD yield as a function of temperature led to the following branching ratio of the H atom abstraction channel: k2b/k2 = (0.07 ± 0.03) × exp((460 ± 140)/T) for T = (253-355) K.

  11. Experimental Studies of Hydrogenation and Other Reactions on Surfaces Under Astrophysically Relevant Conditions

    NASA Technical Reports Server (NTRS)

    Vidali, Gianfranco

    1998-01-01

    The goal of our project is to study hydrogen recombination reactions on solid surfaces under conditions that are relevant in astrophysics. Laboratory experiments were conducted using low-flux, cold atomic H and D beams impinging on a sample kept under ultra high vacuum conditions. Realistic analogues of interstellar dust grains were used. Our results show that current models for hydrogen recombination reactions have to be modified to take into account the role of activated diffusion of H on surfaces even at low temperature.

  12. Experimental and theoretical analysis of the kinetics of the reaction of atomic bromine with 1,4-dioxane.

    PubMed

    Giri, Binod Raj; Roscoe, John M; González-García, Núria; Olzmann, Matthias

    2010-01-14

    The rate coefficient for the reaction of atomic bromine with 1,4-dioxane was measured from approximately 300 to 340 K using the relative rate method. Iso-octane and iso-butane were used as reference compounds, and the experiments were made in a bath of argon containing up to 210 Torr of O(2) at total pressures between 200 and 820 Torr. The rate coefficients were not affected by changes in pressure or O(2) concentration over our range of experimental conditions. The ratios of rate coefficients for the reaction of dioxane relative to the reference compound were put on an absolute basis by using the published absolute rate coefficients for the reference reactions. The variation of the experimentally determined rate coefficients with temperature for the reaction of Br with 1,4-dioxane can be given by k(1)(exp)(T) = (1.4 +/- 1.0) x 10(-11)exp[-23.0 +/- 1.8) kJ mol(-1)/(RT)] cm(3) molecule(-1) s(-1). We rationalized our experimental results in terms of transition state theory with molecular data from quantum chemical calculations. Molecular geometries and frequencies were obtained from MP2/aug-cc-pVDZ calculations, and single-point energies of the stationary points were obtained at CCSD(T)/CBS level of theory. The calculations indicate that the 1,4-dioxane + Br reaction proceeds in an overall endothermic addition-elimination mechanism via a number of intermediates. The rate-determining step is a chair-to-boat conformational change of the Br-dioxane adduct. The calculated rate coefficients, given by k(1)(calc)(T) = 5.6 x 10(-11)exp[-26.6 kJ mol(-1)/(RT)] cm(3) molecule(-1) s(-1), are in very good agreement with the experimental values. Comparison with results reported for the reactions of Br with other ethers suggests that this multistep mechanism differs significantly from that for abstraction of hydrogen from other ethers by atomic bromine. PMID:19848396

  13. Experimental studies on the reaction kinetics of 1,1-dimethylhydrazine and oxygen

    NASA Technical Reports Server (NTRS)

    Just, T.

    1985-01-01

    Measurements behind shock waves in highly diluted 1,1 dimethylhydrazine-O2-Ar mixtures clearly showed a two-stage reaction. In the first stage, UDMH decomposes via a unimolecular step; in the second stage, clearly separated from the first one, the decay products react further with O2. Values for the rate constant of unimolecular decomposition were obtained.

  14. Determination of the Molar Volume of Hydrogen from the Metal-Acid Reaction: An Experimental Alternative.

    ERIC Educational Resources Information Center

    de Berg, Kevin; Chapman, Ken

    1996-01-01

    Describes an alternative technique for determining the molar volume of hydrogen from the metal-acid reaction in which the metal sample is encased in a specially prepared cage and a pipette filler is used to fill an inverted burette with water. Eliminates some difficulties encountered with the conventional technique. (JRH)

  15. Lipase-catalyzed copolymerization of dialkyl carbonate with 1,4-butanediol and ω-pentadecalactone: synthesis of poly(ω-pentadecalactone-co-butylene-co-carbonate).

    PubMed

    Jiang, Zhaozhong

    2011-05-01

    Candida antarctica lipase B (CALB) was successfully used to promote synthesis of aliphatic poly(carbonate-co-ester) copolymers from dialkyl carbonate, diol, and lactone monomers. The polymerization reactions were carried out in two stages: first-stage oligomerization under low vacuum, followed by second-stage polymerization under high vacuum. Therefore, copolymerization of ω-pentadecalactone (PDL), diethyl carbonate (DEC), and 1,4-butanediol (BD) yielded PDL-DEC-BD copolymers with a M(w) of whole product (nonfractionated) up to 33 000 and M(w)/M(n) between 1.2 and 2.3. Desirable reaction temperature for the copolymerization was found to be ∼80 °C. The copolymer compositions, in the range from 10 to 80 mol % PDL unit content versus total (PDL + carbonate) units, were effectively controlled by adjusting the monomer feed ratio. Reprecipitation in chloroform/methanol mixture allowed isolation of the purified copolymers in up to 92% yield. (1)H and (13)C NMR analyses, including statistical analysis on repeat unit sequence distribution, were used to determine the polymer microstructures. The synthesized PDL-DEC-BD copolymers possessed near random structures with all possible combinations of PDL, carbonate, and butylene units via either ester or carbonate linkages in the polymer chains and are more appropriately named as poly(PDL-co-butylene-co-carbonate).

  16. Experimental Constraints on Fluid-Rock Reactions during Incipient Serpentinization of Harzburgite

    NASA Astrophysics Data System (ADS)

    Klein, F.; Grozeva, N. G.; Seewald, J.; McCollom, T. M.; Humphris, S. E.; Moskowitz, B. M.; Berquo, T. S.; Kahl, W. A.

    2014-12-01

    The exposure of mantle peridotite to water at crustal levels leads to a cascade of interconnected dissolution-precipitation and reduction-oxidation reactions - a process referred to as serpentinization. These reactions have major implications for microbial life through the provision of hydrogen (H2). To simulate incipient serpentinization and the release of H2 under well-constrained conditions, we reacted uncrushed harzburgite with chemically modified seawater at 300°C and 35 MPa for ca. 1.5 years (13441 hours), monitored changes in fluid chemistry over time, and examined the secondary mineralogy at the termination of the experiment. Approximately 4 mol % of the protolith underwent alteration forming serpentine, accessory magnetite, chlorite, and traces of calcite and heazlewoodite. Alteration textures bear remarkable similarities to those found in partially serpentinized abyssal peridotites. Neither brucite nor talc precipitated during the experiment. Given that the starting material contained ~3.8 times more olivine than orthopyroxene on a molar basis, mass balance requires that dissolution of orthopyroxene was significantly faster than dissolution of olivine. However, the H2 release rate was not uniform, slowing from ~2 nmol H2(aq) gperidotite-1 s-1 at the beginning of the experiment to ~0.2 nmol H2(aq) gperidotite-1 s-1 at its termination. Serpentinization consumed water but did not release significant amounts of dissolved species (other than H2) suggesting that incipient hydration reactions involved a volume increase of ~40%. The reduced access of water to olivine surfaces due to filling of fractures and coating of primary minerals with alteration products led to decreased rates of serpentinization and H2 release. While this concept might seem at odds with completely serpentinized seafloor peridotites, reaction-driven fracturing offers an intriguing solution to the seemingly self-limiting nature of serpentinization. Indeed, the reacted sample revealed a

  17. Reaction kinetics of Cl atoms with limonene: An experimental and theoretical study

    NASA Astrophysics Data System (ADS)

    Dash, Manas Ranjan; Rajakumar, B.

    2014-12-01

    Rate coefficients for the reaction of Cl atoms with limonene (C10H16) were measured between 278-350 K and 800 Torr of N2, using the relative rate technique, with 1,3-butadiene (C4H6), n-nonane (C9H20), and 1-pentene (C5H10) as reference compounds. Cl atoms were generated by UV photolysis of oxalyl chloride ((COCl)2) at 254 nm. A gas chromatograph equipped with a flame ionization detector (GC-FID) was used for quantitative analysis of the organics. The rate coefficient for the reaction of Cl atoms with limonene at 298 K was measured to be (8.65 ± 2.44) × 10-10 cm3 molecule-1 s-1. The rate coefficient is an average value of the measurements, with two standard deviations as the quoted error, including uncertainties in the reference rate coefficients. The kinetic data obtained over the temperature range of 278-350 K were used to derive the following Arrhenius expression: k(T) = (9.75 ± 4.1) × 10-11 exp[(655 ± 133)/T] cm3 molecule-1 s-1. Theoretical kinetic calculations were also performed for the title reaction using conventional transition state theory (CTST) in combination with G3(MP2) theory between 275 and 400 K. The kinetic data obtained over the temperature range of 275-400 K were used to derive an Arrhenius expression: k(T) = (7.92 ± 0.82) × 10-13 exp[(2310 ± 34)/T] cm3 molecule-1 s-1. The addition channels contributes maximum to the total reaction and H-abstraction channels can be neglected in the range of studied pressures. The Atmospheric lifetime (τ) of limonene due to its reaction with Cl atoms was estimated and concluded that the reaction with chlorine atoms can be an effective tropospheric loss pathway in the marine boundary layer and in coastal urban areas.

  18. Solid phase graft copolymerization of acrylic monomers onto thermoplastics and their use as blend compatibilizers

    NASA Astrophysics Data System (ADS)

    Subramanian, Srinivas

    This research work is an extension of some of the earlier work done on the development of solid phase grafting technique to graft various monomers onto polymers as well as postulation of the usefulness of the graft copolymers thus synthesized. Polystyrene grafted with acrylic acid, previously developed in bench scale, was synthesized in pilot-plant scale batches. Process parameter studies on the grafting of acrylic acid onto polypropylene and developmental studies on the grafting of maleic anhydride onto polystyrene were also done. Polymers grafted with polar molecules such as maleic anhydride and acrylic acid have been used to compatibilize immiscible blends of polar and non-polar polymers. On the same note, the applicability of the solid phase graft copolymers as blend compatibilizers were investigated and their performance was compared to commercially available compatibilizers. Solid phase graft copolymerization process is a technique to synthesize graft copolymers. Some of its salient features are use of minimal solvent to conduct the reaction and easy equipment modification. It is a low pressure and low temperature process. This technique provides a viable alternative to the environmentally hazardous, and time consuming conventional process currently in use. Hence, development of this technique could be beneficial not only to the plastics industry, but also to mankind. Also, this technique provides a low-cost and extremely easy method to develop graft copolymers such as acrylic acid functionalized polymers that are rapidly gaining popularity as blend compatibilizers and polymer reinforcing agents. A study that proves the potential of these solid phase graft copolymers as good blend compatibilizers for industrially important immiscible polymers will develop interest in the industries about this grafting process. The free radical solid phase graft copolymerization process was carried in a modified Brabender-type mixer fitted with specially designed blades to

  19. Experimental results for studies of the 40Ca(α,γ)44Ti reaction rates

    NASA Astrophysics Data System (ADS)

    Robertson, Daniel; Becker, Hans-Werner; Bowers, Matt; Collon, Philippe; Goerres, Joachim; Lu, Wenting; Schmitt, Chris; Wiescher, Michael

    2011-10-01

    Observational studies of galactic γ emitters such as 44Ti have highlighted their use in nucleosynthesis studies of massive stars in their late stage stellar evolution and final explosive demise in core collapse supernova events. Models used in the simulation of such γ emitters rely heavily upon reliable reaction rates for both the creation and annihilation of these isotopes over large temperature ranges. The production of 44Ti mainly through the 40Ca(α,γ)44Ti reaction is thought to take place primarily in the α-rich freeze out phase of a core collapse supernova. However, current supernova models predict lower 44Ti to 56Ni ratios than observed, creating a need for more information about its production mechanism. A number of previous studies include prompt γ-ray measurements, recoil mass separator experiments and the use of AMS, all giving greatly different reaction rates. Aiding in the refinement of these needed rates, the results of experiments at the DTL, Bochum and NSL, Notre Dame will be presented against the backdrop of these previous measurements. Work supported by grant # 0758100 and # 0822648.

  20. Carbon sequestration via reaction with basaltic rocks: geochemical modeling and experimental results

    USGS Publications Warehouse

    Rosenbauer, Robert J.; Thomas, Burt; Bischoff, James L.; Palandri, James

    2012-01-01

    Basaltic rocks are potential repositories for sequestering carbon dioxide (CO2) because of their capacity for trapping CO2 in carbonate minerals. We carried out a series of thermodynamic equilibrium models and high pressure experiments, reacting basalt with CO2-charged fluids over a range of conditions from 50 to 200 °C at 300 bar. Results indicate basalt has a high reactivity to CO2 acidified brine. Carbon dioxide is taken up from solution at all temperatures from 50 to 200 °C, 300 bar, but the maximum extent and rate of reaction occurs at 100 °C, 300 bar. Reaction path simulations utilizing the geochemical modeling program CHILLER predicted an equilibrium carbonate alteration assemblage of calcite, magnesite, and siderite, but the only secondary carbonate identified in the experiments was a ferroan magnesite. The amount of uptake at 100 °C, 300 bar ranged from 8% by weight for a typical tholeite to 26% for a picrite. The actual amount of CO2 uptake and extent of rock alteration coincides directly with the magnesium content of the rock suggesting that overall reaction extent is controlled by bulk basalt Mg content. In terms of sequestering CO2, an average basaltic MgO content of 8% is equivalent to 2.6 × 108 metric ton CO2/km3 basalt.

  1. Dehydration reactions and micro/nanostructures in experimentally-deformed serpentinites

    NASA Astrophysics Data System (ADS)

    Viti, Cecilia; Hirose, Takehiro

    2009-03-01

    High-T torsion experiments on lizardite + chrysotile serpentinites produced mineralogical and micro/nanostructural changes, with important implications in rheological properties. High-resolution TEM showed that specimens underwent ductile [by microkinking and (001) interlayer glide] and brittle deformation (by microfracturing), together with dehydration and break-down reactions. Lizardite is affected by polytypic disorder and microkinking [kink axial planes at high angle with respect to (001) planes], that were not present in the initial ordered 1T-lizardite. Chrysotile fibres are deformed, resulting in elliptical cross-sections, with strong loss of interlayer cohesion. Both lizardite and chrysotile break down to a fine intergrowth of olivine (up to 200 nm), talc (up to 30 nm) and poorly-crystalline material. Lizardite-out reaction preferentially occurs at kink axial planes, representing sites of preferential strain and enhanced reactivity; conversely, chrysotile break-down is a bulk process, resulting in large healed olivine aggregates, up to micrometric in size. Overall observations suggest that dehydration and break-down reactions are more advanced in chrysotile than in lizardite.

  2. Experimental U.S. Census Bureau Race and Hispanic Origin Survey Questions: Reactions from Spanish Speakers

    ERIC Educational Resources Information Center

    Terry, Rodney L.; Fond, Marissa

    2013-01-01

    People of Hispanic origin, including monolingual Spanish speakers, have experienced difficulty identifying with a race category on U.S. demographic surveys. As part of a larger research effort by the U.S. Census Bureau to improve race and Hispanic origin questions for the 2020 Census, we tested experimental versions of race and Hispanic origin…

  3. Mechanism of alkoxy groups substitution by Grignard reagents on aromatic rings and experimental verification of theoretical predictions of anomalous reactions.

    PubMed

    Jiménez-Osés, Gonzalo; Brockway, Anthony J; Shaw, Jared T; Houk, K N

    2013-05-01

    The mechanism of direct displacement of alkoxy groups in vinylogous and aromatic esters by Grignard reagents, a reaction that is not observed with expectedly better tosyloxy leaving groups, is elucidated computationally. The mechanism of this reaction has been determined to proceed through the inner-sphere attack of nucleophilic alkyl groups from magnesium to the reacting carbons via a metalaoxetane transition state. The formation of a strong magnesium chelate with the reacting alkoxy and carbonyl groups dictates the observed reactivity and selectivity. The influence of ester, ketone, and aldehyde substituents was investigated. In some cases, the calculations predicted the formation of products different than those previously reported; these predictions were then verified experimentally. The importance of studying the actual system, and not simplified models as computational systems, is demonstrated. PMID:23601086

  4. Experimental differential cross sections, level densities, and spin cutoffs as a testing ground for nuclear reaction codes

    NASA Astrophysics Data System (ADS)

    Voinov, A. V.; Grimes, S. M.; Brune, C. R.; Bürger, A.; Görgen, A.; Guttormsen, M.; Larsen, A. C.; Massey, T. N.; Siem, S.

    2013-11-01

    Proton double-differential cross sections from 59Co(α,p)62Ni, 57Fe(α,p)60Co, 56Fe(7Li,p)62Ni, and 55Mn(6Li,p)60Co reactions have been measured with 21-MeV α and 15-MeV lithium beams. Cross sections have been compared against calculations with the empire reaction code. Different input level density models have been tested. It was found that the Gilbert and Cameron [A. Gilbert and A. G. W. Cameron, Can. J. Phys.0008-420410.1139/p65-139 43, 1446 (1965)] level density model is best to reproduce experimental data. Level densities and spin cutoff parameters for 62Ni and 60Co above the excitation energy range of discrete levels (in continuum) have been obtained with a Monte Carlo technique. Excitation energy dependencies were found to be inconsistent with the Fermi-gas model.

  5. Experimental study of the p d (d p )→3Heπ π reactions close to threshold

    NASA Astrophysics Data System (ADS)

    Bellemann, F.; Berg, A.; Bisplinghoff, J.; Bohlscheid, G.; Ernst, J.; Henrich, C.; Hinterberger, F.; Ibald, R.; Jahn, R.; Joosten, R.; Kilian, K.; Kozela, A.; Machner, H.; Magiera, A.; Munkel, J.; von Neumann-Cosel, P.; von Rossen, P.; Schnitker, H.; Scho, K.; Smyrski, J.; Tölle, R.; Wilkin, C.; COSY-MOMO Collaboration

    2016-09-01

    New experimental data on the p d → 3Heπ+π- reaction obtained with the COSY-MOMO detector below the three-pion threshold are presented. The reaction was also studied in inverse kinematics with a deuteron beam and the higher counting rates achieved were especially important at low excess energies. The comparison of these data with inclusive p d → 3HeX0 rates allowed estimates also to be made of π0π0 production. The results confirm our earlier findings that, close to threshold, there is no enhancement at low excitation energies in the π+π- system, where the data seem largely suppressed compared with phase space. Possible explanations for this behavior, such as strong p waves in the π+π- system or the influence of two-step processes, are explored.

  6. Experimental differential cross sections, level densities, and spin cutoffs as a testing ground for nuclear reaction codes

    DOE PAGES

    Voinov, Alexander V.; Grimes, Steven M.; Brune, Carl R.; Burger, Alexander; Gorgen, Andreas; Guttormsen, Magne; Larsen, Ann -Cecilie; Massey, Thomas N.; Siem, Sunniva

    2013-11-08

    Proton double-differential cross sections from 59Co(α,p)62Ni, 57Fe(α,p)60Co, 56Fe(7Li,p)62Ni, and 55Mn(6Li,p)60Co reactions have been measured with 21-MeV α and 15-MeV lithium beams. Cross sections have been compared against calculations with the empire reaction code. Different input level density models have been tested. It was found that the Gilbert and Cameron [A. Gilbert and A. G. W. Cameron, Can. J. Phys. 43, 1446 (1965)] level density model is best to reproduce experimental data. Level densities and spin cutoff parameters for 62Ni and 60Co above the excitation energy range of discrete levels (in continuum) have been obtained with a Monte Carlo technique. Furthermore,more » excitation energy dependencies were found to be inconsistent with the Fermi-gas model.« less

  7. Mechanism of Alkoxy Groups Substitution by Grignard Reagents on Aromatic Rings and Experimental Verification of Theoretical Predictions of Anomalous Reactions

    PubMed Central

    Jiménez-Osés, Gonzalo; Brockway, Anthony J.; Shaw, Jared T.; Houk, K. N.

    2013-01-01

    The mechanism of direct displacement of alkoxy groups in vinylogous and aromatic esters by Grignard reagents, a reaction that is not observed with expectedly better tosyloxy leaving groups, is elucidated computationally. The mechanism of this reaction has been determined to proceed through the inner-sphere attack of nucleophilic alkyl groups from magnesium to the reacting carbons via a metalaoxetane transition state. The formation of a strong magnesium chelate with the reacting alkoxy and carbonyl groups dictates the observed reactivity and selectivity. The influence of ester, ketone and aldehyde substituents was investigated. In some cases, the calculations predicted the formation of products different than those previously reported; these predictions were then verified experimentally. The importance of studying the actual system, and not simplified models as computational systems, is demonstrated. PMID:23601086

  8. pH-Sensitive brush polymer-drug conjugates by ring-opening metathesis copolymerization.

    PubMed

    Zou, Jiong; Jafr, Goran; Themistou, Efrosyni; Yap, Yoonsing; Wintrob, Zachary A P; Alexandridis, Paschalis; Ceacareanu, Alice C; Cheng, Chong

    2011-04-21

    Representing a new category of polymer-drug conjugates, brush polymer-drug conjugates were prepared by ring-opening metathesis copolymerization. Following judicious structural design, these conjugates exhibited well-shielded drug moieties, significant water solubility, well-defined nanostructures, and acid-triggered drug release.

  9. Evolution of fracture permeability of ultramafic rocks at hydrothermal conditions: An experimental study on serpentinization reactions

    NASA Astrophysics Data System (ADS)

    Farough, A.; Moore, D. E.; Lockner, D. A.; Lowell, R. P.

    2014-12-01

    Serpentinization of ultramafic rocks, during which olivine and pyroxene minerals are replaced by serpentine, magnetite, brucite and talc, is associated with hydrothermal activity at slow and ultraslow mid-ocean ridges. Serpentinization reactions affect hydrothermal fluid circulation by changing permeability of the oceanic crust. To advance our understanding of the evolution of permeability accompanying serpentinization reactions, we performed a series of flow-through experiments at a temperature of 260˚C, a confining pressure of 50 MPa, and a pore pressure of 20±2 MPa on cylindrical cores of ultramafic rocks (18 mm in diameter and 23 mm length) containing a single through-going tensile fracture. Pore fluid flow was in one direction and was collected routinely for chemical analysis. A 7.5 mm thick layer of the same rock, crushed and sieved (0.18-1.0 mm) was placed on the inlet end of the sample to produce a reactive heated reservoir for the pore fluid before entering the fracture. Multiple peridotite samples were tested, to investigate the effect of mineral assemblage on fluid-rock interaction and permeability. The initial effective permeability of the samples varied between 10-(15-18)m2, and it decreased by about 2 orders of magnitude in 7-10 days, showing that serpentinization reactions result in an initially rapid decrease in permeability. The best fit equation for the observed rate of change in permeability (k) is in the form of dk/dt=Ae-0.01t, where A is a constant and t is time. This result suggests that the rate of serpentine formation is largely controlled by the initial permeability rather than the properties of the reacting rock. Assuming flow between parallel plates, we find the effective crack width decreases by approximately 2 orders of magnitude during the experiments. The fluid chemistry and mineralogy data support the occurrence of serpentinization reactions. The early peak and monotonic decrease in the concentration of Mg, and Si in pore fluid

  10. Experimental Measurements of the Chemical Reaction Zone of Detonating Liquid Explosives

    NASA Astrophysics Data System (ADS)

    Bouyer, Viviane; Sheffield, Stephen A.; Dattelbaum, Dana M.; Gustavsen, Richard L.; Stahl, David B.; Doucet, Michel

    2009-06-01

    We have a joint project between CEA-DAM Le Ripault and Los Alamos National Laboratory (LANL) to study the chemical reaction zone in detonating high explosives using several different laser velocimetry techniques. The short temporal duration of the features (von Neumann spike and sonic locus) of the reaction zone make these measurements difficult. Here, we report results obtained from using and PDV (photon Doppler velocimetry) methods to measure the particle velocity history at a detonating HE (nitromethane)/PMMA interface. Experiments done at CEA were high-explosive-plane-wave initiated and those at LANL were gas-gun-projectile initiated with a detonation run of about 6 charge diameters in all experiments, in either glass or brass confinement. Excellent agreement of the interface particle velocity measurements at both Laboratories were obtained even though the initiation systems and the velocimetry systems were different. Some differences were observed in the von Neumann spike height because of the approximately 2 nanosecond time resolution of the techniques -- in some or all cases the spike top was truncated.

  11. Experimental Measurements of the Chemical Reaction Zone of Detonating Liquid Explosives

    NASA Astrophysics Data System (ADS)

    Bouyer, Viviane; Sheffield, Stephen A.; Dattelbaum, Dana M.; Gustavsen, Richard L.; Stahl, David B.; Doucet, Michel; Decaris, Lionel

    2009-12-01

    We have a joint project between CEA-DAM Le Ripault and Los Alamos National Laboratory (LANL) to study the chemical reaction zone in detonating high explosives using several different laser velocimetry techniques. The short temporal duration of the von Neumann spike and early part of the reaction zone make these measurements difficult. Here, we report results obtained from detonation experiments using VISAR (velocity interferometer system for any reflector) and PDV (photon Doppler velocimetry) methods to measure the particle velocity history at a detonating nitromethane/PMMA interface. Experiments done at CEA were high-explosive-plane-wave initiated and those at LANL were gas-gun-projectile initiated with a detonation run of about 6 charge diameters in all experiments. The experiments had either glass or brass confinement. Excellent agreement of the interface particle velocity measurements at both Laboratories were obtained even though the initiation methods and the velocimetry systems were somewhat different. Some differences were observed in the peak particle velocity because of the ˜2 ns time resolution of the techniques—in all cases the peak was lower than the expected von Neumann spike. This is thought to be because the measurements were not high enough time resolution to resolve the spike.

  12. Experimental evolution for generalists and specialists reveals multivariate genetic constraints on thermal reaction norms.

    PubMed

    Berger, D; Walters, R J; Blanckenhorn, W U

    2014-09-01

    Theory predicts the emergence of generalists in variable environments and antagonistic pleiotropy to favour specialists in constant environments, but empirical data seldom support such generalist-specialist trade-offs. We selected for generalists and specialists in the dung fly Sepsis punctum (Diptera: Sepsidae) under conditions that we predicted would reveal antagonistic pleiotropy and multivariate trade-offs underlying thermal reaction norms for juvenile development. We performed replicated laboratory evolution using four treatments: adaptation at a hot (31 °C) or a cold (15 °C) temperature, or under regimes fluctuating between these temperatures, either within or between generations. After 20 generations, we assessed parental effects and genetic responses of thermal reaction norms for three correlated life-history traits: size at maturity, juvenile growth rate and juvenile survival. We find evidence for antagonistic pleiotropy for performance at hot and cold temperatures, and a temperature-mediated trade-off between juvenile survival and size at maturity, suggesting that trade-offs associated with environmental tolerance can arise via intensified evolutionary compromises between genetically correlated traits. However, despite this antagonistic pleiotropy, we found no support for the evolution of increased thermal tolerance breadth at the expense of reduced maximal performance, suggesting low genetic variance in the generalist-specialist dimension.

  13. [An experimental unit for the recording of the escape reaction of a ground snail to tactile stimulation].

    PubMed

    Moskvitin, A A; Pivovarov, A S

    2003-01-01

    An original working experimental unit for noninvasive objective recording of the magnitude of escape reaction of a ground snail evoked by tactile stimulation is described. A. snail creeps upwards over the cylinder rotating around its horizontal axis. A watching device ensures a constant snail position relative to a light source and a photoelement. A device for tactile stimulation which provides graduated energy of an impact is constructed on the basis of the magnetic circuit of a loudspeaker. In response to a tactile stimulus a snail pulls in its feelers, head, and foot, and the area of snail's shadow decreases. These changes are indicated by the photoelement. PMID:12754854

  14. Modelling of geochemical reactions and experimental cation exchange in MX 80 bentonite.

    PubMed

    Montes-H, G; Fritz, B; Clement, A; Michau, N

    2005-10-01

    Bentonites are widely used for waste repository systems because of their hydrodynamic, surface and chemical-retention properties. MX 80 bentonite (bentonite of Wyoming) contains approximately 85% Na/Ca-montmorillonite and 15% accessory minerals. The dominant presence of Na/Ca-montmorillonite in this clay mineral could cause it to perform exceptionally well as an engineered barrier for a radioactive waste repository because this buffer material is expected to fill up by swelling the void between canisters containing waste and the surrounding ground. However, the Na/Ca-montmorillonite could be transformed to other clay minerals as a function of time under repository conditions. Previous modelling studies based on the hydrolysis reactions have shown that the Na/Ca-montmorillonite-to-Ca-montmorillonite conversion is the most significant chemical transformation. In fact, this chemical process appears to be a simple cation exchange into the engineered barrier. The purpose of the present study was two-fold. Firstly, it was hoped to predict the newly formed products of bentonite-fluid reactions under repository conditions by applying a thermokinetic hydrochemical code (KIRMAT: Kinetic Reactions and Mass Transport). The system modelled herein was considered to consist of a 1-m thick zone of water-saturated engineered barrier. This non-equilibrated system was placed in contact with a geological fluid on one side, which was then allowed to diffuse into the barrier, while the other side was kept in contact with iron-charged water. Reducing initial conditions ( [P(O)2 approximately equals 0] ; Eh=-200 mV) and a constant reaction temperature (100 degrees C) were considered. Secondly, it was hoped to estimate the influence of inter-layer cations (Ca and Na) on the swelling behaviour of the MX 80 bentonite by using an isothermal system of water vapour adsorption and an environmental scanning electron microscope (ESEM) coupled with a digital image analysis (DIA) program. Here, the

  15. Theoretical investigation of ethylene/1-butene copolymerization process using constrained geometry catalyst (CpSiH 2NH)-Ti-Cl 2

    NASA Astrophysics Data System (ADS)

    Malani, Hema; Hayashi, Shigekazu; Zhong, Huifeng; Sahnoun, Riadh; Tsuboi, Hideyuki; Koyama, Michihisa; Hatakeyama, Nozomu; Endou, Akira; Takaba, Hiromitsu; Kubo, Momoji; Del Carpio, Carlos A.; Miyamoto, Akira

    2008-09-01

    The ethylene/1-butene copolymerization using constrained geometry catalyst CpSiH 2-NH-TiCl 2 (CGC) was investigated by the density functional theory and molecular dynamics. Structures and energetics of reactants, π-complexes, transition states, and products during insertion of ethylene and 1-butene monomers into the catalytic reactive site of the CGC were investigated by the density functional theory (DFT) using the software Dmol 3, while dynamics of atoms during copolymerization process was investigated by classical molecular dynamics (MD) using the New-Ryudo-CR program. The calculated results were compared with the available experimental and theoretical ones. It was found that the ethylene insertion into Ti-Me active species is energetically more favorable than the butene one and the 2,1-butene insertion is more favorable than 1,2-butene one. Once the initial ethylene insertion has taken place, the further ethylene insertion occurring with a less energy barrier, in good agreement with experimental findings.

  16. Adobe Flash as a medium for online experimentation: a test of reaction time measurement capabilities.

    PubMed

    Reimers, Stian; Stewart, Neil

    2007-08-01

    Adobe Flash can be used to run complex psychological experiments over the Web. We examined the reliability of using Flash to measure reaction times (RTs) using a simple binary-choice task implemented both in Flash and in a Linux-based system known to record RTs with millisecond accuracy. Twenty-four participants were tested in the laboratory using both implementations; they also completed the Flash version on computers of their own choice outside the lab. RTs from the trials run on Flash outside the lab were approximately 20 msec slower than those from trials run on Flash in the lab, which in turn were approximately 10 msec slower than RTs from the trials run on the Linux-based system (baseline condition). RT SDs were similar in all conditions, suggesting that although Flash may overestimate RTs slightly, it does not appear to add significant noise to the data recorded.

  17. Reaction cross-section calculations using new experimental and theoretical level structure data for deformed nuclei

    SciTech Connect

    Hoff, R.W.; Gardner, D.G.; Gardner, M.A.

    1984-10-05

    A technique for modeling quasiparticle excitation energies and rotational parameters in odd-odd deformed nuclei has been used to construct sets of discrete states with energy 0 to 1.5 MeV in /sup 176/Lu and /sup 236/Np. These data were used as part of the input for calculation of isomer production cross-section ratios in the /sup 175/Lu(n,..gamma..)/sup 176/Lu and /sup 237/Np(n,2n)/sup 236/Np reactions. In order to achieve agreement with experiment, it has been found necessary to include in the modeled set many rotational bands (35 to 95), which are comprised of hundreds of levels with their gamma-ray branching ratios. It is essential that enough bands be included to produce a representative selection of K quantum numbers in the de-excitation cascade. 20 refs., 3 figs., 3 tabs.

  18. Experimental Studies of Fast Protons Originated from Fusion Reactions in Plasma-Focus Discharges

    SciTech Connect

    Malinowska, A.; Malinowski, K.; Sadowski, M. J.; Zebrowski, J.; Szydlowski, A.

    2008-03-19

    The paper describes results of the recent measurements of fusion-reaction protons, which were performed within the PF-360 facility operated at the IPJ in Swierk, Poland. The main aim of those studies was to perform time-integrated measurements of fast protons (of energy of about 3 MeV) by means of ion-pinhole cameras, which were equipped with solid state nuclear track detectors (SSNTD) of the PM-355 type and absorption filters made of thin metal foils. In order to determine the spatial distribution of fusion-produced protons the use was made of several miniature pinhole cameras placed at different angles to the PF-360 axis. The irradiated and etched detectors were analyzed with an optical microscope coupled with a CCD camera and a PC unit.

  19. Combined Experimental and Computational Approach to Predict the Glass-Water Reaction

    SciTech Connect

    Pierce, Eric M; Bacon, Diana

    2011-01-01

    The use of mineral and glass dissolution rates measured in laboratory experiments to predict the weathering of primary minerals and volcanic and nuclear waste glasses in field studies requires the construction of rate models that accurately describe the weathering process over geologic time-scales. Additionally, the need to model the long-term behavior of nuclear waste glass for the purpose of estimating radionuclide release rates requires that rate models are validated with long-term experiments. Several long-term test methods have been developed to accelerate the glass-water reaction [drip test, vapor hydration test, product consistency test-B, and pressurized unsaturated flow (PUF)], thereby reducing the duration required to evaluate long-term performance. Currently, the PUF test is the only method that mimics the unsaturated hydraulic properties expected in a subsurface disposal facility and simultaneously monitors the glass-water reaction. PUF tests are being conducted to accelerate the weathering of glass and validate the model parameters being used to predict long-term glass behavior. A one-dimensional reactive chemical transport simulation of glass dissolution and secondary phase formation during a 1.5-year long PUF experiment was conducted with the subsurface transport over reactive multi-phases code. Results show that parameterization of the computer model by combining direct bench-scale laboratory measurements and thermodynamic data provides an integrated approach to predicting glass behavior over the length of the experiment. Over the 1.5-year long test duration, the rate decreased from 0.2 to 0.01 g/(m2 d) base on B release. The observed decrease is approximately two orders of magnitude higher than the decrease observed under static conditions with the SON68 glass (estimated to be a decrease by 4 orders of magnitude) and suggest the gel-layer properties are less protective under these dynamic conditions.

  20. Combined Experimental and Computational Approach to Predict the Glass-Water Reaction

    SciTech Connect

    Pierce, Eric M.; Bacon, Diana H.

    2011-10-01

    The use of mineral and glass dissolution rates measured in laboratory experiments to predict the weathering of primary minerals and volcanic and nuclear waste glasses in field studies requires the construction of rate models that accurately describe the weathering process over geologic timescales. Additionally, the need to model the long-term behavior of nuclear waste glass for the purpose of estimating radionuclide release rates requires that rate models be validated with long-term experiments. Several long-term test methods have been developed to accelerate the glass-water reaction [drip test, vapor hydration test, product consistency test B, and pressurized unsaturated flow (PUF)], thereby reducing the duration required to evaluate long-term performance. Currently, the PUF test is the only method that mimics the unsaturated hydraulic properties expected in a subsurface disposal facility and simultaneously monitors the glass-water reaction. PUF tests are being conducted to accelerate the weathering of glass and validate the model parameters being used to predict long-term glass behavior. A one-dimensional reactive chemical transport simulation of glass dissolution and secondary phase formation during a 1.5-year-long PUF experiment was conducted with the Subsurface Transport Over Reactive Multiphases (STORM) code. Results show that parameterization of the computer model by combining direct bench scale laboratory measurements and thermodynamic data provides an integrated approach to predicting glass behavior over the length of the experiment. Over the 1.5-year-long test duration, the rate decreased from 0.2 to 0.01 g/(m2 day) based on B release for low-activity waste glass LAWA44. The observed decrease is approximately two orders of magnitude higher than the decrease observed under static conditions with the SON68 glass (estimated to be a decrease by four orders of magnitude) and suggests that the gel-layer properties are less protective under these dynamic

  1. Experimental and theoretical studies on gas-phase reactions of NO3 radicals with three methoxyphenols: Guaiacol, creosol, and syringol

    NASA Astrophysics Data System (ADS)

    Yang, Bo; Zhang, Haixu; Wang, Youfeng; Zhang, Peng; Shu, Jinian; Sun, Wanqi; Ma, Pengkun

    2016-01-01

    Methoxyphenols, lignin pyrolysis products, are major biomass combustion components and are considered potential tracers for wood smoke emissions. Their atmospheric reactivity, however, has not been well characterized. Guaiacol, creosol, and syringol are three typical methoxyphenols generated in relatively high concentrations in fresh wood smoke. In this study, the gas-phase reactions of NO3 radicals with these methoxyphenols were investigated using a laboratory-built vacuum ultraviolet photoionization gas time-of-flight mass spectrometer (VUV-GTOFMS) and off-line GC-MS. By combining experimental and theoretical methods, 4-nitroguaiacol, 6-nitroguaiacol, and 4,6-dinitroguaiacol were determined as the primary degradation products for guaiacol; similarly, 6-nitrocreosol and 3-nitrosyringol were identified for creosol and syringol, respectively. Using the relative rate method, rate constants at 298 K and 1 atm for the gas-phase reactions of guaiacol, creosol, and syringol with NO3 radicals were measured to be 3.2 × 10-12, 2.4 × 10-13, and 4.0 × 10-13 cm3 molecule-1 s-1, respectively. At a typical tropospheric concentration of NO3 radicals (5 × 108 molecule cm-3), atmospheric lifetimes for guaiacol, creosol, and syringol toward NO3 radicals were 0.2, 2.3, and 1.4 h, respectively. These results indicate that the reaction with NO3 radicals can be a major sink for methoxyphenols at night.

  2. Experimental and Computational Induced Aerodynamics from Missile Jet Reaction Controls at Angles of Attack to 75 Degrees

    NASA Technical Reports Server (NTRS)

    Capone, Francis J.; Ashbury, Scott C.; Deere, Karen A.

    1996-01-01

    An investigation was conducted in the Langley 16-Foot Transonic Tunnel to determine induced aerodynamic effects from jet reaction controls of an advanced air-to-air missile concept. The 75-percent scale model featured independently controlled reaction jets located near the nose and tail of the model. Aerodynamic control was provided by four fins located near the tail of the model. This investigation was conducted at Mach numbers of 0.35 and 0.60, at angles of attack up to 75 deg and at nozzle pressure ratios up to 90. Jet-reaction thrust forces were not measured by the force balance but jet-induced forces were. In addition, a multiblock three-dimensional Navier-Stokes method was used to calculate the flowfield of the missile at angles of attack up to 40 deg. Results indicate that large interference effects on pitching moment were induced from operating the nose jets with the the off. Excellent correlation between experimental and computational pressure distributions and pitching moment were obtained a a Mach number of 0.35 and at angles of attack up to 40 deg.

  3. Experimental elaboration of faulting induced by fluid-releasing mineral reactions in subduction zones

    NASA Astrophysics Data System (ADS)

    Green, H.; Zhang, J.; Jung, H.; Dobrzinetskaya, L.

    2003-04-01

    Dehydration embrittlement has been cited repeatedly as a potential mechanism for triggering earthquakes at depths where unassisted brittle failure is impossible due to the normal-stress-dependence of friction. We are investigating two different aspects of this problem in the laboratory: (i) dehydration of antigorite under stress where the ΔV of reaction varies from strongly positive to distinctly negative; (ii) deformation of eclogite in which the nominally anhydrous minerals contain small amounts of dissolved H_2O that can lead to faulting induced by very small amounts of melting stimulated by exsolution of H_2O. (i) Antigorite has the largest stability field of the serpentines and is often cited as potentially being the source of most or all mantle earthquakes to a depth of over 200 km. However, like other low-pressure hydrous phases, the net volume change accompanying antigorite dehydration varies from strongly positive at low P to negative at P > ˜2-2.5 GPa. Fracture mechanics theory predicts that dehydration should not induce shear failure if ΔV<0. To test the effect of ΔV on faulting, we have deformed an extensively-serpentinized peridotite at P = 1-6 GPa. We conducted constant strain rate experiments in a Griggs-type apparatus at P = 1.0 - 3.4 GPa and rapid-pumping experiments in a Walker-type multianvil apparatus, culminating in pressures as high as 6 GPa. Independent of the sign of ΔV, specimens subjected to stress during dehydration yielded extremely thin zones of reaction products with shear offset across them. Some were clearly faults whereas others could be precursors to faulting. Fluid released at grain boundaries between antigorite and relict olivine locally produced Mode I cracks &fluid inclusions. (ii) Deformation of "wet" eclogite at 3 GPa and temperatures between the wet and dry solidi induced exsolution of H_2O and formation of very small amounts (<1%) of melt, leading to faulting. At lower temperature the rock was extremely strong but

  4. Temperature dependence of the OH(-) + CH3I reaction kinetics. experimental and simulation studies and atomic-level dynamics.

    PubMed

    Xie, Jing; Kohale, Swapnil C; Hase, William L; Ard, Shaun G; Melko, Joshua J; Shuman, Nicholas S; Viggiano, Albert A

    2013-12-27

    Direct dynamics simulations and selected ion flow tube (SIFT) experiments were performed to study the kinetics and dynamics of the OH(-) + CH3I reaction versus temperature. This work complements previous direct dynamics simulation and molecular beam ion imaging experiments of this reaction versus reaction collision energy (Xie et al. J. Phys. Chem. A 2013, 117, 7162). The simulations and experiments are in quite good agreement. Both identify the SN2, OH(-) + CH3I → CH3OH + I(-), and proton transfer, OH(-) + CH3I → CH2I(-) + H2O, reactions as having nearly equal importance. In the experiments, the SN2 pathway constitutes 0.64 ± 0.05, 0.56 ± 0.05, 0.51 ± 0.05, and 0.46 ± 0.05 of the total reaction at 210, 300, 400, and 500 K, respectively. For the simulations this fraction is 0.56 ± 0.06, 0.55 ± 0.04, and 0.50 ± 0.05 at 300, 400, and 500 K, respectively. The experimental total reaction rate constant is (2.3 ± 0.6) × 10(-9), (1.7 ± 0.4) × 10(-9), (1.9 ± 0.5) × 10(-9), and (1.8 ± 0.5) × 10(-9) cm(3) s(-1) at 210, 300, 400, and 500 K, respectively, which is approximately 25% smaller than the collision capture value. The simulation values for this rate constant are (1.7 ± 0.2) × 10(-9), (1.8 ± 0.1) × 10(-9), and (1.6 ± 0.1) × 10(-9) cm(3)s(-1) at 300, 400, and 500 K. From the simulations, direct rebound and stripping mechanisms as well as multiple indirect mechanisms are identified as the atomic-level reaction mechanisms for both the SN2 and proton-transfer pathways. For the SN2 reaction the direct and indirect mechanisms have nearly equal probabilities; the direct mechanisms are slightly more probable, and direct rebound is more important than direct stripping. For the proton-transfer pathway the indirect mechanisms are more important than the direct mechanisms, and stripping is significantly more important than rebound for the latter. Calculations were performed with the OH(-) quantum number J equal to 0, 3, and 6 to investigate the effect of

  5. Experimental exploration of the Mulliken-Hush relationship for intramolecular electron transfer reactions.

    PubMed

    Mukherjee, Tamal; Ito, Naoki; Gould, Ian R

    2011-03-17

    The Mulliken-Hush (M-H) relationship provides the critical link between optical and thermal electron transfer processes, and yet very little direct experimental support for its applicability has been provided. Dicyanovinylazaadamantane (DCVA) represents a simple two-state (neutral/charge-transfer) intramolecular electron transfer system that exhibits charge-transfer absorption and emission spectra that are readily measurable in solvents with a wide range of polarities. In this regard it represents an ideal model system for studying the factors that control both optical charge separation (absorption) and recombination (emission) processes in solution. Here we explore the applicability of the M-H relation to quantitative descriptions of the optical charge-transfer processes in DCVA. For DCVA, the measured radiative rate constants exhibit a linear dependence on transition energy, and transition dipole moments exhibit an inverse dependence on transition energy, consistent with the M-H relationship.

  6. Methylene Blue to Treat Protamine-induced Anaphylaxis Reactions. An Experimental Study in Pigs

    PubMed Central

    Albuquerque, Agnes Afrodite S.; Margarido, Edson A.; Menardi, Antonio Carlos; Scorzoni Filho, Adilson; Celotto, Andrea Carla; Rodrigues, Alfredo J.; Vicente, Walter Vilella A.; Evora, Paulo Roberto B.

    2016-01-01

    OBJECTIVE: To examine if methylene blue (MB) can counteract or prevent protamine (P) cardiovascular effects. METHODS: The protocol included five heparinized pig groups: Group Sham -without any drug; Group MB - MB 3 mg/kg infusion; Group P - protamine; Group P/MB - MB after protamine; Group MB/P - MB before protamine. Nitric oxide levels were obtained by the nitric oxide/ozone chemiluminescence method, performed using the Nitric Oxide Analizer 280i (Sievers, Boulder, CO, USA). Malondialdehyde plasma levels were estimated using the thiobarbiturate technique. RESULTS: 1) Groups Sham and MB presented unchanged parameters; 2) Group P - a) Intravenous protamine infusion caused mean arterial pressure decrease and recovery trend after 25-30 minutes, b) Cardiac output decreased and remained stable until the end of protamine injection, and c) Sustained systemic vascular resistance increased until the end of protamine injection; 3) Methylene blue infusion after protamine (Group P/MB) - a) Marked mean arterial pressure decreased after protamine, but recovery after methylene blue injection, b) Cardiac output decreased after protamine infusion, recovering after methylene blue infusion, and c) Sustained systemic vascular resistance increased after protamine infusion and methylene blue injections; 4) Methylene blue infusion before protamine (Group MB/P) - a) Mean arterial pressure decrease was less severe with rapid recovery, b) After methylene blue, there was a progressive cardiac output increase up to protamine injection, when cardiac output decreased, and c) Sustained systemic vascular resistance decreased after protamine, followed by immediate Sustained systemic vascular resistance increase; 5) Plasma nitrite/nitrate and malondialdehyde values did not differ among the experimental groups. CONCLUSION: Reviewing these experimental results and our clinical experience, we suggest methylene blue safely prevents and treats hemodynamic protamine complications, from the endothelium

  7. Toward a Unified Mechanism for Oxoammonium Salt-Mediated Oxidation Reactions: A Theoretical and Experimental Study Using a Hydride Transfer Model.

    PubMed

    Hamlin, Trevor A; Kelly, Christopher B; Ovian, John M; Wiles, Rebecca J; Tilley, Leon J; Leadbeater, Nicholas E

    2015-08-21

    A range of oxoammonium salt-based oxidation reactions have been explored computationally using density functional theory (DFT), and the results have been correlated with experimentally derived trends in reactivity. Mechanistically, most reactions involve a formal hydride transfer from an activated C-H bond to the oxygen atom of the oxoammonium cation. Several new potential modes of reactivity have been uncovered and validated experimentally.

  8. Experimental investigation of the 19F( n, α)16N reaction excitation function in the neutron energy range of 4 to 7.35 MeV

    NASA Astrophysics Data System (ADS)

    Bondarenko, I. P.; Khryachkov, V. A.; Ivanova, T. A.; Kuz'minov, B. D.; Semenova, N. N.; Sergachev, A. I.

    2013-07-01

    The interaction of neutrons with light nuclei study is of interest for understanding nuclear-reaction mechanisms. Fluorine nuclei are worth particular attention because they are abundant in the core of the promising molten-salt reactors and can noticeably affect the chain reaction kinetics. In this work we have experimentally investigated the 19F( n, α)16N reaction cross-section at neutron energies ranging from 4 to 7.35 MeV.

  9. Experimental determination of the activation energies of CH4 , SO2 and O2 reactions on Cr2O3 / γ -Al2O3

    NASA Astrophysics Data System (ADS)

    Hernández Guiance, S. N.; Coria, I. D.; Irurzun, I. M.; Mola, E. E.

    2016-09-01

    In the present work we experimentally determine the activation energies of CH4,SO2 and O2 reactions on Cr2O3 / γ -Al2O3 . To our knowledge there is no previous determination of these parameters, so fundamental information is provided to determine the velocity laws of these reactions and understand their kinetic behavior.

  10. Experimental study of the 66Ni(d ,p ) 67Ni one-neutron transfer reaction

    NASA Astrophysics Data System (ADS)

    Diriken, J.; Patronis, N.; Andreyev, A.; Antalic, S.; Bildstein, V.; Blazhev, A.; Darby, I. G.; De Witte, H.; Eberth, J.; Elseviers, J.; Fedosseev, V. N.; Flavigny, F.; Fransen, Ch.; Georgiev, G.; Gernhauser, R.; Hess, H.; Huyse, M.; Jolie, J.; Kröll, Th.; Krücken, R.; Lutter, R.; Marsh, B. A.; Mertzimekis, T.; Muecher, D.; Orlandi, R.; Pakou, A.; Raabe, R.; Randisi, G.; Reiter, P.; Roger, T.; Seidlitz, M.; Seliverstov, M.; Sotty, C.; Tornqvist, H.; Van De Walle, J.; Van Duppen, P.; Voulot, D.; Warr, N.; Wenander, F.; Wimmer, K.

    2015-05-01

    The quasi-SU(3) sequence of the positive parity ν g9 /2,d5 /2,s1 /2 orbitals above the N =40 shell gap are assumed to induce strong quadrupole collectivity in the neutron-rich Fe (Z =26 ) and Cr (Z =24 ) isotopes below the nickel region. In this paper the position and strength of these single-particle orbitals are characterized in the neighborhood of 68Ni (Z =28 ,N =40 ) through the 66Ni(d ,p )67Ni one-neutron transfer reaction at 2.95 MeV/nucleon in inverse kinematics, performed at the REX-ISOLDE facility in CERN. A combination of the Miniball γ -array and T-REX particle-detection setup was used and a delayed coincidence technique was employed to investigate the 13.3-μ s isomer at 1007 keV in 67Ni. Excited states up to an excitation energy of 5.8 MeV have been populated. Feeding of the ν g9 /2 (1007 keV) and ν d5 /2 (2207 keV and 3277 keV) positive-parity neutron states and negative parity (ν p f ) states have been observed at low excitation energy. The extracted relative spectroscopic factors, based on a distorted-wave Born approximation analysis, show that the ν d5 /2 single-particle strength is mostly split over these two excited states. The results are also compared to the distribution of the proton single-particle strength in the 90Zr region (Z =40 ,N =50 ) .

  11. Parylene-encapsulated copolymeric membranes as localized and sustained drug delivery platforms.

    PubMed

    Chen, Mark; Huang, Houjin; Pierstorff, Erik; Shin, Eric; Robinson, Erik; Ho, Dean

    2009-10-01

    Parylene is a biologically inert material capable of being deposited in conformal nanoscale layers on virtually any surface, making it a viable structural material for the fabrication of drug delivery devices, as well as implant coatings, sensors, and other biomedical technologies. Here we explore its novel drug delivery applications by using parylene to package the polymethyloxazoline-polydimethylsiloxane-polymethyloxazoline (PMOXA-PDMS-PMOXA) block copolymer membrane of a nanoscale thickness (approximately 4 nm/layer) mixed with a therapeutic element, creating an active parylene-encapsulated copolymeric (APC) membrane for slow release drug delivery of dexamethasone (Dex), a potent anti-inflammatory and immunosuppressant synthetic glucocorticoid. Given current needs for localized therapeutic release for conditions such as cancer, post-surgical inflammation, wound healing, regenerative medicine, to name a few, this stand-alone and minimally invasive implantable technology may impact a broad range of medical scenarios. To evaluate the applicability of the APC membrane as a biocompatible drug delivery system, real-time polymerase chain reaction (RT-PCR) was performed to investigate the expression of cytokines that regulate cellular stress and inflammation as a result of in vitro RAW264.7 macrophage cell growth on the APC membrane. Significant decreases in relative mRNA levels of IL-6, TNF-alpha, and iNOS were observed. Dex functionalized APC membranes were further found to effectively slow-elute the drug via confocal microscopy, with a confirmed extended elution capability over a period of several days, undergoing phosphate buffered saline washes between time points. In addition, we examined the membrane surface through atomic force microscopy (AFM) to examine Dex/copolymer deposition, and to characterize the surface of the APC membrane. Furthermore, we evaluated the effects of incubation with the APC membrane in solution on macrophage growth behavior and cellular

  12. Free radical (co)polymerization of methyl methacrylate and styrene in room temperature ionic liquids

    NASA Astrophysics Data System (ADS)

    Zhang, Hongwei

    Conventional free radical polymerizations were carried out in a variety of room temperature ionic liquids (RTILs). Generally, methyl methacrylate (MMA) and styrene (St) were used as typical monomers to compare the polymerization behavior both in RTILs and in common volatile organic compound solvents (VOCs). In most cases, it was observed that both yields and molecular weights are enhanced in the RTIL. While we believe the "diffusion-controlled termination" mechanism makes the termination of the radical propagating chains difficult due to the highly viscous nature of RTIL, other researchers have suggested that the rapid polymerization rates are due to the high polarity of these reaction media. By employing more than a dozen RTILs with a wide range of anions and cations, we attempted to correlate the viscosity and polarity of the RTILs with the molecular weights and polymerization rates. This correlation was not successful, suggesting that other parameters may also play a role in affecting the polymerization behavior. Other kinds of polymerizations have also been attempted including nitroxide-mediated living radical polymerizations of St and MMA in 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM]PF6), and redox initiation system initiated polymerization of MMA through redox pair formed by cation of trihexyl-tetradecyl-phosphonium bis(2,4,4-trimethylpentyl) phosphinate ([H3TDP] [(PM3) 2P]) and BPO. The formation of PSt-b-PMMA by sequential monomer addition through the standard free radical polymerization mechanism, using BPO as initiator, can be realized in [BMIM]PF6 due to the insolubility of polymerized first block---PSt in [BMIM]PF6. The macroradicals wrapped inside the chain coils have prolonged lifetimes because of the diminished termination, which allow some of these radicals to initiate polymerization of MMA at room temperature to form diblock copolymer. Solvents effects on reactivity ratios for free radical statistical copolymerization have been

  13. Theoretical and experimental investigation of carnosine and its oxygenated adducts. The reaction with the nickel ion

    NASA Astrophysics Data System (ADS)

    Pavlos, Dimitrios; Petropouleas, Panayiotis; Hatzipanayioti, Despina

    2015-11-01

    DFT theoretical calculations at B3LYP/TZVP or LANL2DZ level of theory, for neutral, zwitterions, protonated and anionic carnosine, were performed. Energies, the structural and spectroscopic parameters were calculated in the gas phase and aqueous medium. Additional H-bonds stabilize the ionized forms of carnosine, creating "nests" into which metal ions or bio-molecules may be sheltered. Based on Fukui functions, the reactivity of the abovementioned forms of carnosine, with 1O2, may lead to oxygenated species. The theoretical spectroscopic parameters have been correlated to our experimental results. The effect of H2O2 and the electrochemistry of aqueous carnosine solutions were examined. Theoretical models containing Ni(II), carnosine and water were constructed. In the isolated mauve solid, formulated [Ni(carn)2(H2O)5], the COOsbnd , Nπ and/or NH2 were bonded. When H2O2 was added, the imidazole NMR signals disappeared. A redox couple clearly indicates one electron process, the electron coming from either the oxidation of imidazole ring or the nickel(II)/Ni(III) couple.

  14. Angelica Sinensis attenuates inflammatory reaction in experimental rat models having spinal cord injury.

    PubMed

    Xu, Jun; E, Xiao-Qiang; Liu, Hui-Yong; Tian, Jun; Yan, Jing-Long

    2015-01-01

    This study was aimed to evaluate the effect of Angelica Sinensis on experimental rat models in which spinal cord injury was induced by studying different factors. Different factors causing inflammation play a key role in pathophysiology of SCI. Here three groups of rats (n=15, each was used). These included a sham control group where only laminectomy was performed, SCI group where SCI was induced and AS/SCI group where although SCI was induced but Angelica Sinensis was also administered to study its effect and draw a comparison with control. The expression of I-kBα and NF-kB p65 was also studied using western blotting and after recording optical density (OD) values of western blots. MPO activity was used to measure the effect of 20 mg/kg Angelica Sinensis. The levels of proinflammatory cytokines TNF-α, IL-1β and IL-6 were also studied. As compared with SCI group and sham control it was observed that Angelica Sinensis significantly reduced the expression of I-kBα and NF-kB p65, (P<0.05), while MPO activity was also significantly reduced. Proinflammatory cytokine level was also reduced in treated group as compared to both other groups. On the basis of this study we concluded that the use of 20 mg/kg Angelica Sinensis in rat models can attenuate the secondary damage caused by SCI and thus help in controlling the pathology of SCI in rats.

  15. The reaction mechanism of allene oxide synthase: Interplay of theoretical QM/MM calculations and experimental investigations.

    PubMed

    Cho, Kyung-Bin; Lai, Wenzhen; Hamberg, Mats; Raman, C S; Shaik, Sason

    2011-03-01

    A combined theoretical and experimental study highlights the reaction mechanism of allene oxide synthase (AOS) and its possible link to hydroperoxide lyase (HPL) pathway. A previously published study (Lee et al., Nature 455 (2008) 363) has shown that the F137 residue is of central importance in differentiating between the AOS and HPL pathways after initial identical steps. In the experimental part of this study, we show that wild-type AOS from Arabidopsis or rice in fact produces both AOS and HPL products in a ratio of about 80:15, something that was found only in trace amounts before. Theoretical calculations successfully map the whole AOS pathway with 13(S)-hydroperoxy linolenic and linoleic acid as substrates. Subsequent calculations investigated the effects of in silico F137L mutation at the suggested diverging point of the two pathways. The results show that QM/MM calculations can reasonably reproduce three out of four experimentally available cases, and confirm that the pathways are energetically very close to each other, thus making a switch from one path to other plausible under different circumstances.

  16. The kinetics of clumped-isotope reactions in calcite and apatite from natural and experimental samples

    NASA Astrophysics Data System (ADS)

    Stolper, D. A.; Eiler, J. M.

    2014-12-01

    Measurements of clumped isotopes of carbonate-bearing minerals are a powerful tool for reconstructing past surface temperatures and thermal histories of shallow crustal rocks. Because the clumped-isotope thermometer is based on homogenous-phase equilibrium, a sample's clumped-isotope temperature is susceptible to resetting through, for example, intracrystalline diffusion and redistribution of C and O isotopes during (re)heating or slow cooling. Quantitative knowledge of the kinetics of this resetting have received increasing attention (1-3) and is critical for understanding the meaning of clumped-isotope temperatures of samples with complex burial histories. To better constrain these kinetics and complement previous work (1-3) we performed heating experiments (400-700°C) on optical calcites and carbonate-bearing apatites. As previously observed (2-3), calcites exhibit non-first-order kinetics. The data were fit using a model that incorporates both diffusion and isotope-exchange reactions (4). The kinetics derived with this model using the optical-calcite heating experiments of (2) and those measured here are indistinguishable. The model predicts that subtle changes (>10°C) in measured calcite clumped-isotope temperatures can occur at burial temperatures between 60-100°C on million-year timescales. Though small, such changes may have an impact on clumped-isotope-based reconstructions of past surface temperatures and thermal histories. The derived kinetics were compared to clumped-isotope measurements of cogenetic calcites and apatites from slowly cooled carbonatite intrusions. Apparent temperatures are 70-140°C for apatites and 120-190°C for calcites. Measured temperatures for calcites match modeled temperatures using reasonable geological cooling rates. Natural apatite samples yield lower apparent temperatures than predicted based on the model. We propose that this difference is the result of annealment of structural damage in apatites (e.g., generated by

  17. Gut pain reactions in man: an experimental investigation using short and long duration transmucosal electrical stimulation.

    PubMed

    Arendt-Nielsen, L; Drewes, A M; Hansen, J B; Tage-Jensen, U

    1997-02-01

    Visceral pain is a substantial, clinical problem but unfortunately few experimental models are available to study this phenomenon in man. In the present study we inserted a stimulation catheter 5-10 cm into the ileo-sigmoidostomy of nine patients. The catheter contained six small, flexible electrodes separated by 4 mm. The gut was stimulated by single burst, repeated burst (five stimuli delivered at 2 Hz), or continuous burst stimuli (4 Hz for 30, 60, 90, and 120 s). The sensation (ST), pain detection (PDT), and pain tolerance (PTT) thresholds to single/repeated burst stimuli were determined. The location/size/sensitivity of referred pain after repeated/continuous stimulation were characterized. The brain potentials to single burst stimuli and to increasing stimulus intensity were measured. ST to single burst stimuli was easy to determine (8 mA) and to reproduce. The patients found it difficult to determine the PDT and PTT to single burst stimuli, however both thresholds were easily determined for repeated burst stimuli. The pain thresholds to single burst stimuli were twice as high as the thresholds to repeated burst stimuli, indicating the importance of central temporal summation for visceral pain. Minor changes in the stimulus location resulted in changes of the referred pain projection site. The words most frequently selected (78%) from the McGill Pain Questionnaire to describe repeated burst stimulations were shooting, pricking, flashing, and boring. The amplitude of the brain potentials increased at increasing stimulus intensity. A stimulus intensity giving an initial pain rating of around 5 on a 0-10 visual analog scale (VAS) was used for continuous stimulation. A general increase of the pain intensity and the area of referred pain was found during this stimulation. It was concluded that electrical stimulation of the human gut provokes pain and especially long sequences of visceral stimuli are adequate to evoke referred pain mimicking pain profiles of

  18. Zwitterionic monomer graft copolymerization onto polyurethane surface through a PEG spacer

    NASA Astrophysics Data System (ADS)

    Huang, Jingjing; Xu, Weilin

    2010-04-01

    A new zwitterionic surface was obtained by a novel three-step grafting procedure. The zwitterionic monomer was introduced by cerium-induced graft copolymerization in the presence of N,N'-methylene bisacrylamide (MBAA) as cross-linking agent. Attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS) analysis confirmed the MBAA could stimulate zwitterionic monomer grafting onto the membrane surface. Surface properties were also determined by atomic force microscope (AFM) and water contact angle. The hemocompatibility of the modified PU membranes was evaluated by the activated partial thromboplastin time (APTT), thrombin time (TT) and prothrombin time (PT). The TT and APTT of PU were significantly prolonged by the zwitterion of sulfobetaine monomer grafting copolymerization. The new polyurethane membrane could have a great potential in biomedical applications.

  19. Antimicrobial cotton containing N-halamine and quaternary ammonium groups by grafting copolymerization

    NASA Astrophysics Data System (ADS)

    Liu, Ying; Liu, Yin; Ren, Xuehong; Huang, T. S.

    2014-03-01

    The monomer (3-acrylamidopropyl)trimethylammonium chloride (APTMAC) was used to treat cotton fibers by grafting copolymerization. The grafted cotton fabrics were characterized by SEM image and FTIR spectra. The treated samples with quaternary ammonium groups could decrease 96.08% of Staphylococcus aureus and 48.74% of Escherichia coli O157:H7 within 30 min. After chlorination with dilute sodium hypochlorite, the treated cotton fabrics containing both N-halamine and quaternary ammonium groups effectively inactivated 100% (log reduction 5.82) of S. aureus and 100% (log reduction 6.26) of E. coli O157:H7 within 5 min of contact time. The grafting process of cotton fabric has small effect on the thermal stability and tensile strength, which favors the practical application. Compared to the traditional pad-dry-cure method to produce antibacterial materials, the radical grafting copolymerization method occurred in water without any organic solvents involved in the whole treatment.

  20. Fabrication of microarray of gel-immobilized compounds on a chip by copolymerization.

    SciTech Connect

    Vasiliskov, A. V.; Timofeev, E. N.; Surzhikov, S. A.; Drobyshev, A. L.; Shick, V. V.; Mirzabekov, A. D.; Biochip Technology Center; Engelhardt Inst. of Molecular Biology; Moscow Inst. of Physics and Technology

    1999-09-01

    The manufacturing of microchips containing oligonucleotides and proteins immobilized within gel pads, ranging in size from 10 x 10 to 100 x 100 {mu}m, is described. The microchips are produced by photo- or persulfate-induced copolymerization of unsaturated derivatives of biomolecules with acrylamide-bisacrylamide mixture. Oligonucleotides containing 5'-allyl or 5'-butenediol units were synthesized using standard phosphoramidite chemistry. Acryloyl residues were attached to a protein by a twostep procedure. Photopolymerization was induced by illumination of the monomer solution containing initiator with UV light through the mask. The mask was applied directly over the monomer solution or projected through a microscope. Alternatively, copolymerization was carried out in drops of aqueous solution of monomers containing ammonium persulfate. Drops with different allyl-oligonucleotides were distributed on a glass slide, and the polymerization was induced by diffusion of N,N,N',N'-tetramethylethylenediamine (TEMED) from a hexane solution that covered the aqueous drops.

  1. Asymmetric Alternating Copolymerization of Meso-epoxides and Cyclic Anhydrides: Efficient Access to Enantiopure Polyesters.

    PubMed

    Li, Jie; Liu, Ye; Ren, Wei-Min; Lu, Xiao-Bing

    2016-09-14

    Synthesis of stereoregular polyesters with main-chain chirality was achieved for the first time by the asymmetric copolymerization of meso-epoxides and cyclic anhydrides using catalyst systems based on enantiopure bimetallic complexes. The combination of the biphenol-linked dinuclear aluminum complex with tert-butyl groups in the phenolate ortho-positions and a nucleophilic co-catalyst was found to be more efficient in catalyzing this asymmetric copolymerization, affording enantiomerically enriched polyesters (up to 91% ee) with completely alternating structure and narrow molecular weight distribution. It was discovered that the isotactic-enriched poly(cyclopentene phthalate) is a typical semicrystalline material with a melting endothermic peak at 221 °C. This study is expected to provide a promising route to prepare various stereoregular polyesters having a wide variety of physical properties and degradability. PMID:27562940

  2. Aluminum pigment encapsulated by in situ copolymerization of styrene and maleic acid

    NASA Astrophysics Data System (ADS)

    Liu, Hui; Ye, Hongqi; Tang, Xinde

    2007-11-01

    To improve its anticorrosion property, aluminum pigment was encapsulated by in situ copolymerization of styrene (St) and maleic acid (MA). It was found that the conversion of monomers (C), the percentage of grafting (PG) and the grafting efficiency (GE) could attain 92%, 12%, 25%, respectively, when m(BPO)/ m(St + MA) = 10% and m(St + MA)/ m(Al) = 10%. The optimum condition for protection factor was studied according to an orthogonal testing. When m(St + MA)/ m(Al) was 20%, the encapsulated aluminum pigment simultaneously showed good anticorrosion property and luster. FTIR, SEM and particle size analysis indicated that aluminum pigment had been successfully encapsulated with styrene-maleic acid copolymer by in situ copolymerization, which remarkably improved its anticorrosion property and the chelate complex formed between SMA and Al(III) was possibly the actual corrosion inhibitor.

  3. Experimental study of bound states in 12Be through low-energy 11Be(d,p)-transfer reactions

    NASA Astrophysics Data System (ADS)

    Johansen, J. G.; Bildstein, V.; Borge, M. J. G.; Cubero, M.; Diriken, J.; Elseviers, J.; Fraile, L. M.; Fynbo, H. O. U.; Gaffney, L. P.; Gernhäuser, R.; Jonson, B.; Koldste, G. T.; Konki, J.; Kröll, T.; Krücken, R.; Mücher, D.; Nilsson, T.; Nowak, K.; Pakarinen, J.; Pesudo, V.; Raabe, R.; Riisager, K.; Seidlitz, M.; Tengblad, O.; Törnqvist, H.; Voulot, D.; Warr, N.; Wenander, F.; Wimmer, K.; De Witte, H.

    2013-10-01

    The bound states of 12Be have been studied through a 11Be(d,p)12Be transfer reaction experiment in inverse kinematics. A 2.8 MeV/u beam of 11Be was produced using the REX-ISOLDE facility at CERN. The outgoing protons were detected with the T-REX silicon detector array. The MINIBALL germanium array was used to detect gamma rays from the excited states in 12Be. The gamma-ray detection enabled a clear identification of the four known bound states in 12Be, and each of the states has been studied individually. Differential cross sections over a large angular range have been extracted. Spectroscopic factors for each of the states have been determined from distorted wave Born approximation (DWBA) calculations and have been compared to previous experimental and theoretical results.

  4. Reactions of ruthenium and rhodium atoms with carbon monoxide and dinitrogen mixtures: a combined experimental and theoretical study.

    PubMed

    Jiang, Ling; Lu, Zhang-Hui; Xu, Qiang

    2010-02-01

    Laser-ablated Ru and Rh atoms react with CO and N(2) mixture in excess neon to produce the carbonylmetal dinitrogen complexes, (NN)(n)MCO (M=Ru,Rh; n=1,2) and NNRu(CO)(2), as well as metal carbonyls and dinitrogen complexes. These carbonylmetal dinitrogen complexes are characterized using infrared spectroscopy on the basis of the results of the isotopic substitution and mixed isotopic splitting patterns. Density functional theory calculations have been performed on these complexes. Overall agreement between the experimental and calculated vibrational frequencies, relative absorption intensities, and isotopic shifts supports the identification of these species from the matrix infrared spectra. Furthermore, a plausible reaction pathway for the formation of the products has been proposed. This work reveals that the reactivity of Ru and Rh atoms toward CO is prior to N(2).

  5. Preparation and characterization of PVDF-glass fiber composite membrane reinforced by interfacial UV-grafting copolymerization.

    PubMed

    Luo, Nan; Xu, Rongle; Yang, Min; Yuan, Xing; Zhong, Hui; Fan, Yaobo

    2015-12-01

    A novel inorganic-organic composite membrane, namely poly(vinylidene fluoride) PVDF-glass fiber (PGF) composite membrane, was prepared and reinforced by interfacial ultraviolet (UV)-grafting copolymerization to improve the interfacial bonding strength between the membrane layer and the glass fiber. The interfacial polymerization between inorganic-organic interfaces is a chemical cross-linking reaction that depends on the functionalized glass fiber with silane coupling (KH570) as the initiator and the polymer solution with acrylamide monomer (AM) as the grafting block. The Fourier transform infrared spectrometer-attenuated total reflectance (FTIR-ATR) spectra and the energy dispersive X-ray (EDX) pictures of the interface between the glass fiber and polymer matrix confirmed that the AM was grafted to the surface of the glass fiber fabric and that the grafting polymer was successfully embedded in the membrane matrix. The formation mechanisms, permeation, and anti-fouling performance of the PGF composite membrane were measured with different amounts of AM in the doping solutions. The results showed that the grafting composite membrane improved the interfacial bonding strength and permeability, and the peeling strength was improved by 32.6% for PGF composite membranes with an AM concentration at 2wt.%.

  6. Synthesis of α(1→4)-linked non-natural mannoglucans by α-glucan phosphorylase-catalyzed enzymatic copolymerization.

    PubMed

    Baba, Ryotaro; Yamamoto, Kazuya; Kadokawa, Jun-Ichi

    2016-10-20

    α-Glucan phosphorylase catalyzes enzymatic polymerization of α-d-glucose 1-phosphate (Glc-1-P) as a monomer from a maltooligosaccharide primer to produce α(1→4)-glucan, i.e., amylose, with liberating inorganic phosphate (Pi). Because of quite weak specificity for the recognition of substrates by thermostable α-glucan phosphorylase (from Aquifex aeolicus VF5), in this study, we investigated the enzymatic copolymerization of Glc-1-P with its analogue monomer, α-d-mannose 1-phosphate (Man-1-P) under the conditions for removal of Pi as the precipitate with ammonium and magnesium in ammonia buffer containing Mg(2+) ion to produce α(1→4)-linked non-natural mannoglucans composed of Glc/Man units. The reaction was conducted in different feed ratios using the maltotriose primer at 40°C for 7days. The MALDI-TOF mass and (1)H NMR spectra of the products fully supported the mannoglucan structures. PMID:27474652

  7. Porous polymer monoliths with large surface area and functional groups prepared via copolymerization of protected functional monomers and hypercrosslinking.

    PubMed

    Maya, Fernando; Svec, Frantisek

    2013-11-22

    A new approach to the preparation of porous polymer monoliths possessing both large surface area and functional groups has been developed. The chloromethyl groups of poly(styrene-co-4-acetoxystyrene-co-vinylbenzyl chloride-co-divinylbenzene) monolith enable post-polymerization hypercrosslinking catalyzed by ferric chloride in dichloroethane leading to a multitude of small pores thus enhancing the surface area. The acetoxy functionalities are easily deprotected using hydrazine to produce polar phenolic hydroxyl groups, which would be difficult to obtain by direct copolymerization of hydroxyl-containing monomers. The hypercrosslinking and deprotection reactions as well as their sequence were studied in detail with bulk polymer monoliths containing up to 50% 4-acetoxystyrene and its progress monitored by infrared spectrometry and nitrogen adsorption/desorption measurements. No significant difference was found for both possible successions. All monoliths were also prepared in a capillary column format, then deprotected and hypercrosslinked. Capillary columns were tested for the separation of small molecules using reversed phase and normal phase chromatographic modes. For polymer monoliths containing 50% deprotected 4-acetoxystyrene, column efficiencies of 40,000 plates/m for benzene in reversed phase mode and 31,800 plates/m for nitrobenzene in normal phase mode, were obtained. The percentage of hydroxyl groups in the monoliths enables modulation of polarity of the stationary phase. They also represent functionalities that are potentially suitable for further modifications and formation of new types of stationary phases for liquid chromatography.

  8. Influence of experimental parameters on sonochemistry dosimetries: KI oxidation, Fricke reaction and H2O2 production.

    PubMed

    Merouani, Slimane; Hamdaoui, Oualid; Saoudi, Fethi; Chiha, Mahdi

    2010-06-15

    Central events of the ultrasonic action are the cavitation bubbles that can be considered as microreactors. Adiabatic collapse of cavitation bubbles leads to the formation of reactive species such as hydroxyl radicals (*OH), hydrogen peroxide (H(2)O(2)) and hydroperoxyl radicals (HOO*). Several chemical methods were used to detect the production of these reactive moieties in sonochemistry. In this work, the influence of several operational parameters on the sonochemistry dosimetries namely KI oxidation, Fricke reaction and H(2)O(2) production using 300 kHz ultrasound was investigated. The main experimental parameters showing significant effect in KI oxidation dosimetry were initial KI concentration, acoustic power and pH. The solution temperature showed restricted influence on KI oxidation. The acoustic power and liquid temperature highly affected Fricke reaction dosimetry. Operational conditions having important influence on H(2)O(2) formation were acoustic power, solution temperature and pH. For the three tested dosimetries, the sonochemical efficiency was independent of liquid volume. PMID:20211524

  9. Immunologic and inflammatory reactions to exogenous stem cells implications for experimental studies and clinical trials for myocardial repair.

    PubMed

    Buja, L Maximilian; Vela, Deborah

    2010-11-16

    Intense research is under way to determine the optimal stem cell type and regimen for repairing diseased myocardium. Although initial studies in humans focused on the use of homologous stem cells, allogeneic or xenogeneic stem cells have been studied extensively in experimental work. Clinical trials with allogeneic stem cells are now under way, an approach based on the premise that stem cells and precursor cells are characterized as being immunotolerant. However, evidence indicates that stem cells may gain immune potency in vivo, especially when delivered to inflamed tissue, such as acutely infarcted myocardium. Histopathologic studies show the presence of a lymphohistiocytic inflammatory reaction at the sites of delivery of allogeneic stem cells, a response that is exaggerated with the use of xenogeneic stem cells. The immune-mediated inflammatory reaction to allogeneic and xenogeneic stem cells may elicit a spectrum of effects, ranging from beneficial (e.g., increased paracrine activity) to detrimental (e.g., accelerated damage and removal of stem cells). Although the issue of immune-mediated inflammatory responses to non-self stem cells requires further evaluation, non-self stem cells should not be considered as immunologically inert or exclusively immunosuppressive in vivo.

  10. Experimental differential cross sections, level densities, and spin cutoffs as a testing ground for nuclear reaction codes

    SciTech Connect

    Voinov, Alexander V.; Grimes, Steven M.; Brune, Carl R.; Burger, Alexander; Gorgen, Andreas; Guttormsen, Magne; Larsen, Ann -Cecilie; Massey, Thomas N.; Siem, Sunniva

    2013-11-08

    Proton double-differential cross sections from 59Co(α,p)62Ni, 57Fe(α,p)60Co, 56Fe(7Li,p)62Ni, and 55Mn(6Li,p)60Co reactions have been measured with 21-MeV α and 15-MeV lithium beams. Cross sections have been compared against calculations with the empire reaction code. Different input level density models have been tested. It was found that the Gilbert and Cameron [A. Gilbert and A. G. W. Cameron, Can. J. Phys. 43, 1446 (1965)] level density model is best to reproduce experimental data. Level densities and spin cutoff parameters for 62Ni and 60Co above the excitation energy range of discrete levels (in continuum) have been obtained with a Monte Carlo technique. Furthermore, excitation energy dependencies were found to be inconsistent with the Fermi-gas model.

  11. Hydration of periclase at 350 ∘ C to 620 ∘ C and 200 MPa: experimental calibration of reaction rate

    NASA Astrophysics Data System (ADS)

    Kuleci, H.; Schmidt, C.; Rybacki, E.; Petrishcheva, E.; Abart, R.

    2016-02-01

    The hydration of periclase to brucite was investigated experimentally. Single crystals of periclase machined to millimeter sized cubes with (100) surfaces were reacted with distilled water at temperatures of 350 to 620 ∘C and a pressure of 200 MPa for run durations of 5 to 40 minutes. Hydration produced a layer of brucite covering the surface of periclase. While the shrinking periclase largely retained its cube shape a surface roughness developed on the μm scale and eventually outward pointing spikes bounded by (111) faces emerged on the retreating faces of the periclase due to kinetic selection of less reactive (111) and (110) surfaces. The periclase to brucite conversion followed a linear rate law, where the reaction rate increased from 350 to 530 ∘C and then decreased towards higher temperature and finally vanished at about 630 ∘C, where periclase, brucite, and water are in equilibrium at 200 MPa. The overall kinetics of the hydration reaction is conveniently described in terms of a phenomenological interface mobility. Measuring the velocity of the hydration front relative to the lattice of the reactant periclase, the temperature dependence of its mobility is described by an Arrhenius relation with pre-exponential factor 1.7.10-12 m 4/s.J and activation energy of E A =55 kJ/mol.

  12. Random and block copolymerization in metal oxide gel synthesis from metalorganic compounds

    NASA Technical Reports Server (NTRS)

    Mukherjee, S. P.

    1985-01-01

    The introduction and development of the block copolymerization concept in metal oxide gel synthesis will in the future generate a new class of glass/microcrystalline materials. By the year 2004, better scientific understanding of the chemical principles controlling the distribution of network formers or modifiers in silicate gels will permit the synthesis of architecturally well-defined block polymers with unique high-performance behavior.

  13. Nickel(0)-catalyzed cycloaddition copolymerization involving two diynes and carbon dioxide to poly(2-pyrone)

    SciTech Connect

    Tsuda, Tetsuo; Ooi, Osamu; Maruta, Ken-ichi )

    1993-08-01

    A copolymerizability order of five diynes, i.e., 3,11-tetradecadiyne (A), 2,6-octadiyne (B), 1,4-di(2-hexynyl)benzene (C), 1,3-di(2-hexynyl)benzene (D), and 1,7-cyclotridecadiyne (E), in the nickel(0)-catalyzed 1:1 cycloaddition copolymerization of the diyne with CO[sub 2] to the poly(2-pyrone) was determined by the nickel(0)-catalyzed copolymerization involving two diynes and CO[sub 2]. The copolymerizability order obtained by analyzing the copolymer composition using [sup 1]H NMR spectroscopy was A [gt] E [gt] B [gt] C [gt] D. This order was explained in terms of the steric hindrance exerted by the substituent on the terminal C[triple bond]C bond of the cooligomer or the copolymer to its cycloaddition along with mobility of its terminal C[triple bond]C bond moiety for the cycloaddition. An order of cycloaddition reactivity of the diyne, which is related to formation of the cooligomer, was determined by measuring the unreacted diyne in the copolymerization involving five diynes and CO[sub 2] using gas chromatography. The result was E [gt] B [gt] C [gt] D [gt] A. Thus high copolymerizability of diyne A is noteworthy.

  14. A comparison of tissue reaction to MTA and an experimental root-end restorative material in rats.

    PubMed

    Modaresi, Jalil; Yavari, S Amir Saeid; Dianat, S Omid; Shahrabi, Shokufeh

    2005-08-01

    The purpose of this study was to compare the biocompatibility of a new experimental root-end filling material, "Cold Ceramic" (CC), with mineral trioxide aggregate (MTA) in rats. After anaesthetising 10 rats and raising tissue flaps, tablets of the material were placed subcutaneously. Five rats were followed for seven days and five for 30 days. An incision without any implanted material was used as a control. Histological analyses were performed with regard to number, type and location of the inflammatory cells and type of surrounding tissue. Kruskal-Wallis and Mann-Whitney statistical tests were used. Comparing inflammatory reactions between the two experimental groups (MTA and CC) and the control group showed significant differences after seven days (p = 0.031). There were no significant differences between CC and MTA groups after seven days (p = 0.222) and after 30 days (p = 0.063). The results suggested that MTA and CC are both biocompatible. It appears that MTA induces less inflammatory response in short periods of observation, but CC may be more biocompatible for slightly longer periods.

  15. An experimental study of catalytic and non-catalytic reaction in heat recirculating reactors and applications to power generation

    NASA Astrophysics Data System (ADS)

    Ahn, Jeongmin

    An experimental study of the performance of a Swiss roll heat exchanger and reactor was conducted, with emphasis on the extinction limits and comparison of results with and without Pt catalyst. At Re<40, the catalyst was required to sustain reaction; with the catalyst self-sustaining reaction could be obtained at Re less than 1. Both lean and rich extinction limits were extended with the catalyst, though rich limits were extended much further. At low Re, the lean extinction limit was rich of stoichiometric and rich limit had equivalence ratios 80 in some cases. Non-catalytic reaction generally occurred in a flameless mode near the center of the reactor. With or without catalyst, for sufficiently robust conditions, a visible flame would propagate out of the center, but this flame could only be re-centered with catalyst. Gas chromatography indicated that at low Re, CO and non-C3 H8 hydrocarbons did not form. For higher Re, catalytic limits were slightly broader but had much lower limit temperatures. At sufficiently high Re, catalytic and gas-phase limits merged. Experiments with titanium Swiss rolls have demonstrated reducing wall thermal conductivity and thickness leads to lower heat losses and therefore increases operating temperatures and extends flammability limits. By use of Pt catalysts, reaction of propane-air mixtures at temperatures 54°C was sustained. Such low temperatures suggest that polymers may be employed as a reactor material. A polyimide reactor was built and survived prolonged testing at temperatures up to 500°C. Polymer reactors may prove more practical for microscale devices due to their lower thermal conductivity and ease of manufacturing. Since the ultimate goal of current efforts is to develop combustion driven power generation devices at MEMS like scales, a thermally self-sustaining miniature power generation device was developed utilizing a single-chamber solid-oxide-fuel-cell (SOFC) placed in a Swiss roll. With the single-chamber design

  16. The dynamical role of solvent on the ICN photodissociation reaction: connecting experimental observables directly with molecular dynamics simulations.

    PubMed

    Rivera, Christopher A; Winter, Nicolas; Harper, Rachael V; Benjamin, Ilan; Bradforth, Stephen E

    2011-05-14

    The ICN photodissociation reaction is the prototype system for understanding energy disposal and curve crossing in small molecule bond-breaking. The wide knowledge base on this reaction in the gas phase makes it an excellent test case to explore and understand the influence of a liquid solvent on the photo-induced reaction dynamics. Molecular dynamics simulations that include surface-hopping have addressed numerous aspects of how the solvent should influence non-adiabatic transitions and energy flow and ultimately determine product branching for this reaction system. In this paper, we report femtosecond transient absorption work directly combined with new molecular dynamics simulations that make direct connection with the spectroscopic observables. The full spectral evolution after initiating ICN photodissociation at 266 nm in water and ethanol is recorded with unprecedented time resolution, fast enough to see the nascent products emerge before interacting with the solvent cage. Use of a 266 nm pump maximizes the probability of subsequent caging on the upper diabat while launching large rotational energy release for trajectories emerging on the lower diabat. The 2D dataset yields a map of the different products and how they interconvert. In particular, information on the branching ratio and spectral evolution of the product bands is revealed as the products relax their electronic and rotational degrees of freedom. An evolution from rotationally hot gas-phase like CN (sharp band, at 390 nm) to equilibrated and solvated CN radicals (broad, at 326 nm in water and 415 nm in ethanol) is clearly observed in both solvents, and signals assignable to I* are also captured. The non-adiabatic molecular dynamics simulations focus on identifying when trajectories curve cross, filtering the trajectory ensemble into spectroscopically distinct sub-populations and analyzing the rotational energy for the CN product population. The experimental results, taken together with the MD

  17. Photomediated Controlled Radical Polymerization and Block Copolymerization of Vinylidene Fluoride.

    PubMed

    Asandei, Alexandru D

    2016-02-24

    This review summarizes recent research on novel photochemical methods for the initiation and control of the polymerization of main chain fluorinated monomers as exemplified by vinylidene fluoride (VDF) and for the synthesis of their block copolymers. Such reactions can be carried out at ambient temperature in glass tubes using visible light. Novel, original protocols include the use of hypervalent iodide carboxylates alone or in conjunction with molecular iodine, as well as the use of photoactive transition metal carbonyls in the presence of alkyl, fluoroalkyl, and perfluoroalkyl halides. An in-depth study of the reaction parameters highlights the use of dimethyl carbonate as a preferred polymerization solvent and outlines the structure-property relationship for hypervalent iodide carboxylates and halide initiators in both the free radical and iodine degenerative transfer controlled radical polymerization (IDT-CRP) of VDF. Finally, the rational selection of metal carbonyls that are successful not only as IDT mediators but, more importantly, in the quantitative activation of both PVDF-CH2-CF2-I and PVDF-CF2-CH2-I chain ends toward the synthesis of well-defined PVDF block copolymers is presented. PMID:26760676

  18. X-ray structure determination of new monomers to establish their polymerizability: copolymerization of two tetrasubstituted electrophilic olefins with electron-rich styrenes giving polymers with an average 1. 25 functional groups per chain carbon atom. [Tetramethyl ethylenetetracarboxylate and dimethyl dicyanofumate; gamma radiation

    SciTech Connect

    Hall, H.K. Jr.; Reineke, K.E.; Ried, J.H.; Sentman, R.C.; Miller, D.

    1982-02-01

    X-ray crystal structure determination for two tetrasubstituted electrophilic olefins, tetramethyl ethylenetetracarboxylate TMET and dimethyl dicyanofumarate DDCF, revealed two fundamentally different molecular structures. TMET is a nonplanar molecule that possesses two opposite ester groups planar and the others above and below the molecular plane. In contrast, DDCF is a molecule for which both ester groups lie in the plane of the double bond and nitrile groups. DDCF underwent thermal spontaneous copolymerization with electron-rich styrenes to give 1:1 alternating copolymers in moderate yields and molecular weights. These copolymers, which result from the first copolymerization of a tetrasubstituted olefin, possess an average functionality of 1.25 per chain carbon atom. Polymerization is made possible by low steric hindrance and the high delocalization in the propagating radical. The yields were limited by competing cycloaddition reaction. The corresponding diethyl ester also copolymerized, but not so well. Neither electrophilic olefin homopolymerized under ..gamma..-irradiation. TMET did not copolymerize at all when treated under identical conditions.

  19. Methyl iodide oxidative addition to [Rh(acac)(CO)(PPh3)]: an experimental and theoretical study of the stereochemistry of the products and the reaction mechanism.

    PubMed

    Conradie, Marrigje M; Conradie, Jeanet

    2011-08-28

    Density functional theory was used to investigate the oxidative addition and subsequent carbonyl insertion and deinsertion steps of the reaction of methyl iodide to a rhodium(I) acetylacetonato complex of the formula [Rh(acac)(CO)(PPh(3))] (Hacac = acetylacetone). This process has been studied experimentally for many rhodium β-diketonato complexes, but, to the best of our knowledge, this is the first systematic computational study of the complete reaction sequence. Experimental (1)H techniques complement the theoretical results on the stereochemistry of the reaction intermediates and products. (1)H NMR also revealed the existence of a second rhodium(III)-acyl product, which has not been previously observed in this reaction. The calculated Gibbs free energy of activation of the oxidative addition reaction is 71 kJ mol(-1), which is in agreement with the experimental value of 82(1) kJ mol(-1). The DFT-calculated oxidative addition corresponds to an associative S(N)2 nucleophilic attack by the rhodium metal centre on the methyl iodide, which is in agreement with calculated and experimental (in brackets) activation parameters of the reaction, 27 (38.8) kJ mol(-1) for ΔH((≠)) and -147 (-146) J K(-1) mol(-1) for ΔS((≠)). PMID:21761056

  20. Experimental and theoretical studies of the products of addition-elimination reactions between benzil dihydrazone and three isomeric chlorobenzaldehydes.

    PubMed

    Liu, Yun-Na; Cheng, Shuang-Shuang; Wang, Chao; Xing, Dian-Xiang; Liu, Yun; Tan, Xue-Jie

    2015-07-01

    A series of mono- and di-Schiff bases formed between benzil dihydrazone {BDH; systematic name: (1Z)-[(2E)-2-hydrazinylidene-1,2-diphenylethylidene]hydrazine} and three isomeric chlorobenzaldehydes were designed and synthesized to be used as model compounds to help to explain the reaction mechanisms for the formation of Schiff bases. These compounds are 1-(2-chlorobenzylidene)-2-{2-[2-(2-chlorobenzylidene)hydrazin-1-ylidene]-1,2-diphenylethylidene}hydrazine (BDHOCB), and the 3-chloro (BDHMCB) and 4-chloro (BDHPCB) analogues, all having the formula C28H20Cl2N4. Surprisingly, only di-Schiff bases were obtained; our attempts to push the reaction in favour of the mono-Schiff bases all failed. Density functional theory (DFT) calculations were performed to explain the trend in the experimental results. In the case of the systems studied, the type of Schiff base produced exhibits a clear dependence on the HOMO-LUMO energy gaps (ΔE(HOMO-LUMO)), i.e. the product is mainly governed by its stability. The compounds were characterized by single-crystal X-ray diffractometry, elemental analysis, melting point, (1)H NMR and (13)C NMR spectroscopy. The structural features of the three new Schiff bases are similar. For instance, they have the same chemical formula, all the molecules have a symmetrical double helix structure, with each Ph-C=N-N=C-Ph arm exhibiting an anti conformation, and their supramolecular interactions include intermolecular π-π and weak C-H...π stacking interactions. The crystal systems are different, however, viz. triclinic (space group P1¯) for BDHPCB, monoclinic (space group P2(1)/n) for BDHOCB and orthorhombic (space group Pnna) for BDHMCB.

  1. Understanding reactivity and regioselectivity in Diels-Alder reactions of a sugar-derived dienophile bearing two competing EWGs. An experimental and computational study.

    PubMed

    Giri, Germán F; Sarotti, Ariel M; Spanevello, Rolando A

    2015-10-13

    The effect of an extra EWG in the reactivity and regioselectivity in Diels-Alder reactions of β-cyanolevoglucosenone and 4 different dienes was studied by a joint computational and experimental study. Conceptual DFT analysis successfully predicted an important enhancement in the reactivity, and correctly anticipated the regioselectivity in the reactions with isoprene. However, this static treatment failed when dealing the regiochemical preference of the reactions involving a substituted anthracene as diene. MPW1K/6-31G* calculations correctly reproduced the experimental observations. Based on the collected data, we found that when dealing with dienes and dienophiles with no clear electronically activated position, the ease of pyramidalization of the interacting atoms dictates the regioselectivity of the DA reaction. PMID:26318382

  2. 4'-CyanoPLP presents better prospect for the experimental detection of elusive cyclic intermediate radical in the reaction of lysine 5,6-aminomutase.

    PubMed

    Maity, Amarendra Nath; Ke, Shyue-Chu

    2015-02-01

    The results of our calculations suggest that the reaction of 4'-cyanoPLP with lysine 5,6-aminomutase offers better prospect for the experimental detection of elusive cyclic azacyclopropylcarbinyl radical (I), which is proposed to be a key intermediate in the reaction of pyridoxal-5'-phosphate dependent radical aminomutases. We have calculated the corresponding hyperfine coupling constants (HFCCs) for (14)N and (13)C of cyano group using several basis sets to help the characterization of 4'-cyanoI.

  3. Catalytic Upgrading of Biomass-Derived Compounds via C-C Coupling Reactions. Computational and Experimental Studies of Acetaldehyde and Furan Reactions in HZSM-5

    SciTech Connect

    Liu, Cong; Evans, Tabitha J.; Cheng, Lei; Nimlos, Mark R.; Mukarakate, Calvin; Robichaud, David J.; Assary, Rajeev S.; Curtiss, Larry A.

    2015-10-02

    These catalytic C–C coupling and deoxygenation reactions are essential for upgrading of biomass-derived oxygenates to fuel-range hydrocarbons. Detailed understanding of mechanistic and energetic aspects of these reactions is crucial to enabling and improving the catalytic upgrading of small oxygenates to useful chemicals and fuels. Using periodic density functional theory (DFT) calculations, we have investigated the reactions of furan and acetaldehyde in an HZSM-5 zeolite catalyst, a representative system associated with the catalytic upgrading of pyrolysis vapors. Comprehensive energy profiles were computed for self-reactions (i.e., acetaldehyde coupling and furan coupling) and cross-reactions (i.e., acetaldehyde + furan) of this representative mixture. Major products proposed from the computations are further confirmed using temperature controlled mass spectra measurements. Moreover, the computational results show that furan interacts with acetaldehyde in HZSM-5 via an alkylation mechanism, which is more favorable than the self-reactions, indicating that mixing furans with aldehydes could be a promising approach to maximize effective C–C coupling and dehydration while reducing the catalyst deactivation (e.g., coke formation) from aldehyde condensation.

  4. Experimental measurements of low temperature rate coefficients for neutral-neutral reactions of interest for atmospheric chemistry of Titan, Pluto and Triton: reactions of the CN radical.

    PubMed

    Morales, Sébastien B; Le Picard, Sébastien D; Canosa, André; Sims, Ian R

    2010-01-01

    The kinetics of the reactions of cyano radical, CN (X2sigma+) with three hydrocarbons, propane (CH3CH2CH3), propene (CH3CH=CH2) and 1-butyne (CH[triple band]CCH2CH3) have been studied over the temperature range of 23-298 K using a CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme or Reaction Kinetics in Uniform Supersonic Flow) apparatus combined with the pulsed laser photolysis-laser induced fluorescence technique. These reactions are of interest for the cold atmospheres of Titan, Pluto and Triton, as they might participate in the formation of nitrogen and carbon bearing molecules, including nitriles, that are thought to play an important role in the formation of hazes and biological molecules. All three reactions are rapid with rate coefficients in excess of 10(-10) cm3 molecule(-1) s(-1) at the lowest temperatures of this study and show behaviour characteristic of barrierless reactions. Temperature dependences, different for each reaction, are compared to those used in the most recent photochemical models of Titan's atmosphere. PMID:21302546

  5. Experimental measurements of low temperature rate coefficients for neutral-neutral reactions of interest for atmospheric chemistry of Titan, Pluto and Triton: reactions of the CN radical.

    PubMed

    Morales, Sébastien B; Le Picard, Sébastien D; Canosa, André; Sims, Ian R

    2010-01-01

    The kinetics of the reactions of cyano radical, CN (X2sigma+) with three hydrocarbons, propane (CH3CH2CH3), propene (CH3CH=CH2) and 1-butyne (CH[triple band]CCH2CH3) have been studied over the temperature range of 23-298 K using a CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme or Reaction Kinetics in Uniform Supersonic Flow) apparatus combined with the pulsed laser photolysis-laser induced fluorescence technique. These reactions are of interest for the cold atmospheres of Titan, Pluto and Triton, as they might participate in the formation of nitrogen and carbon bearing molecules, including nitriles, that are thought to play an important role in the formation of hazes and biological molecules. All three reactions are rapid with rate coefficients in excess of 10(-10) cm3 molecule(-1) s(-1) at the lowest temperatures of this study and show behaviour characteristic of barrierless reactions. Temperature dependences, different for each reaction, are compared to those used in the most recent photochemical models of Titan's atmosphere.

  6. Theoretical and Experimental Investigation of Thermodynamics and Kinetics of Thiol-Michael Addition Reactions: A Case Study of Reversible Fluorescent Probes for Glutathione Imaging in Single Cells.

    PubMed

    Chen, Jianwei; Jiang, Xiqian; Carroll, Shaina L; Huang, Jia; Wang, Jin

    2015-12-18

    Density functional theory (DFT) was applied to study the thermodynamics and kinetics of reversible thiol-Michael addition reactions. M06-2X/6-31G(d) with the SMD solvation model can reliably predict the Gibbs free energy changes (ΔG) of thiol-Michael addition reactions with an error of less than 1 kcal·mol(-1) compared with the experimental benchmarks. Taking advantage of this computational model, the first reversible reaction-based fluorescent probe was developed that can monitor the changes in glutathione levels in single living cells.

  7. Nitrogen fixation on early Mars and other terrestrial planets: experimental demonstration of abiotic fixation reactions to nitrite and nitrate.

    PubMed

    Summers, David P; Khare, Bishun

    2007-04-01

    Understanding the abiotic fixation of nitrogen is critical to understanding planetary evolution and the potential origin of life on terrestrial planets. Nitrogen, an essential biochemical element, is certainly necessary for life as we know it to arise. The loss of atmospheric nitrogen can result in an incapacity to sustain liquid water and impact planetary habitability and hydrological processes that shape the surface. However, our current understanding of how such fixation may occur is almost entirely theoretical. This work experimentally examines the chemistry, in both gas and aqueous phases, that would occur from the formation of NO and CO by the shock heating of a model carbon dioxide/nitrogen atmosphere such as is currently thought to exist on early terrestrial planets. The results show that two pathways exist for the abiotic fixation of nitrogen from the atmosphere into the crust: one via HNO and another via NO(2). Fixation via HNO, which requires liquid water, could represent fixation on a planet with liquid water (and hence would also be a source of nitrogen for the origin of life). The pathway via NO(2) does not require liquid water and shows that fixation could occur even when liquid water has been lost from a planet's surface (for example, continuing to remove nitrogen through NO(2) reaction with ice, adsorbed water, etc.).

  8. Face-selective Diels-Alder reactions between unsymmetrical cyclohexadienes and symmetric trans-dienophile: an experimental and computational investigation.

    PubMed

    Lahiri, Saswati; Yadav, Somnath; Banerjee, Srirupa; Patil, Mahendra P; Sunoj, Raghavan B

    2008-01-18

    A combined experimental and theoretical study of the Diels-Alder reactions between 2-trimethylsiloxy-1,3-cyclohexadienes (2-11) and (E)-1,4-diphenylbut-2-ene-1,4-dione (1) is reported. Two diastereomeric products, 5-endo-6-exo- (nx) and 5-exo-6-endo- (xn) dibenzoyl derivatives, are possible with symmetric trans-dienophile (1). While in many cases 5-endo-6-exo product is preferred over the corresponding 5-exo-6-endo product, the product ratio nx:xn is found to vary with the position of substituents on the diene. The density functional theory studies with the mPW1PW91/6-31G* as well as the B3LYP/6-31G* levels reveal that the electrostatic repulsion between the oxygen lone pairs on the diene and the dienophile is critical to the observed product selectivities. The optimized transition state geometries though appeared to involve secondary orbital interactions, careful examination of the frontier Kohn-Sham orbitals as well as calculations with the natural bond orbital (NBO) analyses confirm the absence of SOI in these transition states. In the case of methyl-substituted dienes, a cumulative effect of steric and electrostatic interactions between the diene and the dienophile is found to be the controlling element toward the observed selectivity. PMID:18088142

  9. Nitrogen Fixation on Early Mars and Other Terrestrial Planets: Experimental Demonstration of Abiotic Fixation Reactions to Nitrite and Nitrate

    NASA Astrophysics Data System (ADS)

    Summers, David P.; Khare, Bishun

    2007-05-01

    Understanding the abiotic fixation of nitrogen is critical to understanding planetary evolution and the potential origin of life on terrestrial planets. Nitrogen, an essential biochemical element, is certainly necessary for life as we know it to arise. The loss of atmospheric nitrogen can result in an incapacity to sustain liquid water and impact planetary habitability and hydrological processes that shape the surface. However, our current understanding of how such fixation may occur is almost entirely theoretical. This work experimentally examines the chemistry, in both gas and aqueous phases, that would occur from the formation of NO and CO by the shock heating of a model carbon dioxide/nitrogen atmosphere such as is currently thought to exist on early terrestrial planets. The results show that two pathways exist for the abiotic fixation of nitrogen from the atmosphere into the crust: one via HNO and another via NO2. Fixation via HNO, which requires liquid water, could represent fixation on a planet with liquid water (and hence would also be a source of nitrogen for the origin of life). The pathway via NO2 does not require liquid water and shows that fixation could occur even when liquid water has been lost from a planet's surface (for example, continuing to remove nitrogen through NO2 reaction with ice, adsorbed water, etc.).

  10. Thermodynamic Properties of CO{sub 2} Capture Reaction by Solid Sorbents: Theoretical Predictions and Experimental Validations

    SciTech Connect

    Duan, Yuhua; Luebke, David; Pennline, Henry; Li, Liyu; King, David; Zhang,; Keling,; Zhao,; Lifeng,; Xiao, Yunhan

    2012-01-01

    It is generally accepted that current technologies for capturing CO{sub 2} are still too energy intensive. Hence, there is a critical need for development of new materials that can capture CO{sub 2} reversibly with acceptable energy costs. Accordingly, solid sorbents have been proposed to be used for CO{sub 2} capture applications through a reversible chemical transformation. By combining thermodynamic database mining with first principles density functional theory and phonon lattice dynamics calculations, a theoretical screening methodology to identify the most promising CO{sub 2} sorbent candidates from the vast array of possible solid materials has been proposed and validated. The calculated thermodynamic properties of different classes of solid materials versus temperature and pressure changes were further used to evaluate the equilibrium properties for the CO{sub 2} adsorption/desorption cycles. According to the requirements imposed by the pre- and post- combustion technologies and based on our calculated thermodynamic properties for the CO{sub 2} capture reactions by the solids of interest, we were able to screen only those solid materials for which lower capture energy costs are expected at the desired pressure and temperature conditions. These CO{sub 2} sorbent candidates were further considered for experimental validations. In this presentation, we first introduce our screening methodology with validating by solid dataset of alkali and alkaline metal oxides, hydroxides and bicarbonates which thermodynamic properties are available. Then, by studying a series of lithium silicates, we found that by increasing the Li{sub 2}O/SiO{sub 2} ratio in the lithium silicates their corresponding turnover temperatures for CO{sub 2} capture reactions can be increased. Compared to anhydrous K{sub 2}CO{sub 3}, the dehydrated K{sub 2}CO{sub 3}1.5H{sub 2}O can only be applied for post-combustion CO{sub 2} capture technology at temperatures lower than its phase transition (to

  11. Simulation of 3He(d,p) 4He reaction and recent results of the experimental investigation of dp breakup reaction

    NASA Astrophysics Data System (ADS)

    Janek, M.; Kurilkin, P. K.; Tarjanyiova, G.; Ladygin, V. P.; Gurchin, Yu V.; Isupov, A. Yu; Karachuk, J.-T.; Khrenov, A. N.; Kurilkin, A. K.; Livanov, A. N.; Martinska, G.; Piyadin, S. M.; Reznikov, S. G.; Merts, S. P.; Batyuk, P. N.; Terekhin, A. A.; Vnukov, I. E.

    2016-02-01

    The feasibility study for the measurements of the polarization observables in the 3He(d,p) 4He reaction for DSS project using a part of the BM@N setup have been performed. Deuteron beam with energy of 1.5 GeV, magnet, 12 stations GEM tracker and TOF wall were used in simulations in order to obtain momentum resolution and to prove the separation of the secondary protons and deuterons. Summarized results of the dp breakup reactions with detection of two protons in coincidence for some kinematic configurations at energies from 300 to 500 MeV obtained in Nuclotron are presented.

  12. Synthesis and structural characterization of double metal cyanides of iron and zinc: catalyst precursors for the copolymerization of carbon dioxide and epoxides.

    PubMed

    Darensbourg, Donald J; Adams, M Jason; Yarbrough, Jason C; Phelps, Andrea L

    2003-12-01

    Several synthetic approaches for the preparation of double metal cyanide (DMC) derivatives of iron(II) and zinc(II) are described. These include (1) metathesis reactions of ZnCl(2) or ZnI(2) with KCpFe(CN)(2)CO in aqueous solution, (2) reactions of KCpFe(CN)(2)CO and its phosphine-substituted analogues with Zn(CH(3)CN)(4)(BF(4))(2) and subsequent displacement of acetonitrile at the zinc centers by the addition of a neutral (phosphine) or anionic (phenoxide) ligand, and (3) reactions of the protonated HCpFe(CN)(2)(phosphine) complexes with Zn(N(SiMe(3))(2))(2), followed by the addition of phenols. All structures are based on a diamond-shaped planar arrangement of the Fe(2)(CN)(4)Zn(2) core with various appended ligands at the metal sites. Although attempts to replace the iodide ligands in [CpFe(mu-CN)(2)PPh(3)ZnI(THF)](2) with acetate using silver acetate failed, two novel cationic mixed-metal cyanide salts based on the [CpFe(PPh(3))(mu-CN)(2)Zn(NC(5)H(5))](2)(2+) framework were isolated from pyridine solution and their structures were defined by X-ray crystallography. The anionic ligand bound to zinc in these derivatives, which serve as an anionic polymerization initiator, was shown to be central to the catalytic copolymerization reaction of CO(2)/epoxide to provide polycarbonates and cyclic carbonates. The structurally stabilized phosphine-strapped complexes [CpFe(mu-CN)(2)Zn(X)THF](2)(mu-dppp), where X = I or phenolate, were shown to be thermally stable under the conditions (80 degrees C) of the copolymerization reaction by in situ infrared spectroscopy. Both of these derivatives were proposed to serve as mimics for the heterogeneous DMC catalysts in the patent literature, with the derivative where the initiator is a phenolate being more active for the production of polycarbonates. PMID:14632496

  13. Experimental growth of åkermanite reaction rims between wollastonite and monticellite: evidence for volume diffusion control

    NASA Astrophysics Data System (ADS)

    Joachim, Bastian; Gardés, Emmanuel; Abart, Rainer; Heinrich, Wilhelm

    2011-03-01

    Growth rates of monomineralic, polycrystalline åkermanite (Ca2MgSi2O7) rims produced by solid-state reactions between monticellite (CaMgSiO4) and wollastonite (CaSiO3) single crystals were determined at 0.5 GPa dry argon pressure, 1,000-1,200°C and 5 min to 60 h, using an internally heated pressure vessel. Inert Pt-markers, initially placed at the monticellite-wollastonite interface, indicate symmetrical growth into both directions. This and mass balance considerations demonstrate that rim growth is controlled by transport of MgO. At 1,200°C and run durations between 5 min and 60 h, rim growth follows a parabolic rate law with rim widths ranging from 0.4 to 16.3 μm indicating diffusion-controlled rim growth. The effective bulk diffusion coefficient D_{{eff,MgO}}^{{Ak}} is calculated to 10-15.8±0.1 m2 s-1. Between 1,000°C and 1,200°C, the effective bulk diffusion coefficient follows an Arrhenius law with E a = 204 ± 18 kJ/mol and D 0 = 10-8.6±1.6 m2 s-1. Åkermanite grains display a palisade texture with elongation perpendicular to the reaction interface. At 1,200°C, average grain widths measured normal to elongation, increase with the square root of time and range from 0.4 to 5.4 μm leading to a successive decrease in the grain boundary area fraction, which, however, does not affect D_{{eff,MgO}}^{{Ak}} to a detectible extent. This implies that grain boundary diffusion only accounts for a minor fraction of the overall chemical mass transfer, and rim growth is essentially controlled by volume diffusion. This is corroborated by the agreement between our estimates of the effective MgO bulk diffusion coefficient and experimentally determined volume diffusion data for Mg and O in åkermanite from the literature. There is sharp contrast to the MgO-SiO2 binary system, where grain boundary diffusion controls rim growth.

  14. Near-infrared luminescent copolymerized hybrid materials built from tin nanoclusters and PMMA.

    PubMed

    Fan, Weiqiang; Feng, Jing; Song, Shuyan; Lei, Yongqian; Zhou, Liang; Zheng, Guoli; Dang, Song; Wang, Song; Zhang, Hongjie

    2010-10-01

    Novel near-infrared (NIR) luminescent copolymerized hybrid materials were prepared by covalently grafting and physically doping Ln complexes (Ln = Er, Sm, Yb, and Nd) into a copolymer matrix built from nanobuilding blocks. The structures of the obtained hybrid materials were investigated by Fourier transform infrared (FTIR) spectra, nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), and thermogravimetric analysis (TGA). In the photoluminescence studies, the hybrid materials showed characteristic NIR luminescence of corresponding Ln(3+) ions through intramolecular energy transfer from ligands to Ln(3+) ions. Transparent films of these materials can be easily prepared through spin-coating on indium tin oxide (ITO) glasses taking advantage of the matrix nature.

  15. Relative rates for plasma homo- and copolymerizations of olefins in a homologous series of fluorinated ethylenes

    NASA Technical Reports Server (NTRS)

    Golub, M. A.; Wydeven, T.

    1997-01-01

    It is well known that the rate of plasma polymerization, or deposition rate, of a given monomer depends on various plasma process parameters, e.g., monomer flow rate, pressure, power, frequency (DC, rf or microwave), location of the substrate in the reactor, reactor geometry or configuration, and temperature. In contrast, little work has been done to relate deposition rates to monomer structures for a homologous series of monomers where the rates are obtained under identical plasma process parameters. For the particular series of fluorinated ethylenes (C2HxF4-x; x = 0-4), deposition rates were reported for ethylene (ET), vinyl fluoride, vinylidene fluoride and tetrafluoroethylene (TFE), but for plasma polymerizations carried out under different discharge conditions, e.g., pressure, current density, and electrode temperature. Apparently, relative deposition rates were reported for only two members of that series (ET, x = 4, and TFE, x = 0) for which the plasma polymerizations were conducted under identical conditions. We now present relative deposition rates for both homopolymerizations and copolymerizations of the entire series of fluorinated ethylenes (x = 0-4). Our interest in such rates stems from prior work on the plasma copolymerization of ET and TFE in which it was found that the deposition rates for the plasma copolymers, when plotted versus mol % TFE in the ET/TFE feed stock, followed a concave-downward curve situated above the straight line joining the deposition rates for the plasma homopolymers. This type of plot (observed also for an argon-ET/TFE plasma copolymerization) indicated a positive interaction between ET and TFE such that each monomer apparently "sensitized" the plasma copolymerization of the other. Since the shape of that plot is not altered if mol % TFE is replaced by F/C, the fluorine-to-carbon ratio, this paper aims (1) to show how the relative deposition rates for plasma copolymers drawn from all pairs of monomers in the C2HxF4-x series

  16. A joint experimental and theoretical investigation of kinetics and mechanistic study in a synthesis reaction between triphenylphosphine and dialkyl acetylenedicarboxylates in the presence of benzhydrazide.

    PubMed

    Kazemian, Mohammad Amin; Habibi-Khorassani, Sayyed Mostafa; Ebrahimi, Ali; Maghsoodlou, Malek Taher; Jahani, Peyman Mohammadzadeh; Ghahramaninezhad, Mahbobeh

    2012-12-01

    Stable crystalline phosphorus ylides were obtained in excellent yields from the 1:1:1 addition reaction between triphenylphosphine (TPP) and dialkyl acetylenedicarboxylates, in the presence of NH-acids, such as benzhydrazide. To determine the kinetic parameters of the reactions, they were monitored by UV spectrophotometery. The second order fits were automatically drawn and the values of the second order rate constant (k(2)) were calculated using standard equations within the program. At the temperature range studied the dependence of the second order rate constant (Ln k(2)) on reciprocal temperature was compatible with Arrhenius equation. This provided the relevant plots to calculate the activation energy of all reactions. Furthermore, useful information were obtained from studies of the effect of solvent, structure of reactants (different alkyl groups within the dialkyl acetylenedicarboxylates) and also concentration of reactants on the rate of reactions. On the basis of experimental data the proposed mechanism was confirmed according to the obtained results and a steady state approximation and the first step (k(2)) and third (k(3)) steps of the reactions were recognized as the rate determining steps, respectively. In addition, three speculative proposed mechanisms were theoretically investigated using quantum mechanical calculation. The results, arising from the second and third speculative mechanisms, were far from the experimental data. Nevertheless, there was a good agreement between the theoretical kinetic data, emerge from the first speculative mechanism, and experimental kinetic data of proposed mechanism.

  17. New Insights of the Fenton Reaction Using Glycerol as the Experimental Model. Effect of O2, Inhibition by Mg(2+), and Oxidation State of Fe.

    PubMed

    Vitale, Arturo Alberto; Bernatene, Eduardo A; Vitale, Martín Gustavo; Pomilio, Alicia Beatriz

    2016-07-21

    The use of iron ions as catalyst of oxidation with hydrogen peroxide, known as the Fenton reaction, is important for industry and biological systems. It has been widely studied since its discovery in the 19th century, but important aspects of the reaction as which is the oxidant, the role of oxygen, and the oxidation state of Fe still remain unclear. In this work new mechanistic insights of the oxidation of carbohydrates by the Fenton reaction using glycerol as experimental model are described. The reaction was studied by means of oxidation reduction potential (ORP) measures. The stoichiometry was measured, showing the important role of oxygen for lowering H2O2 consumption under aerobic conditions. Evidence is provided to demonstrate that in this system Fe(2+) generates a catalyst by reacting with a substrate to produce a complex, which gives rise to singlet oxygen after reacting with H2O2. This is the first time that the inhibitor effect of Mg(2+) is reported in this reaction, and its participation in the mechanism is described. A rational mechanism for the oxidation of glycerol using the Fenton reaction under these specific conditions is proposed. The role of oxygen, the participation of Fe(2+), and the inhibition by Mg(2+) are fully demonstrated experimentally.

  18. Experimental study of the effects of CO{sub 2} on the noncatalytic reduction reaction of NO by carbonaceous materials

    SciTech Connect

    Weidong Fan; Zhengchun Lin; Youyi Li; Jinguo Kuang

    2009-05-15

    In a fixed bed reactor with a quartz tube, the effects of the concentration of CO{sub 2} in the feed gas on the uncatalyzed reaction between soot produced in a natural gas diffusion flame and NO were investigated. They were compared with CO{sub 2} effects on reactions involving candle soot and bituminous coal char. The presence of CO{sub 2} in the feed gas exerted no influence on the reaction of NO with natural gas soot. However, it did result in a lower initial temperature in the reaction of candle soot or coal char with NO, and separated the whole initial reaction process into two stages. At higher CO{sub 2} concentrations, more NO reduction occurred in the reaction with candle soot or coal char during the initial reaction process. However, no dramatic changes in the amount of NO reduction were observed for natural gas soot. The addition of CO{sub 2} seemed to have no effect on the apparent activation energy of the NO-natural gas soot reaction, while a lowering of the apparent activation energy was observed in the reaction of NO with candle soot or coal char as the CO{sub 2} concentration increased. The abundant C(O) complexes formed during sample gasification by CO{sub 2} were assumed to play an important role in the enhancement of the reaction. 20 refs., 12 figs., 2 tabs.

  19. RAFT Dispersion Alternating Copolymerization of Styrene with N-Phenylmaleimide: Morphology Control and Application as an Aqueous Foam Stabilizer

    PubMed Central

    2016-01-01

    We report a new nonaqueous polymerization-induced self-assembly (PISA) formulation based on the reversible addition–fragmentation chain transfer (RAFT) dispersion alternating copolymerization of styrene with N-phenylmaleimide using a nonionic poly(N,N-dimethylacrylamide) stabilizer in a 50/50 w/w ethanol/methyl ethyl ketone (MEK) mixture. The MEK cosolvent is significantly less toxic than the 1,4-dioxane cosolvent reported previously [YangP.; Macromolecules2013, 46, 8545−8556]. The core-forming alternating copolymer block has a relatively high glass transition temperature (Tg), which leads to vesicular morphologies being observed during PISA, as well as the more typical sphere and worm phases. Each of these copolymer morphologies has been characterized by transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) studies. TEM studies reveal micrometer-sized elliptical particles with internal structure, with SAXS analysis suggesting an oligolamellar vesicle morphology. This structure differs from that previously reported for a closely related PISA formulation utilizing a poly(methacrylic acid) stabilizer block for which unilamellar platelet-like particles are observed by TEM and SAXS. This suggests that interlamellar interactions are governed by the nature of the steric stabilizer layer. Moreover, using the MEK cosolvent also enables access to a unilamellar vesicular morphology, despite the high Tg of the alternating copolymer core-forming block. This was achieved by simply conducting the PISA synthesis at a higher temperature for a longer reaction time (80 °C for 24 h). Presumably, MEK solvates the core-forming block more than the previously utilized 1,4-dioxane cosolvent, which leads to greater chain mobility. Finally, preliminary experiments indicate that the worms are much more efficient stabilizers for aqueous foams than either the spheres or the oligolamellar elliptical vesicles.

  20. RAFT Dispersion Alternating Copolymerization of Styrene with N-Phenylmaleimide: Morphology Control and Application as an Aqueous Foam Stabilizer

    PubMed Central

    2016-01-01

    We report a new nonaqueous polymerization-induced self-assembly (PISA) formulation based on the reversible addition–fragmentation chain transfer (RAFT) dispersion alternating copolymerization of styrene with N-phenylmaleimide using a nonionic poly(N,N-dimethylacrylamide) stabilizer in a 50/50 w/w ethanol/methyl ethyl ketone (MEK) mixture. The MEK cosolvent is significantly less toxic than the 1,4-dioxane cosolvent reported previously [YangP.; Macromolecules2013, 46, 8545−8556]. The core-forming alternating copolymer block has a relatively high glass transition temperature (Tg), which leads to vesicular morphologies being observed during PISA, as well as the more typical sphere and worm phases. Each of these copolymer morphologies has been characterized by transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) studies. TEM studies reveal micrometer-sized elliptical particles with internal structure, with SAXS analysis suggesting an oligolamellar vesicle morphology. This structure differs from that previously reported for a closely related PISA formulation utilizing a poly(methacrylic acid) stabilizer block for which unilamellar platelet-like particles are observed by TEM and SAXS. This suggests that interlamellar interactions are governed by the nature of the steric stabilizer layer. Moreover, using the MEK cosolvent also enables access to a unilamellar vesicular morphology, despite the high Tg of the alternating copolymer core-forming block. This was achieved by simply conducting the PISA synthesis at a higher temperature for a longer reaction time (80 °C for 24 h). Presumably, MEK solvates the core-forming block more than the previously utilized 1,4-dioxane cosolvent, which leads to greater chain mobility. Finally, preliminary experiments indicate that the worms are much more efficient stabilizers for aqueous foams than either the spheres or the oligolamellar elliptical vesicles. PMID:27708458

  1. Copolymerization of Epichlorohydrin and CO2 Using Zinc Glutarate: An Additional Application of ZnGA in Polycarbonate Synthesis.

    PubMed

    Sudakar, Padmanaban; Sivanesan, Dharmalingam; Yoon, Sungho

    2016-05-01

    The use of zinc glutarate (ZnGA) as a heterogeneous catalyst for the copolymerization of epichlorohydrin, an epoxide with an electron-withdrawing substituent, and CO2 is reported. This catalyst shows the highest selectivity (98%) for polycarbonate over the cyclic carbonate in epichlorohydrin/CO2 copolymerization under mild conditions. The (epichlorohydrin-co-CO2 ) polymer exhibits a high glass transition temperature (Tg ), 44 °C, which is the maximum Tg value obtained for the (epichlorohydrin-co-CO2 ) polymer to date.

  2. An experimental and theoretical study on the kinetic isotope effect of C2H6 and C2D6 reaction with OH

    NASA Astrophysics Data System (ADS)

    Khaled, Fethi; Giri, Binod Raj; Szőri, Milán; Viskolcz, Béla; Farooq, Aamir

    2015-11-01

    We report experimental and theoretical results for the deuterated kinetic isotope effect (DKIE) of the reaction of OH with ethane (C2H6) and deuterated ethane (C2D6). The reactions were investigated behind reflected shock waves over 800-1350 K by monitoring OH radicals near 306.69 nm using laser absorption. In addition, high level CCSD(T)/cc-pV(T,Q)Z//MP2/cc-pVTZ quantum chemical and statistical rate theory calculations were performed which agreed very well with the experimental findings. The results reported herein provide the first experimental evidence that DKIE asymptotes to a value of 1.4 at high temperatures.

  3. A general theory of kinetics and thermodynamics of steady-state copolymerization.

    PubMed

    Shu, Yao-Gen; Song, Yong-Shun; Ou-Yang, Zhong-Can; Li, Ming

    2015-06-17

    Kinetics of steady-state copolymerization has been investigated since the 1940s. Irreversible terminal and penultimate models were successfully applied to a number of comonomer systems, but failed for systems where depropagation is significant. Although a general mathematical treatment of the terminal model with depropagation was established in the 1980s, a penultimate model and higher-order terminal models with depropagation have not been systematically studied, since depropagation leads to hierarchically-coupled and unclosed kinetic equations which are hard to solve analytically. In this work, we propose a truncation method to solve the steady-state kinetic equations of any-order terminal models with depropagation in a unified way, by reducing them into closed steady-state equations which give the exact solution of the original kinetic equations. Based on the steady-state equations, we also derive a general thermodynamic equality in which the Shannon entropy of the copolymer sequence is explicitly introduced as part of the free energy dissipation of the whole copolymerization system.

  4. The use of polydisulfides and copolymeric disulfides in the Li/PEO/SRPE battery system

    SciTech Connect

    Doeff, M.M.; Lerner, M.M.; Visco, S.J.; DeJonghe, L.C. )

    1982-08-01

    This paper reports that solid redox polymerization electrodes (SRPEs) have recently been used successfully as cathodes in lithium solid polymer electrolyte batteries. SRPEs contain organopolydisulfides (SRS) as the electroactive material; upon cell discharge these materials are reductively depolymerized via scission of the disulfide linkages to di- or trithiolate salts. The thiolate slats are reoxidized to the polymeric disulfides when the cell is recharged. Organopolydisulfides are easily synthesized via a one-step process, are inexpensive, and exhibit high performance levels in batteries. A characteristic unique to the ability to combine the desirable features of several compounds by copolymerization. The discharge characteristics of several different polymeric and copolymeric disulfides are presented in this paper. In general aliphatic organopoly-disulfides exhibit a flat discharge potential of about 2 V vs. Li, while other have higher cell voltages. The low equivalent weight and the high utilization of thick cathodes of-(SCH[sub 2]CH[sub 2]S)[sub n](X8) translate into high energy densities for lithium polymer electrolytes cells.

  5. The Introduction of High-Throughput Experimentation Methods for Suzuki-Miyaura Coupling Reactions in University Education

    ERIC Educational Resources Information Center

    Hoogenboom, Richard; Meier, Michael A. R.; Schubert, Ulrich S.

    2005-01-01

    A laboratory project permits for the discussion of the reaction mechanism of the Suzuki-Miyaura coupling reaction. The practical part of the project makes the students familiar with working under inert atmosphere but if the appropriate equipment for working under inert atmosphere is not available in a laboratory, novel catalysts that do not…

  6. Experimental determination of particle range and dose distribution in thick targets through fragmentation reactions of stable heavy ions.

    PubMed

    Inaniwa, Taku; Kohno, Toshiyuki; Tomitani, Takehiro; Urakabe, Eriko; Sato, Shinji; Kanazawa, Mitsutaka; Kanai, Tatsuaki

    2006-09-01

    In radiation therapy with highly energetic heavy ions, the conformal irradiation of a tumour can be achieved by using their advantageous features such as the good dose localization and the high relative biological effectiveness around their mean range. For effective utilization of such properties, it is necessary to evaluate the range of incident ions and the deposited dose distribution in a patient's body. Several methods have been proposed to derive such physical quantities; one of them uses positron emitters generated through projectile fragmentation reactions of incident ions with target nuclei. We have proposed the application of the maximum likelihood estimation (MLE) method to a detected annihilation gamma-ray distribution for determination of the range of incident ions in a target and we have demonstrated the effectiveness of the method with computer simulations. In this paper, a water, a polyethylene and a polymethyl methacrylate target were each irradiated with stable (12)C, (14)N, (16)O and (20)Ne beams. Except for a few combinations of incident beams and targets, the MLE method could determine the range of incident ions R(MLE) with a difference between R(MLE) and the experimental range of less than 2.0 mm under the circumstance that the measurement of annihilation gamma rays was started just after the irradiation of 61.4 s and lasted for 500 s. In the process of evaluating the range of incident ions with the MLE method, we must calculate many physical quantities such as the fluence and the energy of both primary ions and fragments as a function of depth in a target. Consequently, by using them we can obtain the dose distribution. Thus, when the mean range of incident ions is determined with the MLE method, the annihilation gamma-ray distribution and the deposited dose distribution can be derived simultaneously. The derived dose distributions in water for the mono-energetic heavy-ion beams of four species were compared with those measured with an

  7. Dynamics of alkali ions-neutral molecules reactions: Radio frequency-guided beam experimental cross-sections and direct quasiclassical trajectory studies

    SciTech Connect

    Aguilar, J.; Andres, J. de; Lucas, J. M.; Alberti, M.; Huarte-Larranaga, F.; Bassi, D.; Aguilar, A.

    2012-11-27

    Different reactive processes taking place in collisions between alkali ions and neutral i-C{sub 3}H{sub 7}Cl molecules in the low (center of mass frame) energy range have been studied using an octopole radiofrequency guided-ion-beam apparatus developed in our laboratory. Cross-section energy dependences for all these reactions have been obtained in absolute units. Ab initio electronic structure calculations for those colliding systems evolving on the ground single potential surface have given relevant information on the main topological features of the surfaces. For some of the reactions a dynamic study by 'on the fly' trajectories has complemented the available experimental and electronic structure information.

  8. EXPERIMENTAL STUDY OF CO{sub 2} FORMATION BY SURFACE REACTIONS OF NON-ENERGETIC OH RADICALS WITH CO MOLECULES

    SciTech Connect

    Oba, Yasuhiro; Watanabe, Naoki; Kouchi, Akira; Hama, Tetsuya; Pirronello, Valerio

    2010-04-01

    Surface reactions between carbon monoxide and non-energetic hydroxyl radicals were carried out at 10 K and 20 K in order to investigate possible reaction pathways to yield carbon dioxide in dense molecular clouds. Hydroxyl radicals, produced by dissociating water molecules in microwave-induced plasma, were cooled down to 100 K prior to the introduction of CO. The abundances of species were monitored in situ using a Fourier transform infrared spectrometer. Formation of CO{sub 2} was clearly observed, even at 10 K, suggesting that reactions of CO with OH proceed with little or no activation barrier. The present results indicate that CO{sub 2} formation, due to reactions between CO and OH, occurs in tandem with H{sub 2}O formation, and this may lead to the formation of CO{sub 2} ice in polar environments, as typically observed in molecular clouds.

  9. Negative Index Refraction in the Complex Ginzburg—Landau Equation in Connection with the Experimental CIMA Reaction

    NASA Astrophysics Data System (ADS)

    Yuan, Xu-Jin

    2012-09-01

    In comparison with the phenomenon of negative index refraction observed in artificial meta-materials, it is interesting to ask if this type of behavior also exists or not in reaction-diffusion systems that support nonlinear chemical waves. Previous studies indicate that the negative index refraction could occur on a interface between a medium of a normal wave and a medium that supports anti-waves. Here we investigate the phenomenon in the complex Ginzburg—Landau equation (CGLE) in a close relationship with the quantitative model for the chloriteiodide-malonic acid (CIMA) reaction. The amplitude equation CGLE is deduced from the CIMA reaction, and simulations with mapped parameters from the reaction-diffusion equation reveal that the competition between normal waves and anti-waves on the interface determines whether the negative index refraction occurs or not.

  10. Alternating copolymerization of dihydrocoumarin and epoxides catalyzed by chromium salen complexes: a new route to functional polyesters.

    PubMed

    Van Zee, Nathan J; Coates, Geoffrey W

    2014-06-18

    We report the alternating ring-opening copolymerization of dihydrocoumarin with epoxides catalyzed by chromium(III) salen complexes. This process provides access to a range of perfectly alternating polyesters with high molecular weights and narrow molecular weight distributions. Atactic poly(cyclohexene dihydrocoumarate) and poly(cyclopentene dihydrocoumarate) were found to be semi-crystalline by differential scanning calorimetry.

  11. Radiation synthesis of temperature-responsive hydrogels by copolymerization of [2-(methacryloyloxy)ethyl]trimethylammonium chloride with /N-isopropylacrylamide

    NASA Astrophysics Data System (ADS)

    Mun, Grigoriy A.; Nurkeeva, Zauresh S.; Khutoryanskiy, Vitaliy V.; Sergaziyev, Aibek D.; Rosiak, Janusz M.

    2002-08-01

    Novel cationic hydrogels were synthesized by γ-irradiation copolymerization of [2-(methacryloyloxy)ethyl]trimethylammonium chloride with N-isopropylacrylamide in the presence of cross-linking agent. The synthesis regularities have been studied. The swelling behavior of hydrogels as a function of copolymers composition and temperature was evaluated.

  12. Efficient catalyst removal and recycling in copolymerization of epoxides with carbon dioxide via simple liquid-liquid phase separation.

    PubMed

    Nakano, Koji; Fujie, Ryuhei; Shintani, Ryo; Nozaki, Kyoko

    2013-10-18

    A simple and efficient catalyst removal system has been developed in the cobalt-salen-catalyzed copolymerization of propylene oxide with carbon dioxide. The present system requires no prior modification of the catalyst, and the removal is achieved by simple addition of myristic acid, followed by organic liquid-liquid phase separation.

  13. Experimental study of neutron-rich nuclei near the N = 82 closed shell using the 4096Zr +50124Sn reaction with GASP and PRISMA-CLARA arrays

    NASA Astrophysics Data System (ADS)

    Rodríguez, W.; Torres, D. A.; Cristancho, F.; Medina, N. H.; Chapman, R.; Smith, J. F.; Mengoni, D.; Truesdale, V.; Grocutt, L.; Mulholland, K.; Kumar, V.; Hadinia, B.; Labiche, M.; Liang, X.; O'Donell, D.; Ollier, J.; Orlandi, R.; Smith, J. F.; Spohr, K. M.; Wady, P.; Wang, Z. M.; Gadea, A.; Ur, C. A.; Lenzi, S. M.; Capponi, L.; Michelangnoli, C.; Bazzacco, D.; Beghini, S.; Mǎrginean, R.; Mengoni, D.; Montagnoli, G.; Recchia, F.; Scarlassara, F.; Lunardi, S.; Kröll, T.; Napoli, D. R.; Corradi, L.; Fioretto, E.; de Angelis, G.; Mǎrginean, N.; Sahin, E.; Stefanini, A. M.; Valiente-Dobon, J. J.; Vedova, F. D.; Axiotis, M.; Martinez, T.; Szilner, S.; Freeman, S. J.; Smith, A. G.; Jones, G.; Thompson, N.; Pollarolo, G.

    2014-11-01

    In this contribution an experimental study of the deep-inelastic reaction 4096Zr +50124Sn at 530 MeV, using the GASP and PRISMA-CLARA arrays, is presented. The experiments populate a wealth of projectile-like and target-like binary fragments, in a large neutron-rich region around N ≥ 50 and Z ≈ 40. Preliminary results on the study of the yrast and near-yrast states for 95Nb will be shown, along with a comparison of the experimental yields obtained in the experiments.

  14. Dinuclear and Trinuclear Nickel Complexes as Effective Catalysts for Alternating Copolymerization on Carbon Dioxide and Cyclohexene Oxide.

    PubMed

    Tsai, Chen-Yen; Cheng, Fu-Yin; Lu, Kuan-Yeh; Wu, Jung-Tsu; Huang, Bor-Hunn; Chen, Wei-An; Lin, Chu-Chieh; Ko, Bao-Tsan

    2016-08-15

    A series of novel nickel complexes 1-9 supported by NNO-tridentate Schiff-base derivatives have been synthesized and characterized. Treatment of the pro-ligands [L(1)-H = 2,4-di-tert-butyl-6-(((2-(dimethylamino)ethyl)imino)methyl)phenol, L(2)-H = 2-(((2-(dimethylamino)ethyl)imino)methyl)-4,6-bis(2-phenylpropan-2-yl)phenol, L(3)-H = 2-(((2-(dimethylamino)ethyl)imino)methyl)phenol] with Ni(OAc)2·4H2O in refluxing ethanol afforded mono- or bimetallic nickel complexes {[(L(1))Ni(OAc)] (1); (L(2))Ni(OAc)] (2); (L(3))2Ni2(OAc)2(H2O)] (3)}. Alcohol-solvated trimetallic nickel acetate complexes {[(L(3))2Ni3(OAc)4(MeOH)2] (4); (L(3))2Ni3(OAc)4(EtOH)2] (5)} could be generated from the reaction of L(3)-H and anhydrous nickel(II) acetate with a ratio of 2:3 in refluxing anhydrous MeOH or EtOH. The reaction of nickel acetate tetrahydrate and L(4)-H to L(6)-H [L(4)-H = 2-(((2-(dimethylamino)ethyl)imino)methyl)-5-methoxyphenol, L(5)-H = 2-(((2-(dimethylamino)ethyl)imino)methyl)-4-methoxy-phenol, L(6)-H = 2-(((2-(dimethylamino)ethyl)imino)(phenyl)methyl)phenol] produced, respectively, the alcohol-free trinuclear nickel complexes {[(L(4))2Ni3(OAc)4] (7); [(L(5))2Ni3(OAc)4] (8); [(L(6))2Ni3(OAc)4] (9)} with the same ratio in refluxing EtOH under the atmospheric environment. Interestingly, recrystallization of [(L(3))2Ni3(OAc)4(MeOH)] (4) or [(L(3))2Ni3(OAc)4(EtOH)] (5) in the mixed solvent of CH2Cl2/hexane gives [(L(3))2Ni3(OAc)4] (6), which is isostructural with analogues 7-9. All bi- and trimetallic nickel complexes exhibit efficient activity and good selectivity for copolymerization of CO2 with cyclohexene oxide, resulting in copolymers with a high alternating microstructure possessing ≥99% carbonate-linkage content. This is the first example to apply well-defined trinuclear nickel complexes as efficient catalysts for the production of perfectly alternating poly(cyclohexene carbonate). PMID:27479795

  15. Design of highly active binary catalyst systems for CO2/epoxide copolymerization: polymer selectivity, enantioselectivity, and stereochemistry control.

    PubMed

    Lu, Xiao-Bing; Shi, Lei; Wang, Yi-Ming; Zhang, Rong; Zhang, Ying-Ju; Peng, Xiao-Jun; Zhang, Zhi-Chao; Li, Bo

    2006-02-01

    Asymmetric, regio- and stereoselective alternating copolymerization of CO(2) and racemic aliphatic epoxides proceeds effectively under mild temperature and pressure by using a binary catalyst system of a chiral tetradentate Schiff base cobalt complex [SalenCo(III)X] as the electrophile in conjunction with an ionic organic ammonium salt or a sterically hindered strong organic base as the nucleophile. The substituent groups on the aromatic rings, chiral diamine backbone, and axial X group of the electrophile, as well as the nucleophilicity, leaving ability, and coordination ability of the nucleophile, all significantly affect the catalyst activity, polymer selectivity, enantioselectivity, and stereochemistry. A bulky chiral cyclohexenediimine backbone complex [SalcyCo(III)X] with an axial X group of poor leaving ability as the electrophile, combined with a bulky nuclephile with poor leaving ability and low coordination ability, is an ideal binary catalyst system for the copolymerization of CO(2) and a racemic aliphatic epoxide to selectively produce polycarbonates with relatively high enantioselectivity, >95% head-to-tail connectivity, and >99% carbonate linkages. A fast copolymerization of CO(2) and epoxides was observed when the concentration of the electrophile or/and the nucleophile was increased, and the number of polycarbonate chains was proportional to the concentration of the nucleophile. Electrospray ionization mass spectrometry, in combination with a kinetic study, showed that the copolymerization involved the coordination activation of the monomer by the electrophile and polymer chain growth predominately occurring in the nucleophile. Both the enantiomorphic site effect resulting from the chiral electrophile and the polymer chain end effect mainly from the bulky nucleophile cooperatively control the stereochemistry of the CO(2)/epoxide copolymerization.

  16. Experimental determination of the minimum onset temperature of runaway reaction from a radioactive salt disposal in asphalt.

    PubMed

    Li, Xin-Rui; Sun, Jin-Hua; Koseki, Hiroshi; Hasegawa, Kazutoshi

    2005-04-11

    In order to clarify the reason for the most hazardous explosion in the history of the Japanese nuclear power development by a radioactive salt disposal in asphalt, an adiabatic process was developed using a Dewar vessel to minimize the temperature difference between the reactants and the surroundings. By this means, the heat evolution from a reaction which is readily lost can be detected at a lower temperature imitating the accidental condition. A series of ambient temperature-tracking Dewar experiments on asphalt salt mixtures were conducted under different initial ambient temperatures, such as 230, 210, 190, and 170 degrees C, respectively. As a result, it was observed that from 190 degrees C the sample's temperature rose until a runaway reaction occurred. The minimum onset temperature for the runaway reaction of the asphalt salt mixture was determined to be 190 degrees C, which is close to the initial temperature of approximately 180 degrees C, the same temperature as the real accident. This implies that at near this operational temperature, initial faint chemical reactions may occur and lead to further rapid reactions if heat is accumulated at this stage.

  17. Exploring the Complexities of Experimental Design: Using an On-line Reaction Time Program as a Teaching Tool for Diverse Student Populations

    PubMed Central

    Pollack, Alexia E.

    2010-01-01

    Students are rarely given an opportunity to think deeply about experimental design or asked to develop experimental protocols on their own. Without participating in these endeavors, they are often unaware of the many decisions necessary to construct a precise methodology. This article describes an on-line reaction time program, and how I have used this program as a teaching tool for students to explore experimental design. This approach can be tailored to meet the level of any undergraduate student – from non-science majors to upper-level biology/psychology/neuroscience majors, affording all students the opportunity to think like a scientist. Described is how I use the reaction time program for a whole class demonstration and discussion, as well as, how it can be used for a written assignment in which each student designs and conducts his/her own experiment outside of the classroom. Comments from several students, who did the written assignment, are included to provide a sense of their thoughts and considerations. When students are given a simple method, such as the measurement of reaction time, it allows them to focus exclusively on developing precise methodology, which taps into types of thinking that they are not often asked to exhibit in other science classes. PMID:23494764

  18. Crystalline Isotactic Polar Polypropylene from the Palladium-Catalyzed Copolymerization of Propylene and Polar Monomers.

    PubMed

    Ota, Yusuke; Ito, Shingo; Kobayashi, Minoru; Kitade, Shinichi; Sakata, Kazuya; Tayano, Takao; Nozaki, Kyoko

    2016-06-20

    Moderately isospecific homopolymerization of propylene and the copolymerization of propylene and polar monomers have been achieved with palladium complexes bearing a phosphine-sulfonate ligand. Optimization of substituents on the phosphorus atom of the ligand revealed that the presence of bulky alkyl groups (e.g. menthyl) is crucial for the generation of high-molecular-weight polypropylenes (Mw ≈10(4) ), and the substituent at the ortho-position relative to the sulfonate group influences the molecular weight and isotactic regularity of the obtained polypropylenes. Statistical analysis suggested that the introduction of substituents at the ortho-position relative to the sulfonate group favors enantiomorphic site control over chain end control in the chain propagation step. The triad isotacticity could be increased to mm=0.55-0.59, with formation of crystalline polar polypropylenes, as supported by the presence of melting points and sharp peaks in the corresponding X-ray diffraction patterns. PMID:27161896

  19. Polylactide-based microspheres prepared using solid-state copolymerized chitosan and d,l-lactide.

    PubMed

    Demina, T S; Akopova, T A; Vladimirov, L V; Zelenetskii, A N; Markvicheva, E A; Grandfils, Ch

    2016-02-01

    Amphiphilic chitosan-g-poly(d,l-lactide) copolymers have been manufactured via solid-state mechanochemical copolymerization and tailored to design polyester-based microspheres for tissue engineering. A single-step solid-state reactive blending (SSRB) using low-temperature co-extrusion has been used to prepare these copolymers. These materials have been valorized to stabilize microspheres processed by an oil/water emulsion evaporation technique. Introduction of the copolymers either in water or in the oil phase of the emulsion allowed to replace a non-degradable emulsifier typically used for microparticle preparation. To enhance cell adhesion, these copolymers were also tailored to bring amino-saccharide positively charged segments to the microbead surface. Size distribution, surface morphology, and total microparticle yield have been studied and optimized as a function of the copolymer composition. PMID:26652381

  20. Graft copolymerization of ethyl acrylate onto tamarind kernel powder, and evaluation of its biodegradability.

    PubMed

    del Real, Alicia; Wallander, Daniela; Maciel, Alfredo; Cedillo, Gerardo; Loza, Herminia

    2015-03-01

    In the present study, tamarind kernel powder and ethyl acrylate were reacted by free radical polymerization to synthesize a grafted copolymer soluble in water. The grafted copolymer was analyzed by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR); FTIR showed a shift of the vibration of R-CO-OR' from 1258 cm(-1) to 1253 cm(-1). This shift appeared because of the grafting copolymerization. Films were prepared to study the mechanical properties and the biodegradation of this material. The mechanical properties of the grafted copolymer were found to lie between those of the parent polymers, suitable for disposable products. The new grafted copolymer manifested a steady process of biodegradation under incubation with the bacterial strain Alicycliphilus sp. BQ1; this was proved by scanning electron microscopy (SEM) and near infrared spectroscopy (NIR).

  1. Polylactide-based microspheres prepared using solid-state copolymerized chitosan and d,l-lactide.

    PubMed

    Demina, T S; Akopova, T A; Vladimirov, L V; Zelenetskii, A N; Markvicheva, E A; Grandfils, Ch

    2016-02-01

    Amphiphilic chitosan-g-poly(d,l-lactide) copolymers have been manufactured via solid-state mechanochemical copolymerization and tailored to design polyester-based microspheres for tissue engineering. A single-step solid-state reactive blending (SSRB) using low-temperature co-extrusion has been used to prepare these copolymers. These materials have been valorized to stabilize microspheres processed by an oil/water emulsion evaporation technique. Introduction of the copolymers either in water or in the oil phase of the emulsion allowed to replace a non-degradable emulsifier typically used for microparticle preparation. To enhance cell adhesion, these copolymers were also tailored to bring amino-saccharide positively charged segments to the microbead surface. Size distribution, surface morphology, and total microparticle yield have been studied and optimized as a function of the copolymer composition.

  2. Graft copolymerization of ethyl acrylate onto tamarind kernel powder, and evaluation of its biodegradability.

    PubMed

    del Real, Alicia; Wallander, Daniela; Maciel, Alfredo; Cedillo, Gerardo; Loza, Herminia

    2015-03-01

    In the present study, tamarind kernel powder and ethyl acrylate were reacted by free radical polymerization to synthesize a grafted copolymer soluble in water. The grafted copolymer was analyzed by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR); FTIR showed a shift of the vibration of R-CO-OR' from 1258 cm(-1) to 1253 cm(-1). This shift appeared because of the grafting copolymerization. Films were prepared to study the mechanical properties and the biodegradation of this material. The mechanical properties of the grafted copolymer were found to lie between those of the parent polymers, suitable for disposable products. The new grafted copolymer manifested a steady process of biodegradation under incubation with the bacterial strain Alicycliphilus sp. BQ1; this was proved by scanning electron microscopy (SEM) and near infrared spectroscopy (NIR). PMID:25498603

  3. Metal-Catalyzed Cyclization Reactions of 2,3,4-Trien-1-ols: A Joint Experimental-Computational Study.

    PubMed

    Alcaide, Benito; Almendros, Pedro; Cembellín, Sara; Fernández, Israel; Martínez Del Campo, Teresa

    2016-08-01

    Controlled preparation of tri- and tetrasubstituted furans, as well as carbazoles has been achieved through chemo- and regioselective metal-catalyzed cyclization reactions of cumulenic alcohols. The gold- and palladium-catalyzed cycloisomerization reactions of cumulenols, including indole-tethered 2,3,4-trien-1-ols, to trisubstituted furans was effective, due to a 5-endo-dig oxycyclization by attack of the hydroxy group onto the central cumulene double bond. In contrast, palladium-catalyzed heterocyclization/coupling reactions with 3-bromoprop-1-enes furnished tetrasubstituted furans. Also studied was the palladium-catalyzed cyclization/coupling sequence involving protected indole-tethered 2,3,4-trien-1-ols and 3-bromoprop-1-enes that exclusively generated trisubstituted carbazole derivatives. These results could be explained through a selective 6-endo-dig cumulenic hydroarylation, followed by aromatization. DFT calculations were carried out to understand this difference in reactivity. PMID:27383332

  4. Experimental and theoretical assessment of the mechanism involved in the reaction of steroidal ketone semicarbazone with hydrogen peroxide

    NASA Astrophysics Data System (ADS)

    Sharma, Kamlesh; Mishra, Shivani B.; Mishra, Ajay K.

    2011-09-01

    3β-Acetoxy-5α-cholestan-6-one semicarbazone 1 on reaction with hydrogen peroxide affords selectively 3β-acetoxy-5α-cholestan-6-spiro-1',2',4'-triazolidine-3'-one 2. The structural assignment of the product was confirmed by spectral data and elemental analysis. A free radical mechanism of the present reaction was described successfully by calculating theoretical models of 1, A, B and 2, using DFT with B3LYP/6-31G* basis set. It was found that the reaction undergoes through the formation of two radical intermediates and the only one isomer of the product in which -NH-CO- group is cis with respect C5α-H, was selectively obtained. Frontier molecular orbital, spin electronic density, electrostatic potential and atomic charges were discussed.

  5. Inverse opal pH sensors with various protic monomers copolymerized with polyhydroxyethylmethacrylate hydrogel.

    PubMed

    Shin, Jinsub; Han, Sung Gu; Lee, Wonmok

    2012-11-01

    pH sensitive inverse opal sensors were synthesized using various vinyl monomers containing acidic or basic substituents. Acrylic acid (AA), vinylphosphonic acid (VPA), vinylimidazole (VI), and dimethylaminoethylmethacrylic acid (DMAEMA) were respectively copolymerized with hydroxyethylmethacrylate (HEMA), the building block monomer of the hydrogel via UV-initiated photopolymerization. Opal templating and subsequent template removal enabled the fabrication of four inverse opal (IO) hydrogel colorimetric sensors, which responded to pH in different fashions. pH-dependent swelling of the IO hydrogel induced the red-shift of the diffracted color. The sensors containing AA or VPA, the proton donating monomers showed the color shifts from green to red with pH increase due to the increased concentration of carboxylate anions bound to the hydrogel. Diprotic VPA sensor exhibited two-step increases of diffracted wavelengths at its pK(a1) and pK(a2) respectively. The sensors containing proton acceptors, VI and DMAEMA showed the pH-dependent color changes in an opposite way to the AA sensor and the VPA sensor since their ionizations take place by lowering pH due to the protonation at the amino groups. The shapes of pH response curves of VI and DMAEMA sensors were similar but pK(b)s were different from each other. Optical diffraction responses of four sensors were compared with the calculated concentration ratios of the ionized species to the total monomer with pH variation, and a deswelling effect in the vicinities of pK(a)s of phosphate buffer on the swelling response could be explained by shrinkage of PHEMA hydrogel under high ionic environment. In addition, copolymerization of AA, VPA and HEMA was carried out which resulted in a pH sensor exhibiting a wider range of pH for color change.

  6. Diphenylbutadienes Syntheses by Means of the Wittig Reaction: Experimental Introduction to the Use of Phase Transfer Catalysis.

    ERIC Educational Resources Information Center

    Gillois, J.; And Others

    1980-01-01

    The synthesis of 1,4-diphenylbutadiene by means of the Wittig reaction is presented as suitable for organic chemistry students at the end of a basic laboratory program to apply laboratory skills and display understanding of the use of phase transfer catalysis and its application in syntheses. (CS)

  7. Gas-phase reactions of aryl radicals with 2-butyne: experimental and theoretical investigation employing the N-methyl-pyridinium-4-yl radical cation.

    PubMed

    Lam, A K Y; Li, C; Khairallah, G; Kirk, B B; Blanksby, S J; Trevitt, A J; Wille, U; O'Hair, R A J; da Silva, G

    2012-02-21

    Aromatic radicals form in a variety of reacting gas-phase systems, where their molecular weight growth reactions with unsaturated hydrocarbons are of considerable importance. We have investigated the ion-molecule reaction of the aromatic distonic N-methyl-pyridinium-4-yl (NMP) radical cation with 2-butyne (CH(3)C≡CCH(3)) using ion trap mass spectrometry. Comparison is made to high-level ab initio energy surfaces for the reaction of NMP and for the neutral phenyl radical system. The NMP radical cation reacts rapidly with 2-butyne at ambient temperature, due to the apparent absence of any barrier. The activated vinyl radical adduct predominantly dissociates via loss of a H atom, with lesser amounts of CH(3) loss. High-resolution Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry allows us to identify small quantities of the collisionally deactivated reaction adduct. Statistical reaction rate theory calculations (master equation/RRKM theory) on the NMP+2-butyne system support our experimental findings, and indicate a mechanism that predominantly involves an allylic resonance-stabilized radical formed via H atom shuttling between the aromatic ring and the C(4) side-chain, followed by cyclization and/or low-energy H atom β-scission reactions. A similar mechanism is demonstrated for the neutral phenyl radical (Ph˙)+2-butyne reaction, forming products that include 3-methylindene. The collisionally deactivated reaction adduct is predicted to be quenched in the form of a resonance-stabilized methylphenylallyl radical. Experiments using a 2,5-dichloro substituted methyl-pyridiniumyl radical cation revealed that in this case CH(3) loss from the 2-butyne adduct is favoured over H atom loss, verifying the key role of ortho H atoms, and the shuttling mechanism, in the reactions of aromatic radicals with alkynes. As well as being useful phenyl radical analogues, pyridiniumyl radical cations may form in the ionosphere of Titan, where they could undergo rapid

  8. Extension of the energy range of experimental activation cross-sections data of deuteron induced nuclear reactions on indium up to 50MeV.

    PubMed

    Tárkányi, F; Ditrói, F; Takács, S; Hermanne, A; Ignatyuk, A V

    2015-11-01

    The energy range of our earlier measured activation cross-sections data of longer-lived products of deuteron induced nuclear reactions on indium were extended from 40MeV up to 50MeV. The traditional stacked foil irradiation technique and non-destructive gamma spectrometry were used. No experimental data were found in literature for this higher energy range. Experimental cross-sections for the formation of the radionuclides (113,110)Sn, (116m,115m,114m,113m,111,110g,109)In and (115)Cd are reported in the 37-50MeV energy range, for production of (110)Sn and (110g,109)In these are the first measurements ever. The experimental data were compared with the results of cross section calculations of the ALICE and EMPIRE nuclear model codes and of the TALYS 1.6 nuclear model code as listed in the on-line library TENDL-2014.

  9. Examination and experimental constraints of the stellar reaction rate factor NA<σv> of the 18Ne(α,p)21Na reaction at temperatures of x-ray bursts

    NASA Astrophysics Data System (ADS)

    Mohr, P.; Matic, A.

    2013-03-01

    The 18Ne(α,p)21Na reaction is one key for the breakout from the hot CNO cycles to the rp-process. Recent papers have provided reaction rate factors NA<σv> which are discrepant by at least one order of magnitude. The compatibility of the latest experimental results is tested, and a partial explanation for the discrepant NA<σv> is given. A new rate factor is derived from the combined analysis of all available data. The new rate factor is located slightly below the higher rate factor found by Matic [Phys. Rev. CPRVCAN0556-281310.1103/PhysRevC.80.055804 80, 055804 (2009)] at low temperatures and significantly below at higher temperatures whereas it is about a factor of 5 higher than the lower rate factor recently published by Salter [Phys. Rev. Lett.PRLTAO0031-900710.1103/PhysRevLett.108.242701 108, 242701 (2012)].

  10. Experimental disentangling of spatial-compatibility and interhemispheric-relay effects in simple reaction time (Poffenberger paradigm).

    PubMed

    Braun, Claude M J; Larocque, Caroline; Achim, André

    2004-08-01

    Spatial-compatibility effects can be obtained in simple reaction time (SRT) provided that spatially distinct responses are frequently required. Since this effect is limited to trials with relatively long reaction times (RTs), Hommel (1996b) proposed that if the response does not occur shortly after stimulus detection, then the spatial code of the stimulus can interfere with that of the response. A series of experiments is reported showing that (a) spatial compatibility in SRT to lateralized stimuli is not an alternative, but rather a complementary, explanation to interhemispheric transfer time (contrary to what Hommel surmised), and (b) the spatial compatibility component is essentially limited to the first trial after shifting response preparation from one-half of the visual fields to the other, suggesting a mechanism akin to an orienting response.

  11. An experimental and theoretical investigation of the N(⁴S) + C₂(¹Σg⁺) reaction at low temperature.

    PubMed

    Loison, Jean-Christophe; Hu, Xixi; Han, Shanyu; Hickson, Kevin M; Guo, Hua; Xie, Daiqian

    2014-07-21

    Rate constants for the N((4)S) + C2((1)Σg(+)) reaction have been measured in a continuous supersonic flow reactor over the range 57 K ≤T≤ 296 K by the relative rate technique employing the N((4)S) + OH(X(2)Π) → H((2)S) + NO(X(2)Π) reaction as a reference. Excess concentrations of atomic nitrogen were produced by the microwave discharge method and C2 and OH radicals were created by the in situ pulsed laser photolysis of precursor molecules C2Br4 and H2O2 respectively. In parallel, quantum dynamics calculations were performed based on an accurate global potential energy surfaces for the three lowest lying quartet states of the C2N molecule. The 1(4)A'' potential energy surface is barrierless, having two deep potential wells corresponding to the NCC and CNC intermediates. Both the experimental and theoretical work show that the rate constant decreases to low temperature, although the experimentally measured values fall more rapidly than the theoretical ones except at the lowest temperatures. Astrochemical simulations indicate that this reaction could be the dominant source of CN in dense interstellar clouds.

  12. Experimental studies of the kinetics of the reaction of hydroxyl (OH) radicals with 3-methylfuran at low pressure

    NASA Astrophysics Data System (ADS)

    Liljegren, J. A.; Stevens, P. S.

    2011-12-01

    In addition to anthropogenic origins from fossil fuel combustion and biomass burning, 3-methylfuran is an atmospheric constituent of interest due to biogenic origins from the OH-initiated oxidation of isoprene. Although the yield of 3-methylfuran produced from the OH-initiated oxidation of isoprene is relatively small (approximately 5%), 3-methylfuran could contribute significantly to atmospheric chemistry due to the high emission rate of isoprene to the atmosphere. A knowledge of the rate constant for the reaction of OH radicals with 3-methylfuran under a variety of conditions is important for determining the overall impact of isoprene emissions on atmospheric chemistry. The rate constant for the reaction of OH with 3-methylfuran has been measured as a function of temperature at low pressure using discharge-flow techniques coupled with laser induced fluorescence detection of OH. These absolute measurements at room temperature will be compared to previous measurements using relative rate techniques. The measurements of the temperature dependence for this reaction are the first to be reported.

  13. Experimental and theoretical rate coefficients for the gas phase reaction of β-Pinene with OH radical

    NASA Astrophysics Data System (ADS)

    Dash, Manas Ranjan; Rajakumar, B.

    2013-11-01

    Rate coefficient for the reaction of β-pinene with OH radicals was determined at 298 K and 800 Torr of N2 using the relative rate technique. Isobutylene was used as a reference compound and the concentrations of the organics were followed by gas chromatographic analysis. The rate coefficient for the reaction of β-pinene with OH radical was measured to be (9.35 ± 2.79) × 10-11 cm3 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). The kinetics data obtained over the temperature range of 200-400 K were used to derive the Arrhenius expression: k(T) = 8.24 × 10-23T3.41 exp[2421/T] cm3 molecule-1 s-1. The OH-driven atmospheric lifetime (τ) and global warming potential (GWP) for β-pinene were computed and concluded that β-pinene is very short lived (2.5 h) in the Earth's atmosphere with a GWP of 1.6 × 10-2 at 20 years horizon of time and which is negligible. The ozone formation potential of β-pinene was also calculated and reported in this present work.

  14. First Experimental Measurement of the {sup 18}O(p,{alpha}){sup 15}N Reaction at Astrophysical Energies

    SciTech Connect

    La Cognata, M.; Sergi, M. L.; Spitaleri, C.; Cherubini, S.; Gulino, M.; Kiss, G.; Lamia, L.; Pizzone, R. G.; Romano, S.; Mukhamedzhanov, A.; Goldberg, V.; Tribble, R.; Coc, A.; Hammache, F.; Sereville, N. de; Tumino, A.

    2010-11-24

    The {sup 18}O(p,{alpha}){sup 15}N and {sup 17}O(p,{alpha}){sup 14}N reactions are of primary importance in several as-trophysical scenarios, including nucleosynthesis inside Asymptotic Giant Branch stars and oxygen and nitrogen isotopic ratios in meteorite grains. They are also key reactions to understand exotic systems such as R-Coronae Borealis stars and novae. Thus, the measurement of their cross sections in the low energy region can be crucial to reduce the nuclear uncertainty on theoretical predictions, because the resonance parameters are poorly determined. The Trojan Horse Method, in its newly developed form particularly suited to investigate low-energy resonances, has been applied to the {sup 2}H({sup 18}O,{alpha}{sup 15}N)n and {sup 2}H({sup 17}O,{alpha}{sup 14}N)n reactions to deduce the {sup 18}O(p,{alpha}){sup 15}N and {sup 17}O(p,{alpha}){sup 14}N cross sections at low energies. Resonances in the {sup 18}O(p,{alpha}){sup 15}N and {sup 17}O(p,{alpha}){sup 14}N excitation functions have been studied and the resonance parameters deduced.

  15. Experimental study of incomplete fusion reactions in the O16 + Te130 system below 6 MeV/nucleon

    NASA Astrophysics Data System (ADS)

    Singh, Devendra P.; Sharma, Vijay R.; Yadav, Abhishek; Singh, Pushpendra P.; Unnati, Sharma, M. K.; Kumar, R.; Singh, B. P.; Prasad, R.

    2014-02-01

    Background: The measurement and analysis of excitation functions may be used as an important tool to understand incomplete fusion reaction dynamics. Purpose: Several studies have been carried out to study incomplete fusion reactions at low energies, but a clear picture of incomplete fusion reaction processes at energies below 6 MeV/nucleon has yet to emerge. Further, there is no theoretical model which may give a good representation of incomplete fusion processes. Method: Off-line γ-ray spectrometry has been used to measure the excitation functions in the 16O+130Te system at energies ≈3-6 MeV/nucleon. Results: Excitation functions for five reaction products populated via complete and/or incomplete fusion processes in the O16 + Te130 system have been measured. Measured cross-sections have been compared with the predictions of the statistical model code pace4. A significant enhancement in the measured excitation functions compared to theoretical predictions for α-emitting channels has been observed and is attributed to incomplete fusion processes. The relative strength of incomplete fusion has been found to increase with projectile energy. In the case of the Xe133(3αn) channel, the isomeric cross-section ratios have been deduced and found to increase rapidly with beam energy, indicating the importance of imparted angular momentum. The angular momentum at different energies has also been calculated. The analysis of the data indicates that incomplete fusion is associated even for angular momentum values smaller than the critical angular momentum for complete fusion. The results have been discussed in terms of the α-cluster structure of the projectile for various fusion reactions. Conclusions: It may be concluded that, apart from complete fusion, incomplete fusion processes are of greater importance even at energies as low as ≈3-6 MeV/nucleon, where fusion evaporation channels are expected to be dominant. The measured isomeric cross-section ratio for the

  16. [The use of polymerase chain reaction for detection of the agents of glanders and melioidosis using experimental infection].

    PubMed

    Altukhova, V V; Antonov, V A; Tkachenko, G A; Zinchenko, O V; Zamaraev, V S; Plekhanova, N G; Iliukhin, V I; Trofimov, D Iu

    2007-01-01

    Glanders and melioidosis are severe infectious diseases of people and animals. The causative agents of these infections refer to the potential agents of bioterrorism of group B. In this work the possibility of use of flagellin-based primers for the identification of B. mallei and B. pseudomallei and for diagnosis of experimental glanders and melioidosis was studied. The obtained results permit to make a conclusion that PCR using the developed primers may be recommended for the incorporation in the scheme of laboratory diagnosis of glanders and melioidosis both for the identification of clean cultures and in experimental clinical material.

  17. Experimental and theoretical study on gas-phase ion/molecule reactions of silver trimer cation, Ag{sub 3}{sup +}, with 12-crown-4

    SciTech Connect

    Kumondai, Kousuke; Toyoda, Michisato; Ishihara, Morio; Katakuse, Itsuo; Takeuchi, Takae; Ikeda, Mai; Iwamoto, Kenichi

    2005-07-08

    The reaction mechanisms of silver trimer cation, Ag{sub 3}{sup +}, with 12-crown-4 (12C4) were studied experimentally and theoretically. Using a cylindrical ion trap time-of-flight mass spectrometer, gas-phase ion/molecule reactions of Ag{sub 3}{sup +} with 12C4 were observed. Metal-ligand complexes of [Ag(12C4)]{sup +}, [Ag{sub 3}(12C4)]{sup +} and [Ag{sub 3}(12C4){sub 2}]{sup +}, and of [Ag(12C4){sub 2}]{sup +} and [Ag{sub 3}(12C4){sub 3}]{sup +}, were observed as the reaction intermediates and terminal products, respectively. The formations of the [Ag(12C4)]{sup +} and [Ag(12C4){sub 2}]{sup +} complexes indicated that the neutral dimer (Ag{sub 2}) had been eliminated from the trimer cation. From the results of ab initio calculations at the HF/LanL2DZ level of theory and the experiments, it is suggested that three 12C4 molecules can attach to Ag{sub 3}{sup +} through consecutive reactions and that neutral Ag{sub 2} can be easily eliminated from [Ag{sub 3}(12C4)]{sup +}.

  18. Generation of 4-hydroxy-2,5-dimethyl-3(2H)-furanone from rhamnose as affected by reaction parameters: experimental design approach.

    PubMed

    Illmann, Silke; Davidek, Tomas; Gouézec, Elisabeth; Rytz, Andreas; Schuchmann, Heike P; Blank, Imre

    2009-04-01

    The formation of 4-hydroxy-2,5-dimethyl-3(2H)-furanone (HDMF) was studied in aqueous model systems containing L-rhamnose and L-lysine. The approach consisted in systematically varying four reaction parameters (rhamnose concentration, rhamnose to lysine ratio, pH, and phosphate concentration) at 3 levels. A fractional factorial design was used to reduce the number of trials. The degradation of rhamnose was followed by high performance anion exchange chromatography and the formation of HDMF by solid phase extraction in combination with GC/MS. The study permitted the identification of critical reaction parameters that affect the formation of HDMF from rhamnose in aqueous systems. Although all studied parameters have some impact on the HDMF formation and rhamnose degradation kinetics, the effect of phosphate is by far the most important, followed by concentration of precursors and pH. The experimental design approach permitted us, with a limited number of experiments, to accurately model the effects of the four investigated reaction parameters on the kinetics of rhamnose degradation and HDMF formation (R(2)>0.93). Overall, the results indicate that rhamnose can be an excellent precursor of HDMF (yield >40 mol%), if the reaction conditions are well mastered. PMID:19256512

  19. Regio- and stereospecific living polymerization and copolymerization of (E)-1,3-pentadiene with 1,3-butadiene by half-sandwich scandium catalysts.

    PubMed

    Nishii, Kei; Kang, Xiaohui; Nishiura, Masayoshi; Luo, Yi; Hou, Zhaomin

    2013-07-01

    The living isospecific-cis-1,4-polymerization and block-copolymerization of (E)-1,3-pentadiene with 1,3-butadiene have been achieved for the first time by using cationic half-sandwich scandium catalysts.

  20. A fully integrated high-throughput screening methodology for the discovery of new polyolefin catalysts: discovery of a new class of high temperature single-site group (IV) copolymerization catalysts.

    PubMed

    Boussie, Thomas R; Diamond, Gary M; Goh, Christopher; Hall, Keith A; LaPointe, Anne M; Leclerc, Margarete; Lund, Cheryl; Murphy, Vince; Shoemaker, James A W; Tracht, Ursula; Turner, Howard; Zhang, Jessica; Uno, Tetsuo; Rosen, Robert K; Stevens, James C

    2003-04-01

    For the first time, new catalysts for olefin polymerization have been discovered through the application of fully integrated high-throughput primary and secondary screening techniques supported by rapid polymer characterization methods. Microscale 1-octene primary screening polymerization experiments combining arrays of ligands with reactive metal complexes M(CH(2)Ph)(4) (M = Zr, Hf) and multiple activation conditions represent a new high-throughput technique for discovering novel group (IV) polymerization catalysts. The primary screening methods described here have been validated using a commercially relevant polyolefin catalyst, and implemented rapidly to discover the new amide-ether based hafnium catalyst [eta(2)-(N,O)[bond](2-MeO[bond]C(6)H(4))(2,4,6-Me(3)C(6)H(2))N]Hf(CH(2)Ph)(3) (1), which is capable of polymerizing 1-octene to high conversion. The molecular structure of 1 has been determined by X-ray diffraction. Larger scale secondary screening experiments performed on a focused 96-member amine-ether library demonstrated the versatile high temperature ethylene-1-octene copolymerization capabilities of this catalyst class, and led to significant performance improvements over the initial primary screening discovery. Conventional one gallon batch reactor copolymerizations performed using selected amide-ether hafnium compounds confirmed the performance features of this new catalyst class, serving to fully validate the experimental results from the high-throughput approaches described herein.

  1. Open Experimentation on Phenomena of Chemical Reactions via the Learning Company Approach in Early Secondary Chemistry Education

    ERIC Educational Resources Information Center

    Beck, Katharina; Witteck, Torsten; Eilks, Ingo

    2010-01-01

    Presented is a case study on the implementation of open and inquiry-type experimentation in early German secondary chemistry education. The teaching strategy discussed follows the learning company approach. Originally adopted from vocational education, the learning company method is used to redirect lab-oriented classroom practice towards a more…

  2. Experimental and quantum-chemical studies of the reactions of 6-methyluracil with succinic and fumaric acids

    NASA Astrophysics Data System (ADS)

    Terent'ev, A. O.; Borisova, N. S.; Khamitov, E. M.; Zimin, Yu. S.; Mustafin, A. G.

    2014-12-01

    Possible structures of 6-methyluracil complexes with succinic and fumaric acids are studied by quantum-chemical means. The possibility of complex formation occurring between 6-methyluracil and the acids in the ionized and nonionized states is evaluated. The form of the complexes containing the nonionized acid is found to dominate. The quantum-chemical calculation data are consistent with the experimental results.

  3. Trans-cinnamic acid and coumarin-3-carboxylic acid: experimental charge-density studies to shed light on [2 + 2] cycloaddition reactions.

    PubMed

    Howard, Judith A K; Mahon, Mary F; Raithby, Paul R; Sparkes, Hazel A

    2009-04-01

    As part of an ongoing series of experimental charge-density investigations into the intra- and intermolecular interactions present in compounds which undergo solid-state [2 + 2] cycloaddition reactions, the charge-density analyses of trans-cinnamic acid and coumarin-3-carboxylic acid are reported. Thus, high-resolution single-crystal X-ray diffraction data were recorded at 100 K for trans-cinnamic acid (sin theta/lambda(max) = 1.03 A(-1)) and coumarin-3-carboxylic acid (sin theta/lambda(max) = 1.19 A(-1)). In addition to the anticipated O-H...O hydrogen bonds weak C-H...O interactions were identified in both structures along with very weak intermolecular interactions between pairs of molecules that undergo solid-state [2 + 2] cycloaddition reactions upon irradiation.

  4. Tunable mechano-responsive organogels by ring-opening copolymerizations of N-carboxyanhydrides

    PubMed Central

    Fan, Jingwei; Zou, Jiong; He, Xun; Zhang, Fuwu; Zhang, Shiyi; Raymond, Jeffery E.; Wooley, Karen L.

    2013-01-01

    The simple copolymerization of N-carboxyanhydride (NCA) monomers is utilized to generate copolypeptides having a combination of α-helix and β-sheet sub-structures that, when grown from a solvophilic synthetic polymer block segment, are capable of driving mechano-responsive supramolecular sol-to-gel-to-sol and sol-to-gel-to-gel transitions reversibly, which allow also for injection-based processing and self-healing behaviors. A new type of polypeptide-based organogelator, methoxy poly(ethylene glycol)-block-poly(γ-benzyl-l-glutamate-co-glycine) (mPEG-b-P(BLG-co-Gly)), is facilely synthesized by statistical ring-opening copolymerizations (ROPs) of γ-benzyl-l-glutamate (BLG) and glycine (Gly) NCAs initiated by mPEG-amine. These systems exhibit tunable secondary structures and result in sonication stimulus responsiveness of the organogels with the polypeptide segment variation, controlled by varying the ratio of BLG NCA to Gly NCA during the copolymerizations. Attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) studies indicate the α-helical component decreases while the β-sheet content increases systematically with a higher mole fraction of Gly in the polypeptide segment. The supramolecular assembly of β-sheet nanofibrils, having a tunable width over the range of 10.4 – 14.5 nm with varied BLG to Gly ratio, are characterized by transmission electron microscopy (TEM). The further self-assembly of these nanostructures into 3-D gel networks within N,N-dimethylformamide (DMF) occurs at low critical gelation concentrations (CGC) (lowest ca. 0.6 wt %). Increased BLG to Gly ratios lead to an increase of the α-helical component in the secondary structures of the polypeptide segments, resulting in wider and more flexible nanofibrils. The presence of α-helical component in the polymers enhances the stability of the organogels against sonication, and instantaneous gel-to-gel transitions are observed as in situ reconstruction of networks

  5. Control of particle size by feed composition in the nanolatexes produced via monomer-starved semicontinuous emulsion copolymerization.

    PubMed

    Sajjadi, Shahriar

    2015-05-01

    Conventional batch and semicontinuous emulsion copolymerizations often produce large particles whose size cannot be easily correlated with the comonomer feed compositions, and are to some degree susceptible to composition drift. In contrast, we found that copolymer nanolatexes made via semicontinuous monomer-starved emulsion copolymerizations are featured with an average nanoparticle size being controlled by the feed composition, a high conversion achieved, and a high degree of particle composition uniformity. This was achieved because the rate of particle growth, during nucleation, was controlled by the rate of comonomer addition, and the copolymer composition, surfactant parking area on the particles, and nucleation efficiency determined by the comonomer feed composition. Two model systems, methyl methacrylate/styrene and vinyl acetate/butyl acrylate, with significant differences in water solubility were studied. Monomers were added to the aqueous solution of sodium dodecylsulfate and potassium persulfate at a low rate to achieve high instantaneous conversions. PMID:25617612

  6. Reactivity of vinyl ethers and vinyl ribosides in UV-initiated free radical copolymerization with acceptor monomers.

    PubMed

    Pichavant, Loic; Guillermain, Céline; Coqueret, Xavier

    2010-09-13

    The reactivity of various vinyl ethers and vinyloxy derivatives of ribose in the presence of diethyl fumarate or diethyl maleate was investigated for evaluating the potential of donor-acceptor-type copolymerization applied to unsaturated monomers derived from renewable feedstock. The photochemically induced polymerization of model monomer blends in the bulk state was monitored by infrared spectroscopy. The method allowed us to examine the influence of monomer pair structure on the kinetic profiles. The simultaneous consumption of both monomers was observed, supporting an alternating copolymerization mechanism. A lower reactivity of the blends containing maleates compared with fumarates was confirmed. The obtained kinetic data revealed a general correlation between the initial polymerization rate and the Hansen parameter δ(H) associated with the H-bonding aptitude of the donor monomer.

  7. Preparation of a DNA matrix via an electrochemically directed copolymerization of pyrrole and oligonucleotides bearing a pyrrole group.

    PubMed Central

    Livache, T; Roget, A; Dejean, E; Barthet, C; Bidan, G; Téoule, R

    1994-01-01

    A new methodology for the preparation of addressed DNA matrices is described. The process includes an electrochemically directed copolymerization of pyrrole and oligonucleotides bearing on their 5' end a pyrrole moiety introduced by phosphoramidite chemistry. The electro-controlled synthesis of the copolymer (poly-pyrrole) gives, in one step, a solid conducting film deposited on the surface of an electrode. The resulting polymer consists of pyrrole chains bearing covalently linked oligonucleotide. The polymer growth is limited to the electrode surface, so that it is possible to prepare a DNA matrix on a multiple electrode device by successive copolymerizations. A support bearing four oligonucleotides was used to detect three ras mutations on a synthetic DNA fragment. PMID:8065902

  8. Functional Degradable Polymers by Radical Ring-Opening Copolymerization of MDO and Vinyl Bromobutanoate: Synthesis, Degradability and Post-Polymerization Modification

    PubMed Central

    2015-01-01

    The synthesis of vinyl bromobutanoate (VBr), a new vinyl acetate monomer derivative obtained by the palladium-catalyzed vinyl exchange reaction between vinyl acetate (VAc) and 4-bromobutyric acid is reported. The homopolymerization of this new monomer using the RAFT/MADIX polymerization technique leads to the formation of novel well-defined and controlled polymers containing pendent bromine functional groups able to be modified via postpolymerization modification. Furthermore, the copolymerization of vinyl bromobutanoate with 2-methylene-1,3-dioxepane (MDO) was also performed to deliver a range of novel functional degradable copolymers, poly(MDO-co-VBr). The copolymer composition was shown to be able to be tuned to vary the amount of ester repeat units in the polymer backbone, and hence determine the degradability, while maintaining a control of the final copolymers’ molar masses. The addition of functionalities via simple postpolymerization modifications such as azidation and the 1,3-dipolar cycloaddition of a PEG alkyne to an azide is also reported and proven by 1H NMR spectroscopy, FTIR spectroscopy, and SEC analyses. These studies enable the formation of a novel class of hydrophilic functional degradable copolymers using versatile radical polymerization methods. PMID:25997518

  9. Spontaneously Healable Thermoplastic Elastomers Achieved through One-Pot Living Ring-Opening Metathesis Copolymerization of Well-Designed Bulky Monomers.

    PubMed

    Yang, Ji-Xing; Long, Ying-Yun; Pan, Li; Men, Yong-Feng; Li, Yue-Sheng

    2016-05-18

    We report here a series of novel spontaneously healable thermoplastic elastomers (TPEs) with a combination of improved mechanical and good autonomic self-healing performances. Hard-soft diblock and hard-soft-hard triblock copolymers with poly[exo-1,4,4a,9,9a,10-hexahydro-9,10(1',2')-benzeno-l,4-methanoanthracene] (PHBM) as the hard block and secondary amide group containing norbornene derivative polymer as the soft block were synthesized via living ring-opening metathesis copolymerization by use of Grubbs third-generation catalyst through sequential monomer addition. The microstructure, mechanical, self-healing, and surface morphologies of the block copolymers were thoroughly studied. Both excellent mechanical performance and self-healing capability were achieved for the block copolymers because of the interplayed physical cross-link of hard block and dynamic interaction formed by soft block in the self-assembled network. Under an optimized hard block (PHBM) weight ratio of 5%, a significant recovery of tensile strength (up to 100%) and strain at break (ca. 85%) was achieved at ambient temperature without any treatment even after complete rupture. Moreover, the simple reaction operations and well-designed monomers offer versatility in tuning the architectures and properties of the resulting block copolymers. PMID:27136676

  10. β-Oxygen effect in the Barton-McCombie deoxygenation reaction: further experimental and theoretical findings.

    PubMed

    Sánchez-Eleuterio, Alma; Sandoval-Lira, Jacinto; García-Sánchez, Jenny; Monterrosas-Pérez, Lorena; Hernández-Pérez, Julio M; Quintero, Leticia; Sartillo-Piscil, Fernando

    2013-09-20

    The chemistry of (S)-methyl xanthates derived from xylo- and ribo-furanose derivatives in the presence of the stannyl radical is investigated. Xanthate derived from β-xylo-furanose affords exclusively a deoxygenated product; whereas, under the same reaction conditions, the α-ribo-furanose xanthate derivative produces quantitatively a hemithioacetal compound. We reasoned that in the case of the β-xylo-furanose derivative, a favorable β-oxygen effect in the Barton-McCombie deoxygenation reaction is operating where, according to theoretical calculations, unusual molecular orbital interactions (and not strain, as previously proposed) are present. These orbital interactions involve the SOMO (intermediary generated from the stannyl radical addition) with the σ* orbital of the bond undergoing cleavage and this with the two C-O antibonding orbitals anti oriented. Such molecular orbital interactions are not present in the α-ribo-furanose; therefore, the β-scission is highly delayed, and due to the reversibly nature of the stannyl radical addition, the ribo-furanose xanthate is forced to take an alternative route: the homolytic substitution (S(H)2) of the sulfide sulfur by stannyl radical. This radical addition gives the alkoxythiocarbonyl radical, which is trapped by Bu3SnH before the elimination of carbonyl sulfide; subsequently, radical stannyl addition followed by radical reduction produces the hemithioacetal.

  11. Anti-Inflammatory Property of Plantago major Leaf Extract Reduces the Inflammatory Reaction in Experimental Acetaminophen-Induced Liver Injury.

    PubMed

    Hussan, Farida; Mansor, Adila Sofea; Hassan, Siti Nazihahasma; Tengku Nor Effendy Kamaruddin, Tg Nurul Tasnim; Budin, Siti Balkis; Othman, Faizah

    2015-01-01

    Hepatic injury induces inflammatory process and cell necrosis. Plantago major is traditionally used for various diseases. This study aimed to determine the anti-inflammatory property of P. major leaf extracts on inflammatory reaction following acetaminophen (APAP) hepatotoxicity. Thirty male Sprague-Dawley rats were divided into 5 groups, namely, normal control (C), APAP, aqueous (APAP + AQ), methanol (APAP + MT), and ethanol (APAP + ET) extract treated groups. All APAP groups received oral APAP (2 g/kg) at day 0. Then, 1000 mg/kg dose of P. major extracts was given for six days. The levels of liver transaminases were measured at day 1 and day 7 after APAP induction. At day 7, the blood and liver tissue were collected to determine plasma cytokines and tissue 11β-HSD type 1 enzyme. The in vitro anti-inflammatory activities of methanol, ethanol, and aqueous extracts were 26.74 ± 1.6%, 21.69 ± 2.81%, and 12.23 ± 3.15%, respectively. The ALT and AST levels were significantly higher in the APAP groups at day 1 whereas the enzyme levels of all groups showed no significant difference at day 7. The extracts treatment significantly reduced the proinflammatory cytokine levels and significantly increased the 11β-HSD type 1 enzyme activity (p < 0.05). In conclusion, the P. major extracts attenuate the inflammatory reaction following APAP-induced liver injury. PMID:26300946

  12. Anti-Inflammatory Property of Plantago major Leaf Extract Reduces the Inflammatory Reaction in Experimental Acetaminophen-Induced Liver Injury.

    PubMed

    Hussan, Farida; Mansor, Adila Sofea; Hassan, Siti Nazihahasma; Tengku Nor Effendy Kamaruddin, Tg Nurul Tasnim; Budin, Siti Balkis; Othman, Faizah

    2015-01-01

    Hepatic injury induces inflammatory process and cell necrosis. Plantago major is traditionally used for various diseases. This study aimed to determine the anti-inflammatory property of P. major leaf extracts on inflammatory reaction following acetaminophen (APAP) hepatotoxicity. Thirty male Sprague-Dawley rats were divided into 5 groups, namely, normal control (C), APAP, aqueous (APAP + AQ), methanol (APAP + MT), and ethanol (APAP + ET) extract treated groups. All APAP groups received oral APAP (2 g/kg) at day 0. Then, 1000 mg/kg dose of P. major extracts was given for six days. The levels of liver transaminases were measured at day 1 and day 7 after APAP induction. At day 7, the blood and liver tissue were collected to determine plasma cytokines and tissue 11β-HSD type 1 enzyme. The in vitro anti-inflammatory activities of methanol, ethanol, and aqueous extracts were 26.74 ± 1.6%, 21.69 ± 2.81%, and 12.23 ± 3.15%, respectively. The ALT and AST levels were significantly higher in the APAP groups at day 1 whereas the enzyme levels of all groups showed no significant difference at day 7. The extracts treatment significantly reduced the proinflammatory cytokine levels and significantly increased the 11β-HSD type 1 enzyme activity (p < 0.05). In conclusion, the P. major extracts attenuate the inflammatory reaction following APAP-induced liver injury.

  13. Anti-Inflammatory Property of Plantago major Leaf Extract Reduces the Inflammatory Reaction in Experimental Acetaminophen-Induced Liver Injury

    PubMed Central

    Hussan, Farida; Mansor, Adila Sofea; Hassan, Siti Nazihahasma; Tengku Nor Effendy Kamaruddin, Tg. Nurul Tasnim; Budin, Siti Balkis; Othman, Faizah

    2015-01-01

    Hepatic injury induces inflammatory process and cell necrosis. Plantago major is traditionally used for various diseases. This study aimed to determine the anti-inflammatory property of P. major leaf extracts on inflammatory reaction following acetaminophen (APAP) hepatotoxicity. Thirty male Sprague-Dawley rats were divided into 5 groups, namely, normal control (C), APAP, aqueous (APAP + AQ), methanol (APAP + MT), and ethanol (APAP + ET) extract treated groups. All APAP groups received oral APAP (2 g/kg) at day 0. Then, 1000 mg/kg dose of P. major extracts was given for six days. The levels of liver transaminases were measured at day 1 and day 7 after APAP induction. At day 7, the blood and liver tissue were collected to determine plasma cytokines and tissue 11β-HSD type 1 enzyme. The in vitro anti-inflammatory activities of methanol, ethanol, and aqueous extracts were 26.74 ± 1.6%, 21.69 ± 2.81%, and 12.23 ± 3.15%, respectively. The ALT and AST levels were significantly higher in the APAP groups at day 1 whereas the enzyme levels of all groups showed no significant difference at day 7. The extracts treatment significantly reduced the proinflammatory cytokine levels and significantly increased the 11β-HSD type 1 enzyme activity (p < 0.05). In conclusion, the P. major extracts attenuate the inflammatory reaction following APAP-induced liver injury. PMID:26300946

  14. An experimental study on evolution of fracture permeability and rate of water-rock reactions in ultramafic rocks at hydrothermal conditions

    NASA Astrophysics Data System (ADS)

    Farough, A.; Lowell, R. P.

    2015-12-01

    We have performed experiments on the evolution of fracture permeability during serpentinization of ultramafic rocks. The experiments were performed using a flow-through triaxial machine on samples of ultramafic rocks with a well-mated through-going tensile fracture at hydrothermal conditions at effective pressure of 30 MPa and temperature of 260°C. By determining the flow rate under a pore pressure gradient during the experiments and assuming a cubic law relating fracture aperture and permeability, the results showed that fracture permeability decreased by one to two orders of magnitude during the 200 to 340 hour experiments. Electron microprobe data and SEM images indicated the formation of needle-shaped crystals of serpentine composition along the walls of the fracture. Assuming the dissolution and precipitation reactions occur simultaneously along the fracture walls we found that the rate of transformation at the beginning of the experiments is ~10-4-5 (molm-2hr-1) and decreases monotonically for about an order of magnitude towards the end of experiments. The rate of transformation is converted to rate of reaction of 10-5-7 s-1 at the beginning of the experiments, which is in agreement with estimates of Martin and Fyfe, [1970] of the rate of serpentinization reactions. The results suggest that the reaction rate slowed with increasing time as available reactive surface area decreased. The results also indicate that the water-rock reactions were the main mechanism contributing to the reduction in fracture aperture and cubic law is a reasonable first approximation for understanding evolution of fracture permeability. The experimental results suggest that the fracture network in long-lived hydrothermal circulation systems can be sealed rapidly as a result of mineral precipitation, and generation of new permeability resulting from a combination of tectonic and crystallization-induced stresses is required to maintain fluid circulation.

  15. Swelling and drug release behavior of poly(2-hydroxyethyl methacrylate/itaconic acid) copolymeric hydrogels obtained by gamma irradiation

    NASA Astrophysics Data System (ADS)

    Tomić, S. Lj.; Mićić, M. M.; Filipović, J. M.; Suljovrujić, E. H.

    2007-05-01

    The new copolymeric hydrogels based on 2-hydroxyethyl methacrylate (HEMA) and itaconic acid (IA) were prepared by gamma irradiation, in order to examine the potential use of these hydrogels in controlled drug release systems. The influence of IA content in the gel on the swelling characteristics and the releasing behavior of hydrogels, and the effect of different drugs, theophylline (TPH) and fenethylline hydrochloride (FE), on the releasing behavior of P(HEMA/IA) matrix were investigated in vitro. The diffusion exponents for swelling and drug release indicate that the mechanisms of buffer uptake and drug release are governed by Fickian diffusion. The swelling kinetics and, therefore, the release rate depends on the matrix swelling degree. The drug release was faster for copolymeric hydrogels with a higher content of itaconic acid. Furthermore, the drug release for TPH as model drug was faster due to a smaller molecular size and a weaker interaction of the TPH molecules with(in) the P(HEMA/IA) copolymeric networks.

  16. Experimental and Mechanistic Understanding of Aldehyde Hydrogenation Using Au25 Nanoclusters with Lewis Acids: Unique Sites for Catalytic Reactions.

    PubMed

    Li, Gao; Abroshan, Hadi; Chen, Yuxiang; Jin, Rongchao; Kim, Hyung J

    2015-11-18

    The catalytic activity of Au25(SR)18 nanoclusters (R = C2H4Ph) for the aldehyde hydrogenation reaction in the presence of a base, e.g., ammonia or pyridine, and transition-metal ions M(z+), such as Cu(+), Cu(2+), Ni(2+) and Co(2+), as a Lewis acid is studied. The addition of a Lewis acid is found to significantly promote the catalytic activity of Au25(SR)18/CeO2 in the hydrogenation of benzaldehyde and a number of its derivatives. Matrix-assisted laser desorption ionization (MALDI) and electrospray ionization (ESI) mass spectrometry in conjunction with UV-vis spectroscopy confirm the generation of new species, Au25-n(SR)18-n (n = 1-4), in the presence of a Lewis acid. The pathways for the speciation of Au24(SR)17 from its parent Au25(SR)18 nanocluster as well as its structure are investigated via the density functional theory (DFT) method. The adsorption of M(z+) onto a thiolate ligand "-SR-" of Au25(SR)18, followed by a stepwise detachment of "-SR-" and a gold atom bonded to "-SR-" (thus an "Au-SR" unit) is found to be the most likely mechanism for the Au24(SR)17 generation. This in turn exposes the Au13-core of Au24(SR)17 to reactants, providing an active site for the catalytic hydrogenation. DFT calculations indicate that M(z+) is also capable of adsorbing onto the Au13-core surface, producing a possible active metal site of a different kind to catalyze the aldehyde hydrogenation reaction. This study suggests, for the first time, that species with an open metal site like adducts [nanoparticle-M]((z-1)+) or fragments Au25-n(SR)18-n function as the catalysts rather than the intact Au25(SR)18.

  17. Calculational and Experimental Investigations of the Pressure Effects on Radical - Radical Cross Combinations Reactions: C2H5 + C2H3

    NASA Technical Reports Server (NTRS)

    Fahr, Askar; Halpern, Joshua B.; Tardy, Dwight C.

    2007-01-01

    Pressure-dependent product yields have been experimentally determined for the cross-radical reaction C2H5 + C2H3. These results have been extended by calculations. It is shown that the chemically activated combination adduct, 1-C4H8*, is either stabilized by bimolecular collisions or subject to a variety of unimolecular reactions including cyclizations and decompositions. Therefore the "apparent" combination/disproportionation ratio exhibits a complex pressure dependence. The experimental studies were performed at 298 K and at selected pressures between about 4 Torr (0.5 kPa) and 760 Torr (101 kPa). Ethyl and vinyl radicals were simultaneously produced by 193 nm excimer laser photolysis of C2H5COC2H3 or photolysis of C2H3Br and C2H5COC2H5. Gas chromatograph/mass spectrometry/flame ionization detection (GC/MS/FID) were used to identify and quantify the final reaction products. The major combination reactions at pressures between 500 (66.5 kPa) and 760 Torr are (1c) C2H5 + C2H3 yields 1-butene, (2c) C2H5 + C2H5 yields n-butane, and (3c) C2H3 + C2H3 yields 1,3-butadiene. The major products of the disproportionation reactions are ethane, ethylene, and acetylene. At moderate and lower pressures, secondary products, including propene, propane, isobutene, 2-butene (cis and trans), 1-pentene, 1,4-pentadiene, and 1,5-hexadiene are also observed. Two isomers of C4H6, cyclobutene and/or 1,2-butadiene, were also among the likely products. The pressure-dependent yield of the cross-combination product, 1-butene, was compared to the yield of n-butane, the combination product of reaction (2c), which was found to be independent of pressure over the range of this study. The [ 1-C4H8]/[C4H10] ratio was reduced from approx.1.2 at 760 Torr (101 kPa) to approx.0.5 at 100 Torr (13.3 kPa) and approx.0.1 at pressures lower than about 5 Torr (approx.0.7 kPa). Electronic structure and RRKM calculations were used to simulate both unimolecular and bimolecular processes. The relative importance

  18. Closed-System One-Pot Block Copolymerization by Temperature-Modulated Monomer Segregation.

    PubMed

    Carmean, R Nicholas; Figg, C Adrian; Becker, Troy E; Sumerlin, Brent S

    2016-07-18

    A biphasic one-pot polymerization method enables the preparation of block copolymers from monomers with similar and competitive reactivities without the addition of external materials. AB diblock copolymers were prepared by encapsulating a frozen solution of monomer B on the bottom of a reaction vessel, while the solution polymerization of monomer A was conducted in a liquid layer above. Physical separation between the solid and liquid phases permitted only homopolymerization of monomer A until heating above the melting point of the lower phase, which released monomer B, allowing the addition of the second block to occur. The triggered release of monomer B allowed for chain extension without additional deoxygenation steps or exogenous monomer addition. A method for the closed (i.e., without addition of external reagents) one-pot synthesis of block copolymers with conventional glassware using straightforward experimental techniques has thus been developed.

  19. Initial fire-suppression reactions of halons, Phase 2 - verification of experimental approach and initial studies. Final report, Jun 88-Apr 89

    SciTech Connect

    Walters, E.A.; Nimitz, J.S.; Tapscott, R.E.; Brabson, G.D.; May, J.H.

    1990-09-01

    The objective of this effort is to evaluate an experimental approach and initiate work to determine the initial chemical reactions occurring when halon firefighting agents extinguish flames. Initial studies using these procedures were also performed. Three techniques were studied to compare their usefulness for determining the concentrations of chemical species in flames: laser Raman spectroscopy, matrix isolation Fourier-transform infrared spectroscopy, and photoionization mass spectrometry. Laser Raman spectroscopy of hydrogen/oxygen flames extinguished with Halon 1301 provided identification of the principal flames species; however, this method was not effective in detecting minor species present in low concentration. The Raman spectrum of the hydrogen molecule was used to calculate flame temperatures. Matrix isolation experiments were used to characterize the fragmentation patterns of Halons 1211, 2402, and 1301. Of the three techniques, photoionization mass spectrometry was the most promising method for characterizing reactions occurring in flames. It was found that Halon 1211 does react with the free radical H, but the cross section of the overall process is small. No evidence was found for reactions between 0 atoms and either Halon 1211 or 1301. A database of fire suspension literature was developed and incorporated into the nmeri halocarbon data base.

  20. Chemically induced graft copolymerization of 2-hydroxyethyl methacrylate onto polyurethane surface for improving blood compatibility

    NASA Astrophysics Data System (ADS)

    He, Chunli; Wang, Miao; Cai, Xianmei; Huang, Xiaobo; Li, Li; Zhu, Haomiao; Shen, Jian; Yuan, Jiang

    2011-11-01

    To improve hydrophilicity and blood compatibility properties of polyurethane (PU) film, we chemically induced graft copolymerization of 2-hydroxyethyl methacrylate (HEMA) onto the surface of polyurethane film using benzoyl peroxide as an initiator. The effects of grafting temperature, grafting time, monomer and initiator concentrations on the grafting yields were studied. The maximum grafting yield value was obtained 0.0275 g/cm2 for HEMA. Characterization of the films was carried out by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), water contact angle measurements. ATR-FTIR data showed that HEMA was successfully grafted onto the PU films surface. Water contact angle measurement demonstrated the grafted films possessed a relatively hydrophilic surface. The blood compatibility of the grafted films was preliminarily evaluated by a platelet-rich plasma adhesion test and hemolysis test. The results of platelet adhesion experiment showed that polyurethane grafted polymerization with monomer of 2-hydroxyethyl methacrylate had good blood compatibility featured by the low platelet adhesion. Hemolysis rate of the PU-g-PHEMA films was dramatically decreased than the ungrafted PU films. This kind of new biomaterials grafted with HEMA monomers might have a potential usage for biomedical applications.

  1. Recent Development of Copolymeric Delivery System for Anticancer Agents Based on Cyclodextrin Derivatives.

    PubMed

    Feng, Runliang; Deng, Peizong; Teng, Fangfang; Song, Zhimei

    2016-01-01

    Core-shell structured aggregates of amphiphilic block copolymer are hopefully drug delivery system because of their ability to encapsulate hydrophobic drugs, and their hydrophilic shell can prolong retention time of drugs in the blood circulation system. Cyclodextrin is a kind of hydrophilic polysaccharide containing multiple hydroxyl groups, providing an inner hole that can load small molecule through host-guest interaction. These hydroxyl groups or their derived functional ones are utilized in conjugation with polymeric chains to form block copolymers. These copolymers can not only encapsulate hydrophobic drugs, but also encapsulate hydrophilic drugs (like DNA, protein, etc) through hydrophobic, host-guest or electrostatic interactions, which strengthen interaction between drugs and materials compared with general copolymers, indicating that formed drug delivery systems are more stable. By introduction of target molecule, they also achieve selective delivery of drugs to specific tissues or organs. So, several researchers are stimulated to carry out many studies for the development of cyclodextrin copolymeric drug delivery systems in recent. In this review, we focus the cyclodextrin copolymers' application in the anticancer agents' delivery. PMID:26349814

  2. Dinuclear Zinc Salen Catalysts for the Ring Opening Copolymerization of Epoxides and Carbon Dioxide or Anhydrides.

    PubMed

    Thevenon, Arnaud; Garden, Jennifer A; White, Andrew J P; Williams, Charlotte K

    2015-12-21

    A series of four dizinc complexes coordinated by salen or salan ligands, derived from ortho-vanillin and bearing (±)-trans-1,2-diaminocyclohexane (L1) or 2,2-dimethyl-1,3-propanediamine (L2) backbones, is reported. The complexes are characterized using a combination of X-ray crystallography, multinuclear NMR, DOSY, and MALDI-TOF spectroscopies, and elemental analysis. The stability of the dinuclear complexes depends on the ligand structure, with the most stable complexes having imine substituents. The complexes are tested as catalysts for the ring-opening copolymerization (ROCOP) of CO2/cyclohexene oxide (CHO) and phthalic anhydride (PA)/CHO. All complexes are active, and the structure/activity relationships reveal that the complex having both L2 and imine substituents displays the highest activity. In the ROCOP of CO2/CHO its activity is equivalent to other metal salen catalysts (TOF = 44 h(-1) at a catalyst loading of 0.1 mol %, 30 bar of CO2, and 80 °C), while for the ROCOP of PA/CHO, its activity is slightly higher than other metal salen catalysts (TOF = 198 h(-1) at a catalyst loading of 1 mol % and 100 °C). Poly(ester-block-carbonate) polymers are also afforded using the most active catalyst by the one-pot terpolymerization of PA/CHO/CO2. PMID:26605983

  3. Singly versus Doubly Reduced Nickel Porphyrins for Proton Reduction: Experimental and Theoretical Evidence for a Homolytic Hydrogen‐Evolution Reaction

    PubMed Central

    Han, Yongzhen; Fang, Huayi; Jing, Huize; Sun, Huiling; Lei, Haitao

    2016-01-01

    Abstract A nickel(II) porphyrin Ni‐P (P=porphyrin) bearing four meso‐C6F5 groups to improve solubility and activity was used to explore different hydrogen‐evolution‐reaction (HER) mechanisms. Doubly reduced Ni‐P ([Ni‐P]2−) was involved in H2 production from acetic acid, whereas a singly reduced species ([Ni‐P]−) initiated HER with stronger trifluoroacetic acid (TFA). High activity and stability of Ni‐P were observed in catalysis, with a remarkable i c/i p value of 77 with TFA at a scan rate of 100 mV s−1 and 20 °C. Electrochemical, stopped‐flow, and theoretical studies indicated that a hydride species [H‐Ni‐P] is formed by oxidative protonation of [Ni‐P]−. Subsequent rapid bimetallic homolysis to give H2 and Ni‐P is probably involved in the catalytic cycle. HER cycling through this one‐electron‐reduction and homolysis mechanism has been proposed previously but rarely validated. The present results could thus have broad implications for the design of new exquisite cycles for H2 generation. PMID:27028563

  4. Prediction of CL-20 chemical degradation pathways, theoretical and experimental evidence for dependence on competing modes of reaction

    SciTech Connect

    Qasim, Mohammad M.; Fredrickson, Herbert L.; Honea, P.; Furey, John; Leszczynski, Jerzy; Okovytyy, S.; Szecsody, Jim E.; Kholod, Y.

    2005-10-01

    Highest occupied and lowest unoccupied molecular orbital energies, formation energies, bond lengths and FTIR spectra all suggest competing CL-20 degradation mechanisms. This second of two studies investigates recalcitrant, toxic, aromatic CL-20 intermediates that absorb from 370 to 430 nm. Our earlier study (Struct. Chem., 15, 2004) revealed that these intermediates were formed at high OH- concentrations via the chemically preferred pathway of breaking the C-C bond between the two cyclopentanes, thereby eliminating nitro groups, forming conjugated π bonds, and resulting in a pyrazine three-ring aromatic intermediate. In attempting to find and make dominant a more benign CL-20 transformation pathway, this current research validates hydroxylation results from both studies and examines CL-20 transformations via photo-induced free radical reactions. This article discusses CL-20 competing modes of degradation revealed through: computational calculation; UV/VIS and SF spectroscopy following alkaline hydrolysis; and photochemical irradiation to degrade CL-20 and its byproducts at their respective wavelengths of maximum absorption.

  5. Prediction of CL-20 chemical degradation pathways, theoretical and experimental evidence for dependence on competing modes of reaction.

    PubMed

    Qasim, M; Fredrickson, H; Honea, P; Furey, J; Leszczynski, J; Okovytyy, S; Szecsody, J; Kholod, Y

    2005-10-01

    Highest occupied and lowest unoccupied molecular orbital energies, formation energies, bond lengths and FTIR spectra all suggest competing CL-20 degradation mechanisms. This second of two studies investigates recalcitrant, toxic, aromatic CL-20 intermediates that absorb from 370 to 430 nm. Our earlier study (Struct. Chem., 15, 2004) revealed that these intermediates were formed at high OH(-) concentrations via the chemically preferred pathway of breaking the C-C bond between the two cyclopentanes, thereby eliminating nitro groups, forming conjugated pi bonds, and resulting in a pyrazine three-ring aromatic intermediate. In attempting to find and make dominant a more benign CL-20 transformation pathway, this current research validates hydroxylation results from both studies and examines CL-20 transformations via photo-induced free radical reactions. This article discusses CL-20 competing modes of degradation revealed through: computational calculation; UV/VIS and SF spectroscopy following alkaline hydrolysis; and photochemical irradiation to degrade CL-20 and its byproducts at their respective wavelengths of maximum absorption. PMID:16272046

  6. Psychometric properties of reaction time based experimental paradigms measuring anxiety-related information-processing biases in children.

    PubMed

    Brown, H M; Eley, T C; Broeren, S; Macleod, C; Rinck, M; Hadwin, J A; Lester, K J

    2014-01-01

    Theoretical frameworks highlight the importance of threat-related information-processing biases for understanding the emergence of anxiety in childhood. The psychometric properties of several tasks measuring these biases and their associations with anxiety were examined in an unselected sample of 9-year-old children (N=155). In each task, threat bias was assessed using bias scores reflecting task performance on threat versus non-threat conditions. Reliability was assessed using split-half and test-retest correlations of mean reaction times (RTs), accuracy and bias indices. Convergence between measures was also examined. Mean RTs showed substantial split-half and test-retest correlations. Bias score reliability coefficients were near zero and non-significant, suggesting poor reliability in children of this age. Additionally, associations between bias scores and anxiety were weak and inconsistent and performance between tasks showed little convergence. Bias scores from RT based paradigms in the current study lacked adequate psychometric properties for measuring individual differences in anxiety-related information-processing in children.

  7. Experimental study of carbon sequestration reactions controlled by the percolation of CO2-rich brine through peridotites.

    PubMed

    Andreani, M; Luquot, L; Gouze, P; Godard, M; Hoisé, E; Gibert, B

    2009-02-15

    Carbonation of ultramafic rocks in geological reservoirs is, in theory, the most efficient way to trap CO2 irreversibly; however, possible feedback effects between carbonation reactions and changes in the reservoir permeability must be considered to realistically assess the efficiency and sustainability of this process. We investigated changes in the hydrodynamic properties of sintered dunite samples by means of percolation experiments, under conditions analogous to that of in situ carbonation. Our results show that carbonation efficiency is controlled by the local renewal of the reactants and the heterogeneity of the pore structure. Preferential flow zones are characterized by the formation of magnetite and of a silica-rich layer at the olivine surfaces, which eventually inhibits olivine dissolution. Conversely, sustainable olivine dissolution together with coprecipitation of magnesite, siderite, and minor Mg-TOT-phyllosilicates, occur in reduced-flow zones. Thus carbonate precipitation only decreases porosity in zones where diffusion-controlled transport is dominant. Consequently, while high flow rates will decrease the carbonation efficiency of the reservoir and low flow rates may reduce the permeability irreversibly close to the injection point, moderate injection rates will ensure a partial carbonation of the rock and maintain the reservoir permeability. PMID:19320184

  8. An experimental and computational study of the reaction of ground-state sulfur atoms with carbon disulfide

    NASA Astrophysics Data System (ADS)

    Gao, Yide; Marshall, Paul

    2011-10-01

    The pulsed laser photolysis/resonance fluorescence technique was used to study the reaction of S(3PJ) with CS2 in an Ar bath gas. Over 290-770 K pressure-dependent kinetics were observed and low- and high-pressure limiting rate constants were derived as k0 = (11.5-0.0133 T/K) × 10-31 cm6 molecule-2 s-1 (error limits ± 20%) and k∞ = (2.2 ± 0.6) × 10-12 cm3 molecule-1 s-1. Equilibration observed at 690-770 K yields a CS2-S bond dissociation enthalpy of 131.7 ± 4.0 kJ mol-1 at 298 K. This agrees with computed thermochemistry for a spin-forbidden C2V adduct, estimated at the coupled-cluster single double triple level extrapolated to the infinite basis set limit. A pressure-independent pathway, assigned to abstraction, was observed from 690 to 1040 K and can be summarized as 1.14 × 10-10 exp(-37.0 kJ mol-1/RT) cm3 molecule-1 s-1 with error limits of ± 40%. The results are rationalized in terms of a computed potential energy surface and transition state theory and Troe's unimolecular formalism.

  9. Experimental cross-sections for proton induced nuclear reactions on mercury up to 65 MeV

    NASA Astrophysics Data System (ADS)

    Hermanne, A.; Tárkányi, F.; Takács, S.; Ditrói, F.; Szücs, Z.; Brezovcsik, K.

    2016-07-01

    Cross-sections for formation of activation products induced by protons on natural mercury targets were measured. Results for 196m,196g,197g(cum), 198m,198g,199g(cum), 200g(cum), 201,202Tl, 194g(cum), 195g(cum), 196g(cum), 198m,199g(cum) Au and 195m,197m,203Hg are presented up to 65 MeV incident particle energy, many of these for the first time. The experimental data are compared with literature values and with the predictions of the TALYS 1.6 code (results taken from TENDL-2015 on-line library), thick target yields were derived and possible applications in biomedical sciences are discussed.

  10. Determining Magma Mixing Duration Prior to the 1915 Eruption of Lassen Peak, California by Comparing Experimental Growth of Reaction Rims and Natural Olivine Crystals in Black Dacite

    NASA Astrophysics Data System (ADS)

    Graham, N. A.; Schwab, B. E.; Castro, J. M.; Clynne, M. A.

    2015-12-01

    Lassen Peak, located in northern California, last erupted in 1915 producing hybrid black dacite containing xenocrystic olivine grains with morphologically complex reaction rims of orthopyroxene. These rims are interpreted to have grown during magma mixing/mingling of admixed basaltic andesite and dacite reservoir magma prior to eruption. Reaction rim growth rates were determined from a series of hydrothermal experiments performed on starting materials consisting of powdered natural dacite pumice from the 1915 eruption and ~5 wt. % of Fo85 olivine separated from a spinel lherzolite xenolith (UM-5) from Kilbourne Hole, NM to constrain the length of time between magma recharge and eruption. Time series experiments were performed with run durations of 50, 100, 200, 400, and 600 hours at 50 and 100 MPa, 825oC and 875oC. The experiments produced a range in reaction rim growth rates where rim thickness generally increased with time. Average rim growth rate for each series is as follows: 0.031 μm²h-1 for 50 MPa at 825oC, 0.010 μm²h-1 for 50 MPa at 875oC, 0.158 μm²h-1 for 100 MPa at 825oC, and 0.088 μm²h-1 for 100 MPa at 875oC. Overall, the 100 MPa experiments resulted in faster growth rates and thicker reaction rims than the 50 MPa experiments. At a given pressure, the higher temperature (875 oC) experiments show slower average growth rates, but thicker reaction rims than the 825oC equivalents. This suggests that growth rate is not constant over time, but likely is more rapid at the early stages of the experiments/heating event, and then slows over time. Reaction rim widths on 100 olivine grains from samples of black dacite were determined by analysis of SEM BSE images and average 26.1 ± 21.7 μm. This average rim width corresponds to a range of mixing durations of 5.8 months (100 MPa, 825oC) to 93 months (50 MPa, 875oC). Average reaction duration of 10.6 months (at 100 MPa, 875oC) is most consistent with our previous experimental work on the 1915 dacite. Reaction

  11. The effects of stress concentrations on reaction progress: an example from experimental growth of magnesio-aluminate spinel at corundum - periclase interfaces under uniaxial load

    NASA Astrophysics Data System (ADS)

    Jerabek, Petr; Abart, Rainer; Rybacki, Erik; Habler, Gerlinde

    2014-05-01

    The study aims to understand the reaction progress and chemical, microstructural and textural evolution of magnesio-aluminate spinel reaction rims formed at varying experimental settings (load, temperature and experiment duration). The spinel rims were grown at the contacts between periclase and corundum at temperatures of 1250°C to 1350°C and dry atmosphere, maintained by a constant argon gas flow, under uniaxial load of 0.026 and 0.26 kN per 9 mm2 of initial contact area. Single crystals of periclase with [100] and of corundum with [0001] perpendicular to the polished reaction interface as well as polycrystalline corundum were used as starting materials. Two loading procedures, immediate application of the load before heating and loading after the desired temperature had been reached, were used. An important byproduct of our experiments stemmed from the immediate application of the load, which led to deformation twinning and fracturing of corundum. This internal deformation of corundum disturbed the reaction interface and introduced loci of concentrated stress due to opening of void spaces in between the reactant crystals. Whenever cracks formed in the initial stages of an experiment, the void space opened immediately and no spinel formed along these interface segments. In the case of deformation twinning, the decreased rim thickness indicates later opening of void spaces. This is because next to twins, the reaction interface is characterized by tight physical contact on the one side and less tight contact on the other side of the twin individual. The tight contacts are characterized by enhanced reaction progress which together with the overall positive volume change of the reaction and limits on plasticity of the studied phases led to the opening of void spaces at places characterized by less tight contacts. The thickness variations are less pronounced in our high load (0.26 kN) experiments where periclase behaves plastically and to some extent reduces the

  12. Experimental determination of equilibrium constant for the complexing reaction of nitric oxide with hexamminecobalt(II) in aqueous solution.

    PubMed

    Mao, Yan-Peng; Chen, Hua; Long, Xiang-Li; Xiao, Wen-de; Li, Wei; Yuan, Wei-Kang

    2009-02-15

    Ammonia solution can be used to scrub NO from the flue gases by adding soluble cobalt(II) salts into the aqueous ammonia solutions. The hexamminecobalt(II), Co(NH3)6(2+), formed by ammonia binding with Co2+ is the active constituent of eliminating NO from the flue gas streams. The hexamminecobalt(II) can combine with NO to form a complex. For the development of this process, the data of the equilibrium constants for the coordination between NO and Co(NH3)6(2+)over a range of temperature is very important. Therefore, a series of experiments were performed in a bubble column to investigate the chemical equilibrium. The equilibrium constant was determined in the temperature range of 30.0-80.0 degrees C under atmospheric pressure at pH 9.14. All experimental data fit the following equation well: [see text] where the enthalpy and entropy are DeltaH degrees = - (44.559 +/- 2.329)kJ mol(-1) and DeltaS degrees = - (109.50 +/- 7.126) J K(-1)mol(-1), respectively.

  13. Factors That Control the Reactivity of Cobalt(III)-Nitrosyl Complexes in Nitric Oxide Transfer and Dioxygenation Reactions: A Combined Experimental and Theoretical Investigation.

    PubMed

    Kumar, Pankaj; Lee, Yong-Min; Hu, Lianrui; Chen, Jianwei; Park, Young Jun; Yao, Jiannian; Chen, Hui; Karlin, Kenneth D; Nam, Wonwoo

    2016-06-22

    Metal-nitrosyl complexes are key intermediates involved in many biological and physiological processes of nitric oxide (NO) activation by metalloproteins. In this study, we report the reactivities of mononuclear cobalt(III)-nitrosyl complexes bearing N-tetramethylated cyclam (TMC) ligands, [(14-TMC)Co(III)(NO)](2+) and [(12-TMC)Co(III)(NO)](2+), in NO-transfer and dioxygenation reactions. The Co(III)-nitrosyl complex bearing 14-TMC ligand, [(14-TMC)Co(III)(NO)](2+), transfers the bound nitrosyl ligand to [(12-TMC)Co(II)](2+) via a dissociative pathway, {[(14-TMC)Co(III)(NO)](2+) → {(14-TMC)Co···NO}(2+)}, thus affording [(12-TMC)Co(III)(NO)](2+) and [(14-TMC)Co(II)](2+) as products. The dissociation of NO from the [(14-TMC)Co(III)(NO)](2+) complex prior to NO-transfer is supported experimentally and theoretically. In contrast, the reverse reaction, which is the NO-transfer from [(12-TMC)Co(III)(NO)](2+) to [(14-TMC)Co(II)](2+), does not occur. In addition to the NO-transfer reaction, dioxygenation of [(14-TMC)Co(III)(NO)](2+) by O2 produces [(14-TMC)Co(II)(NO3)](+), which possesses an O,O-chelated nitrato ligand and where, based on an experiment using (18)O-labeled O2, two of the three O-atoms in the [(14-TMC)Co(II)(NO3)](+) product derive from O2. The dioxygenation reaction is proposed to occur via a dissociative pathway, as proposed in the NO-transfer reaction, and via the formation of a Co(II)-peroxynitrite intermediate, based on the observation of phenol ring nitration. In contrast, [(12-TMC)Co(III)(NO)](2+) does not react with O2. Thus, the present results demonstrate unambiguously that the NO-transfer/dioxygenation reactivity of the cobalt(III)-nitrosyl complexes bearing TMC ligands is significantly influenced by the ring size of the TMC ligands and/or the spin state of the cobalt ion. PMID:27221953

  14. First accurate experimental study of Mu reactivity from a state-selected reactant in the gas phase: the Mu + H2{1} reaction rate at 300 K

    NASA Astrophysics Data System (ADS)

    Bakule, Pavel; Sukhorukov, Oleksandr; Ishida, Katsuhiko; Pratt, Francis; Fleming, Donald; Momose, Takamasa; Matsuda, Yasuyuki; Torikai, Eiko

    2015-02-01

    This paper reports on the experimental background and methodology leading to recent results on the first accurate measurement of the reaction rate of the muonium (Mu) atom from a state-selected reactant in the gas phase: the Mu + H2\\{1\\}\\to MuH + H reaction at 300 K, and its comparison with rigorous quantum rate theory, Bakule et al (2012 J. Phys. Chem. Lett. 3 2755). Stimulated Raman pumping, induced by 532 nm light from the 2nd harmonic of a Nd:YAG laser, was used to produce H2 in its first vibrational (v = 1) state, H2\\{1\\}, in a single Raman/reaction cell. A pulsed muon beam (from ‘ISIS’, at 50 Hz) matched the 25 Hz repetition rate of the laser, allowing data taking in equal ‘Laser-On/Laser-Off’ modes of operation. The signal to noise was improved by over an order of magnitude in comparison with an earlier proof-of-principle experiment. The success of the present experiment also relied on optimizing the overlap of the laser profile with the extended stopping distribution of the muon beam at 50 bar H2 pressure, in which Monte Carlo simulations played a central role. The rate constant, found from the analysis of three separate measurements, which includes a correction for the loss of {{H}2}\\{1\\} concentration due to collisional relaxation with unpumped H2 during the time of each measurement, is {{k}Mu}\\{1\\} = 9.9[(-1.4)(+1.7)] × 10-13 cm3 s-1 at 300 K. This is in good to excellent agreement with rigorous quantum rate calculations on the complete configuration interaction/Born-Huang surface, as reported earlier by Bakule et al, and which are also briefly commented on herein.

  15. Theoretical and experimental investigation of the dynamics of the production of CO from the CH{sub 3} + O and CD{sub 3} + O reactions.

    SciTech Connect

    Marcy, T. P.; Diaz, R. R.; Heard, D.; Leone, S. R.; Harding, L. B.; Klippenstein, S. J.; Chemistry; NIST; Univ. of Colorado; SNL

    2001-09-13

    Combined experimental and theoretical investigations of the title reactions are presented. Time-resolved Fourier transform infrared (FTIR) emission studies of CO (v = 1) produced from the CH{sub 3} + O and CD{sub 3} + O reactions show that there is approximately a one-third reduction in the branching to the CO channel upon deuteration of the methyl radical. Direct dynamics, classical trajectory calculations using a B3LYP potential surface, confirm the existence of the CO producing channel. The calculations show that the CO comes from the decomposition of HCO produced by the elimination of H{sub 2} from highly vibrationally excited methoxy radicals. Scans of the potential surface reveal no saddle point for the direct elimination of H{sub 2} from methoxy. The minimum-energy path for this elimination is a stepwise process involving first a CH bond cleavage, forming H + H{sub 2}CO, followed by an abstraction, forming H{sub 2} + HCO. However, at the high internal energies produced in the initial O + CH{sub 3} addition, trajectories for the direct elimination of H{sub 2} from methoxy are observed. The predicted branching ratio between the CO and H{sub 2}CO channels is in good agreement with previous room-temperature measurements, and there is predicted to be little temperature dependence to it. The observed reduction in the branching to the CO channel upon deuteration is also well reproduced in the calculations.

  16. Uranyl ion uptake capacity of poly (N-isopropylacrylamide/maleic acid) copolymeric hydrogels prepared by gamma rays

    NASA Astrophysics Data System (ADS)

    Kam, Erol; Taşdelen, Betul; Osmanlioglu, A. Erdal

    2012-06-01

    The effect of gel composition, absorbed dose and pH of the solution on the uranyl ion uptake capacity of N-isopropylacrylamide/maleic acid copolymeric hydrogels containing 0-3 mol% of maleic acid at 48 kGy have been investigated. Uranyl uptake capacity of hydrogels are found to increase from 18.5 to 94.8 mg [UO22+]/g dry gel as the mole % of maleic acid content in the gel structure increased from 0 to 3. The percent swelling, equilibrium swelling and diffusion coefficient values have been evaluated for poly(N-isopropylacrylamide/maleic acid) hydrogels at 500 ppm of uranyl nitrate solution.

  17. Aryl C-H amination by diruthenium nitrides in the solid state and in solution at room temperature: experimental and computational study of the reaction mechanism.

    PubMed

    Long, Amanda Kae Musch; Timmer, George H; Pap, József S; Snyder, Jamie Lynn; Yu, Renyuan Pony; Berry, John F

    2011-08-24

    Diruthenium azido complexes Ru(2)(DPhF)(4)N(3) (1a, DPhF = N,N'-diphenylformamidinate) and Ru(2)(D(3,5-Cl(2))PhF)(4)N(3) (1b, D(3,5-Cl(2))PhF = N,N'-bis(3,5-dichlorophenyl)formamidinate) have been investigated by thermolytic and photolytic experiments to investigate the chemical reactivity of the corresponding diruthenium nitride species. Thermolysis of 1b at ~100 °C leads to the expulsion of N(2) and isolation of Ru(2)(D(3,5-Cl(2))PhF)(3)NH(C(13)H(6)N(2)Cl(4)) (3b), in which a nitrogen atom has been inserted into one of the proximal aryl C-H bonds of a D(3,5-Cl(2))PhF ligand. A similar C-H insertion product is obtained upon thawing a frozen CH(2)Cl(2) solution of the nitride complex Ru(2)(DPhF)(4)N (2a), formed via photolysis at -196 °C of 1a to yield Ru(2)(DPhF)(3)NH(C(13)H(10)N(2)) (3a). Evidence is provided here that both reactions proceed via direct intramolecular attack of an electrophilic terminal nitrido nitrogen atom on a proximal aryl ring. Thermodynamic and kinetic data for this reaction are obtained from differential scanning calorimetric measurements and thermal gravimetric analysis of the thermolysis of Ru(2)(D(3,5-Cl(2))PhF)(4)N(3), and by Arrhenius/Eyring analysis of the conversion of Ru(2)(DPhF)(4)N to its C-H insertion product, respectively. These data are used to develop a detailed, experimentally validated DFT reaction pathway for N(2) extrusion and C-H functionalization from Ru(2)(D(3,5-Cl(2))PhF)(4)N(3). The diruthenium nitrido complex is an intermediate in the calculated reaction pathway, and the C-H functionalization event shares a close resemblance to a classical electrophilic aromatic substitution mechanism.

  18. Main-Chain and Side-Chain Sequence-Regulated Vinyl Copolymers by Iterative Atom Transfer Radical Additions and 1:1 or 2:1 Alternating Radical Copolymerization.

    PubMed

    Soejima, Takamasa; Satoh, Kotaro; Kamigaito, Masami

    2016-01-27

    Main- and side-chain sequence-regulated vinyl copolymers were prepared by a combination of iterative atom transfer radical additions (ATRAs) of vinyl monomers for side-chain control and 1:1 or 2:1 alternating radical copolymerization of the obtained side-chain sequenced "oligomonomers" and vinyl comonomers for main-chain control. A complete set of sequence-regulated trimeric vinyl oligomers of styrene (S) and/or methyl acrylate (A) were first synthesized via iterative ATRAs of these monomers to a halide of monomeric S or A unit (X-S or X-A) under optimized conditions with appropriate ruthenium or copper catalysts, which were selected depending on the monomers and halides. The obtained halogen-capped oligomers were then converted into a series of maleimide (M)-ended oligomonomers with different monomer compositions and sequences (M-SSS, M-ASS, M-SAS, M-AAS, M-SSA, M-ASA, M-SAA, M-AAA) by a substitution reaction of the halide with furan-protected maleimide anion followed by deprotection of the furan units. These maleimide-ended oligomonomers were then radically copolymerized with styrene or limonene to enable the 1:1 or 2:1 monomer-sequence regulation in the main chain and finally result in the main- and side-chain sequence-regulated vinyl copolymers with high molecular weights in high yield. The properties of the sequence-regulated vinyl copolymers depended on not only the monomer compositions but also the monomer sequences. The solubility was highly affected by the outer monomer units in the side chains whereas the glass transition temperatures were primarily affected by the two successive monomer sequences. PMID:26761148

  19. Experimental and theoretical study of the ion-ion mutual neutralization reactions Ar{sup +}+SF{sub n}{sup -} (n=6, 5, and 4)

    SciTech Connect

    Bopp, Joseph C.; Miller, Thomas M.; Viggiano, Albert A.; Troe, Juergen

    2008-08-21

    The ion-ion mutual neutralization reactions Ar{sup +}+SF{sub n}{sup -}{yields}Ar+SF{sub n} (n=6, 5, and 4) have been studied in a flowing afterglow-Langmuir probe (FALP) apparatus at 300 K and 1 Torr of He buffer gas. Electron concentrations and product ion fractions were measured, and neutralization rate constants of 4.0x10{sup -8}, 3.8x10{sup -8}, and 4x10{sup -8} cm{sup 3} s{sup -1} for SF{sub 6}{sup -}, SF{sub 5}{sup -}, and SF{sub 4}{sup -}, respectively, were derived, with uncertainties of {+-}25% ({+-}35% for SF{sub 4}{sup -}). During the neutralization process, excited neutrals are generated that are able to dissociate to neutral fragments. In the case of SF{sub 6}, the formation of SF{sub 5} and SF{sub 4}, and similarly in the case of SF{sub 5}, the formation of SF{sub 4} and SF{sub 3} were observed and quantified. The mechanism of primary and secondary reaction was analyzed in detail, and rate constants for the dissociative electron attachments e{sup -}+SF{sub 5}{yields}F{sup -}+SF{sub 4} (k=3x10{sup -9} cm{sup 3} s{sup -1},{+-}40%) and e{sup -}+SF{sub 3}{yields}F{sup -}+SF{sub 2} (k=2x10{sup -8} cm{sup 3} s{sup -1},+400%,-75%) were also derived. The experimental ion-ion neutralization rate constants were found to be in good agreement with estimates from an optimum two-state double-passage Landau-Zener model. It was also found that energy partitioning in the neutralization is related to the extent of electronic excitation of Ar generated by the electron transfer processes.

  20. Mussel-inspired one-step copolymerization to engineer hierarchically structured surface with superhydrophobic properties for removing oil from water.

    PubMed

    Huang, Shouying

    2014-10-01

    In the present study, a superhydrophobic polyurethane (PU) sponge with hierarchically structured surface, which exhibits excellent performance in absorbing oils/organic solvents, was fabricated for the first time through mussel-inspired one-step copolymerization approach. Specifically, dopamine (a small molecular bioadhesive) and n-dodecylthiol were copolymerized in an alkaline aqueous solution to generate polydopamine (PDA) nanoaggregates with n-dodecylthiol motifs on the surface of the PU sponge skeletons. Then, the superhydrophobic sponge that comprised a hierarchical structured surface similar to the chemical/topological structures of lotus leaf was fabricated. The topological structures, surface wettability, and mechanical property of the sponge were characterized by scanning electron microscopy, contact angle experiments, and compression test. Just as a result of the highly porous structure, superhydrophobic property and strong mechanical stability, this sponge exhibited desirable absorption capability of oils/organic solvents (weight gains ranging from 2494% to 8670%), suggesting a promising sorbents for the removal of oily pollutants from water. Furthermore, thanks to the nonutilization of the complicated processes or sophisticated equipment, the fabrication of the superhydrophobic sponge seemed to be quite easy to scale up. All these merits make the sponge a competitive candidate when compared to the conventional absorbents, for example, nonwoven polypropylene fabric.

  1. Olivine-gabbros and olivine-rich troctolites genesis through melt-rock reactions in oceanic spreading lithosphere: an experimental study up to 0.7 GPa

    NASA Astrophysics Data System (ADS)

    Francomme, Justine E.; Fumagalli, Patrizia; Borghini, Giulio

    2016-04-01

    Extensive melt-rock reaction and melt impregnation significantly affect not only the physical and chemical properties at mantle-crust transition, but also control the evolution of migrating melts. We performed reactive dissolution and crystallization experiments at pressure ≤ 0.7 GPa in a piston-cylinder apparatus to provide experimental constraints on genesis of olivine-rich troctolites and olivine-gabbros at mantle-crust transition in oceanic spreading lithosphere by melt-rock reaction. Our experiments are carried out by using Salt-Pyrex-Graphite-Magnesium assemblies and graphite-lined platinum capsules. Experimental charges are prepared with three layers: (1) basalt powder, (2) fine powder (1-10μm) of San Carlos olivine (Fo90.1), and (3) carbon spheres used as a melt trap. Three synthetic MORB-type melts have been used, two tholeiitic basalts (Mg#: 0.62, SiO2: 47.70 wt%, Na2O: 2.28 wt% and Mg#: 0.58, SiO2: 49.25 wt%, Na2O: 2.49 wt%) and a primitive one (Mg#: 0.74, SiO2: 48.25 wt%, Na2O: 1.80 wt%), in order to investigate the effect of melt composition. A rock/melt ratio of 0.7 has been kept fixed. Experiments have been conducted at temperatures from 1200 to 1300°C, at both step cooling and isothermal conditions for different run durations (from 12 to 72 hrs). They resulted in layered samples in which all the initial San Carlos olivine powder, analog of a dunitic pluton infiltrated by basaltic melt, is replaced by different lithologies from olivine-rich troctolite to olivine gabbro. In isothermal experiments, reacted melts have been successfully trapped in the carbon spheres allowing their chemical analysis; as expected the reacted melt has a higher Mg# than the initial one (e.g. from Mg#=0.62 to 0.73). Across the different lithologies Mg# of olivine is decreasing from the olivine-rich troctolite to the gabbro. Replacive olivine-rich troctolite has a poikilitic texture with rounded euhedral olivine and interstitial poikilitic plagioclase and clinopyroxene

  2. Comparison of polymerase chain reaction and culture for detection of Borrelia burgdorferi in naturally infected Peromyscus leucopus and experimentally infected C.B-17 scid/scid mice.

    PubMed

    Hofmeister, E K; Markham, R B; Childs, J E; Arthur, R R

    1992-10-01

    Culture and the polymerase chain reaction (PCR) were compared for detection of Borrelia burgdorferi infection in wild-caught Peromyscus leucopus and experimentally inoculated C.B-17 scid/scid (severe combined immunodeficient) mice. PCR targeted highly conserved regions of the ospA gene and could detect one to five cultured organisms and 10 to 50 copies of molecularly cloned ospA DNA. Organs (kidney, spleen, and urinary bladder) and/or ear biopsy samples were obtained from 108 captured P. leucopus mice, and tissues were obtained from 7 experimentally inoculated mice. A simple sample-processing procedure with proteinase K and detergent treatment was used in the PCR analysis. Overall, B. burgdorferi was detected in 29 of 108 (27%) P. leucopus mice by culture and in 31 of 108 (29%) mice by PCR. As assessed by the kappa statistic, agreement between PCR and culture was high for ear and bladder (kappa = 0.80 and 0.65, respectively) and low for kidney and spleen (kappa = 0.37 and 0.03, respectively). While concordant results were obtained from 98 animals, PCR detected B. burgdorferi from 6 additional mice for which cultures were negative and culture detected B. burgdorferi from 4 animals which were PCR negative. Further phenol-chloroform extraction of DNA in a limited number of samples improved the sensitivity of PCR compared with that of culture. These results indicate that PCR may be as sensitive as culture for detecting B. burgdorferi in ear samples and that PCR analysis is suitable for establishing the infection status of animals in mark-release-recapture studies.

  3. Use of experimental design methodology to prepare Maillard reaction products from glucose and cysteine inhibitors of polyphenol oxidase from eggplant (Solanum melongena).

    PubMed

    Cheriot, Sophie C; Billaud, Catherine; Nicolas, Jacques

    2006-07-12

    Polyphenol oxidase (PPO) from eggplant was extracted and partially purified by a two-step fractionation-precipitation using ammonium sulfate and phenylsepharose hydrophobic interaction chromatography. The eggplant PPO extract was characterized concerning its kinetic properties. Optimal conditions to obtain Maillard reaction products (MRPs) with a maximal inhibitory potency (IP) toward PPO activity were determined using the surface response methodology and a four-factor and five-level experimental design. The MRPs were prepared from cysteine (0.25 M) and glucose (0-1 M), at several initial pH values (2-6) and at differing heating times (3-19 h) and temperatures (95-115 degrees C). The maximal IP was obtained after heating a model system of glucose/cysteine (1/0.25 M) at pH 2 for 3 h 20 min at 115 degrees C. The soluble part of this MRP, called MRP(IPmax), was a noncompetitive inhibitor toward eggplant PPO. The IP of MRP(IPmax) on PPO activity was very potent as compared to that displayed by benzoic, p-coumaric, and t-cinnamic acids, as well as sorbic acid and 4-hexylresorcinol. The activity of preincubated PPO at 0 degrees C with MRP(IPmax) was only slightly restored after dialysis or gel filtration.

  4. Polymerase chain reaction analysis of TNF-alpha and IL-6 mRNA levels in whole blood from cattle naturally or experimentally infected with Mycobacterium paratuberculosis.

    PubMed

    Adams, J L; Collins, M T; Czuprynski, C J

    1996-10-01

    Johne's disease is characterized by a chronic enteritis that results in granulomatous inflammation, cachexia, and eventual death of cattle infected with Mycobacterium paratuberculosis. The cytokines tumor necrosis factor-alpha (TNF-alpha) and interleukin-6 (IL-6) have been associated with granuloma formation and wasting in other disease syndromes. The potential role of these cytokines in the development and progression of Johne's disease has not been investigated. Using the polymerase chain reaction (PCR) and specific bovine oligonucleotide cytokine primers and probes, we examined the expression of messenger RNA for these cytokines in whole blood from M. paratuberculosis infected and uninfected cattle. Cytokine mRNA levels were examined before and after in vitro incubation with E.coli lipopolysaccharide (LPS) and lipoarabinomannan (LAM) purified from M. paratuberculosis. Uninfected calves, experimentally infected calves, and naturally infected cattle all displayed similar cytokine mRNA expression patterns. However, individual animals demonstrated variability in the levels of IL-6 and TNF-alpha mRNA expression as determined by a semiquantitative PCR method using 32P-labelled oligonucleotide probes.

  5. Mechanism of reaction in NaAlCl4 molten salt batteries with nickel felt cathodes and aluminum anodes. 2: Experimental results and comparison with model calculations

    NASA Astrophysics Data System (ADS)

    Knutz, B. C.; Berg, R. W.; Hjuler, H. A.; Bjerrum, N. J.

    1993-12-01

    The battery systems: Al/NaCl-AlCl3-Al2 X3/Ni-felt (X = S, Se, Te) and the corresponding system without chalcogen have been studied experimentally at 175 C. Charge/discharge experiments, performed on cells with NaCl saturated melts, show that advantages with regard to rate capability and cyclability can be obtained with systems containing dissolved chalcogen compared with the chalcogen-free system. Exchange of chalcogen between cathode and electrolyte during cycling was confirmed by performing gravimetric analysis and Raman spectroscopy of the electrolytes. Cathode reactions were studied by coulometric titrations (performed on cells with slightly acidic NaCl-AlCl3 melts and small amounts of chalcogen) and compared with model calculations. Cells containing chalcogen revealed at least three voltage plateaus during cycling. The lowest plateau is associated with formation/decomposition of essentially Ni(y)S(z) an d Ni(y)Se(z) in the sulfide and selenide system, respectively. Cells containing selenide revealed extra capacity below the Ni(y) Se(z)-plateau, most probably associated with a Al(v)Ni(y)Se(z) compound. On the second plateau of sulfide systems NiCl2 or a Ni(y)S(z) Cl(2y - 2z) compound with y greater than (4.4 +/- 0.2), z is formed during charging. Reduction of the formed compound to Ni takes place via consumption of sodium chloride.

  6. The reactions of N-methylformamide and N,N-dimethylformamide with OH and their photo-oxidation under atmospheric conditions: experimental and theoretical studies.

    PubMed

    Bunkan, Arne Joakim C; Hetzler, Jens; Mikoviny, Tomáš; Wisthaler, Armin; Nielsen, Claus J; Olzmann, Matthias

    2015-03-14

    The reactions of OH radicals with CH3NHCHO (N-methylformamide, MF) and (CH3)2NCHO (N,N-dimethylformamide, DMF) have been studied by experimental and computational methods. Rate coefficients were determined as a function of temperature (T = 260-295 K) and pressure (P = 30-600 mbar) by the flash photolysis/laser-induced fluorescence technique. OH radicals were produced by laser flash photolysis of 2,4-pentanedione or tert-butyl hydroperoxide under pseudo-first order conditions in an excess of the corresponding amide. The rate coefficients obtained show negative temperature dependences that can be parameterized as follows: kOH+MF = (1.3 ± 0.4) × 10(-12) exp(3.7 kJ mol(-1)/(RT)) cm(3) s(-1) and kOH+DMF = (5.5 ± 1.7) × 10(-13) exp(6.6 kJ mol(-1)/(RT)) cm(3) s(-1). The rate coefficient kOH+MF shows very weak positive pressure dependence whereas kOH+DMF was found to be independent of pressure. The Arrhenius equations given, within their uncertainty, are valid for the entire pressure range of our experiments. Furthermore, MF and DMF smog-chamber photo-oxidation experiments were monitored by proton-transfer-reaction time-of-flight mass spectrometry. Atmospheric MF photo-oxidation results in 65% CH3NCO (methylisocyanate), 16% (CHO)2NH, and NOx-dependent amounts of CH2[double bond, length as m-dash]NH and CH3NHNO2 as primary products, while DMF photo-oxidation results in around 35% CH3N(CHO)2 as primary product and 65% meta-stable (CH3)2NC(O)OONO2 degrading to NOx-dependent amounts of CH3N[double bond, length as m-dash]CH2 (N-methylmethanimine), (CH3)2NNO (N-nitroso dimethylamine) and (CH3)2NNO2 (N-nitro dimethylamine). The potential for nitramine formation in MF photo-oxidation is comparable to that of methylamine whereas the potential to form nitrosamine and nitramine in DMF photo-oxidation is larger than for dimethylamine. Quantum chemistry supported atmospheric degradation mechanisms for MF and DMF are presented. Rate coefficients and initial branching ratios

  7. Orthogonal gradient networks via post polymerization reaction

    NASA Astrophysics Data System (ADS)

    Chinnayan Kannan, Pandiyarajan; Genzer, Jan

    2015-03-01

    We report a novel synthetic route to generate orthogonal gradient networks through post polymerization reaction using pentaflurophenylmethacrylate (PFPMAc) active ester chemistry. These chemoselective monomers were successfully copolymerized with 5 mole% of the photo (methacryloyloxybenzophenone) and thermal (styrenesulfonylazide) crosslinkers. Subsequently, the copolymers were modified by a series of amines having various alkyl chain lengths. The conversion of post polymerization reaction was monitored using Fourier Transform Infrared Spectroscopy (FT-IR) and noticed that almost all pentaflurophenyl moieties are substituted by amines within in an hour without affecting the crosslinkers. In addition, the incorporation of photo and thermal crosslinkers in the polymer enabled us to achieve stable and covalently surface-bound polymer gradient networks (PGN) in an orthogonal manner, i.e. complete control over the crosslink density of the network in two opposite directions (i.e. heat vs photo). The network properties such as wettability, swelling and tensile modulus of the gradient coatings are studied and revealed in the paper.

  8. Comparative biomechanical and radiological characterization of osseointegration of a biodegradable magnesium alloy pin and a copolymeric control for osteosynthesis.

    PubMed

    Lindtner, Richard A; Castellani, Christoph; Tangl, Stefan; Zanoni, Gerald; Hausbrandt, Peter; Tschegg, Elmar K; Stanzl-Tschegg, Stefanie E; Weinberg, Annelie-Martina

    2013-12-01

    Magnesium alloys offer great advantages as degradable implant material for pediatric fracture fixation and hold the potential to overcome certain critical shortcomings inherent to currently used degradable (co)polymers. Besides good biocompatibility and appropriate degradation kinetics, sufficient implant anchorage in host bone is critical to prevent implant failure. Bone-implant anchorage of biodegradable magnesium alloys, however, has not yet been related and compared to that of copolymers, their degradable counterparts currently in clinical use. The aim of this study, therefore, was to comparatively assess bone-implant interface strength and the amount of peri-implant bone of a biodegradable magnesium alloy pin (Mg-Y-Nd-HRE) and a self-reinforced copolymeric control (85/15 poly(l-lactic-co-glycolic acid)). To this purpose, push-out testing, microfocus computed tomography (μCT), histological and scanning electron microscopic examination was performed after 4, 12 and 24 weeks of transcortical implantation in 72 rats. Biomechanical testing revealed significantly higher ultimate shear strength for the magnesium alloy pins than for the copolymeric controls at all 3 timepoints (P≤0.001 for all comparisons). As evaluated by μCT, the amount of bone present near the interface and in a wider radius (up to 0.5mm) around it was higher in the magnesium alloy implants at 4 weeks, without significant differences at 12 and 24 weeks. Histological examination confirmed direct bone-to-implant contact for both implant types. In vivo degradation of implants did not induce any noticeable local or systemic inflammation. This data suggests that the investigated degradable magnesium alloy rod exhibits markedly superior bone-implant interface strength and a greater amount of peri-implant bone than a self-reinforced copolymeric control currently in use; thus it fulfills a crucial prerequisite for its successful clinical deployment as an alternative degradable orthopedic implant

  9. A combined experimental and DFT study of active structures and self-cycle mechanisms of mononuclear tungsten peroxo complexes in oxidation reactions

    NASA Astrophysics Data System (ADS)

    Jin, Peng; Wei, Donghui; Wen, Yiqiang; Luo, Mengfei; Wang, Xiangyu; Tang, Mingsheng

    2011-04-01

    Tungsten peroxo complexes have been widely used in olefin epoxidation, alcohol oxidation, Baeyer-Villiger oxidation and other oxidation reactions, however, there is still not a unanimous viewpoint for the active structure of mononuclear tungsten peroxo complex by now. In this paper, the catalysis of mononuclear tungsten peroxo complexes 0- 5 with or without acidic ligands for the green oxidation of cyclohexene to adipic acid in the absence of organic solvent and phase-transfer catalyst has been researched in experiment. Then we have suggested two possible kinds of active structures of mononuclear tungsten peroxo complexes including peroxo ring ( nA, n = 0-1) and hydroperoxo ( nB, n = 0-1) structures, which have been investigated using density functional theory (DFT). Moreover, the calculations on self-cycle mechanisms involving the two types of active structures of tungsten peroxo complexes with and without oxalic acid ligand have also been carried out at the B3LYP/[LANL2DZ/6-31G(d, p)] level. The highest energy barrier are 26.17 kcal/mol ( 0A, peroxo ring structure without oxalic acid ligand), 23.91 kcal/mol ( 1A, peroxo ring structure with oxalic acid ligand), 18.19 kcal/mol ( 0B, hydroperoxo structure without oxalic acid ligand) and 13.10 kcal/mol ( 1B, hydroperoxo structure with oxalic acid ligand) in the four potential energy profiles, respectively. The results indicate that both the energy barriers of active structure self-cycle processes with oxalic acid ligands are lower than those without oxalic acid ligands, so the active structures with oxalic acid ligands should be easier to recycle, which is in good agreement with our experimental results. However, due to the higher energy of product than that of the reactant, the energy profile of the self-cycle process of 1B shows that the recycle of 1B could not occur at all in theory. Moreover, the crystal data of peroxo ring structure with oxalic acid ligand could be found in some experimental references. Thus

  10. Synthesis of nano-sized stereoselective imprinted polymer by copolymerization of (S)-2-(acrylamido) propanoic acid and ethylene glycol dimethacrylate in the presence of racemic propranolol and copper ion.

    PubMed

    Alizadeh, Taher; Bagherzadeh, Azam; Shamkhali, Amir Nasser

    2016-06-01

    A new chiral functional monomer of (S)-2-(acrylamido) propanoic acid was obtained by reaction of (l)-alanine with acryloyl chloride. The resulting monomer was characterized by FT-IR and HNMR and then utilized for the preparation of chiral imprinted polymer (CIP). This was carried out by copolymerization of (l)-alanine-derived chiral monomer and ethylene glycol dimethacrylate, in the presence of racemic propranolol and copper nitrate, via precipitation polymerization technique, resulting in nano-sized networked polymer particles. The polymer obtained was characterized by scanning electron microscopy and FT-IR. The non-imprinted polymer was also synthesized and used as blank polymer. Density functional theory (DFT) was also employed to optimize the structures of two diasterometric ternary complexes, suspected to be created in the pre-polymerization step, by reaction of optically active isomers of propranolol, copper ion and (S)-2-(acrylamido) propanoic acid. Relative energies and other characteristics of the described complexes, calculated by the DFT, predicted the higher stability of (S)-propranolol involved complex, compared to (R)-propranolol participated complex. Practical batch extraction test which employed CIP as solid phase adsorbent, indicated that the CIP recognized selectively (S)-propranolol in the racemic mixture of propranolol; whereas, the non-imprinted polymer (NIP) showed no differentiation capability between two optically active isomers of propranolol. PMID:27040217

  11. Exploring Renner-Teller induced quenching in the reaction H(2S)+NH(a 1Delta): a combined experimental and theoretical study.

    PubMed

    Adam, L; Hack, W; McBane, G C; Zhu, H; Qu, Z-W; Schinke, R

    2007-01-21

    Experimental rate coefficients for the removal of NH(a (1)Delta) and ND(a (1)Delta) in collisions with H and D atoms are presented; all four isotope combinations are considered: NH+H, NH+D, ND+H, and ND+D. The experiments were performed in a quasistatic laser-flash photolysis/laser-induced fluorescence system at low pressures. NH(a (1)Delta) and ND(a (1)Delta) were generated by photolysis of HN(3) and DN(3), respectively. The total removal rate coefficients at room temperature are in the range of (3-5)x10(13) cm(3) mol(-1) s(-1). For two isotope combinations, NH+H and NH+D, quenching rate coefficients for the production of NH(X (3)Sigma(-)) or ND(X (3)Sigma(-)) were also determined; they are in the range of 1 x 10(13) cm(3) mol(-1) s(-1). The quenching rate coefficients directly reflect the strength of the Renner-Teller coupling between the (2)A(") and (2)A(') electronic states near linearity and so can be used to test theoretical models for describing this nonadiabatic process. The title reaction was modeled with a simple surface-hopping approach including a single parameter, which was adjusted to reproduce the quenching rate for NH+H; the same parameter value was used for all isotope combinations. The agreement with the measured total removal rate is good for all but one isotope combination. However, the quenching rates for the NH+D combination are only in fair (factor of 2) agreement with the corresponding measured data.

  12. In situ UV-visible spectroelectrochemical studies on the copolymerization of diphenylamine with ortho-methoxy aniline

    NASA Astrophysics Data System (ADS)

    Santhosh, P.; Gopalan, A.; Vasudevan, T.

    2003-05-01

    UV-visible spectroelectrochemical studies on copolymerization of diphenylamine (DPA) with ortho-methoxy aniline (OMA) were carried out for different feed ratios of DPA and OMA using indium tin oxide (ITO)-coated glass as working electrode. The UV-visible spectra show clear dependencies on the molar feed composition of DPA or OMA used in electropolymerization. Derivative cyclic voltabsorptogram (DCVA) was deduced at the wavelengths corresponding to the absorption by the intermediate species and used to confirm the intermediates generated during the electropolymerization. The composition of DPA and OMA in the copolymer for the copolymers synthesized with different molar feed ratios of DPA and OMA was determined by UV-visible spectroscopy. Reactivity ratios of DPA and OMA were deduced by using Fineman-Ross and Kelen-Tudos methods and correlated with spectroelectrochemical results.

  13. Cytoskeleton mimetic reinforcement of a self-assembled N,N'-dialkylimidazolium ionic liquid monomer by copolymerization.

    SciTech Connect

    Grubjesic, S.; Seifert, S.; Firestone, M. A.; Materials Science Division

    2009-08-11

    Preparation and photopolymerization of a decylmethylimidazolium ionic liquid (IL) that possesses an acrylate counteranion are described. This IL monomer self-assembles upon addition of water and can be copolymerized with poly(ethylene glycol) diacrylate (PEGDA) in the presence of a photoinitiator, forming a mechanically durable material that adopts a lamellar structure with in-plane hexagonally ordered pores, as evidenced by small-angle X-ray scattering (SAXS). Thermogravimetric analysis, the extent of polymerization, and solubility-swelling studies indicate the formation of a network copolymer of the IL monomer and the PEGDA. Additional evidence for the formation of a nanostructured copolymer is provided by evaluating the product formed by replacement of the IL monomer with the nonpolymerizable analogue, decylmethylimidazolium chloride. The results demonstrate the possibility of designing a self-assembled amiphiphilic bilayer architecture that is reinforced by polymerization and cross-linking.

  14. Preparation of hybrid thiol-acrylate emulsion-templated porous polymers by interfacial copolymerization of high internal phase emulsions.

    PubMed

    Langford, Caitlin R; Johnson, David W; Cameron, Neil R

    2015-05-01

    Emulsion-templated highly porous polymers (polyHIPEs), containing distinct regions differing in composition, morphology, and/or properties, are prepared by the simultaneous polymerization of two high internal phase emulsions (HIPEs) contained within the same mould. The HIPEs are placed together in the mould and subjected to thiol-acrylate photopolymerization. The resulting polyHIPE material is found to contain two distinct semicircular regions, reflecting the composition of each HIPE. The original interface between the two emulsions becomes a copolymerized band between 100 and 300 μm wide, which is found to be mechanically robust. The separate polyHIPE layers are distinguished from one another by their differing average void diameter, chemical composition, and extent of contraction upon drying.

  15. Extension of the energy range of the experimental activation cross-sections data of longer-lived products of proton induced nuclear reactions on dysprosium up to 65MeV.

    PubMed

    Tárkányi, F; Ditrói, F; Takács, S; Hermanne, A; Ignatyuk, A V

    2015-04-01

    Activation cross-sections data of longer-lived products of proton induced nuclear reactions on dysprosium were extended up to 65MeV by using stacked foil irradiation and gamma spectrometry experimental methods. Experimental cross-sections data for the formation of the radionuclides (159)Dy, (157)Dy, (155)Dy, (161)Tb, (160)Tb, (156)Tb, (155)Tb, (154m2)Tb, (154m1)Tb, (154g)Tb, (153)Tb, (152)Tb and (151)Tb are reported in the 36-65MeV energy range, and compared with an old dataset from 1964. The experimental data were also compared with the results of cross section calculations of the ALICE and EMPIRE nuclear model codes and of the TALYS nuclear reaction model code as listed in the latest on-line libraries TENDL 2013.

  16. A combined experimental and computational study of the catalytic dehydration of glycerol on microporous zeolites: an investigation of the reaction mechanism and acrolein selectivity.

    PubMed

    Lin, Xufeng; Lv, Yanhong; Qu, Yuanyuan; Zhang, Guodong; Xi, Yanyan; Phillips, David L; Liu, Chenguang

    2013-12-14

    The catalytic activity and the acrolein selectivity for liquid phase glycerol dehydration on β zeolites (HNa-β-k) were found to be dependent on the reaction temperature as well as on the amount of acid sites on the zeolites. An increase in the reaction temperature favors the acrolein selectivity. The acrolein selectivity increases with the Na(+)/H(+) ratio and the glycerol conversion decreases with it so that a maximum acrolein yield is obtained when a certain amount of acidic sites are replaced by non-active Na(+) sites. The computational results indicate that 3-hydoxylpropanal (HPA) is an important intermediate that determines the final product selectivity. The relative rates of the different reaction pathways for HAP can be affected by the amount of water molecules involved in its homogeneous reaction. Based on the reaction mechanism proposed, it was hypothesized that smaller pores reduce activity but increase selectivity to acrolein, and results of the H-MFI zeolite were consistent with this hypothesis. Our work provides important insight into the overall landscape of the reaction mechanism and can be used to help design reaction systems that have good acrolein selectivity for the liquid phase glycerol dehydration reactions.

  17. CO2 Reaction Induced Wettability Alteration and its Impacts on CO2 Storage: Pore to Core Scale Reservoir Condition Experimental Studies

    NASA Astrophysics Data System (ADS)

    Wan, J.; Tokunaga, T. K.; Kim, Y.; Jung, J.; Kim, T.; Dong, W.

    2013-12-01

    Wettability of the mineral surfaces plays an important role in subsurface multiphase flow and transport. Wettability affects the capillary pressure-saturation (Pc- S) relations, relative permeability (kr) of each fluid phase, and relative phase occupancy in reservoir pores. Although wettability issues have been studied extensively in other fields, significant knowledge gaps remain when applying the existing understanding to geological carbon sequestration; due largely to the unique physical-chemical properties of supercritical (sc) CO2 relative to other common non-wetting fluids such as air and oil. Here, we report our recent progress on wettability alteration upon reaction with CO2 and the resulting differences in capillary trapping of CO2 versus air. (1) Pore Scale Studies. There are conflict predictions in the literature concerning the effect of wettability on capillary trapping; some find that larger contact angles lead to lower capillary trapping while others have found opposite behavior. We hypothesized that spontaneous imbibition becomes energetically unfavorable with decreased wettability, so that increased residual trapping of scCO2 should occur during the post-injection inbibition stage. We developed a laboratory high-pressure and elevated temperature microscopic-micromodel system that is capable of controlling fine scale capillary pressure of scCO2-brine, and enabled us to conduct imbibition under controlled capillary pressures at the pore scale. We found that the de-wetting enhanced scCO2 capillary trapping is significant. These results suggest that scCO2 reaction induced dewetting can result in higher degrees of CO2 residual trapping in the post-injection stage than previously predicted. (2) Core Scale Studies. Capillary scaling is used routinely to predict Pc(S) relations for scCO2-brine systems at field scale, based on relations measured with air-water or mercury porosimetry. However, scaling-based predictions for CO2-brine systems have not been

  18. Investigating Experimental Effects within the Framework of Structural Equation Modeling: An Example with Effects on Both Error Scores and Reaction Times

    ERIC Educational Resources Information Center

    Schweizer, Karl

    2008-01-01

    Structural equation modeling provides the framework for investigating experimental effects on the basis of variances and covariances in repeated measurements. A special type of confirmatory factor analysis as part of this framework enables the appropriate representation of the experimental effect and the separation of experimental and…

  19. Gas-phase reactions of the bare Th2+ and U2+ ions with small alkanes, CH4, C2H6, and C3H8: experimental and theoretical study of elementary organoactinide chemistry.

    PubMed

    Di Santo, Emanuela; Santos, Marta; Michelini, Maria C; Marçalo, Joaquim; Russo, Nino; Gibson, John K

    2011-02-16

    The gas-phase reactions of two dipositive actinide ions, Th(2+) and U(2+), with CH(4), C(2)H(6), and C(3)H(8) were studied by both experiment and theory. Fourier transform ion cyclotron resonance mass spectrometry was employed to study the bimolecular ion-molecule reactions; the potential energy profiles (PEPs) for the reactions, both observed and nonobserved, were computed by density functional theory (DFT). The experiments revealed that Th(2+) reacts with all three alkanes, including CH(4) to produce ThCH(2)(2+), whereas U(2+) reacts with C(2)H(6) and C(3)H(8), with different product distributions than for Th(2+). The comparative reactivities of Th(2+) and U(2+) toward CH(4) are well explained by the computed PEPs. The PEPs for the reactions with C(2)H(6) effectively rationalize the observed reaction products, ThC(2)H(2)(2+) and UC(2)H(4)(2+). For C(3)H(8) several reaction products were experimentally observed; these and additional potential reaction pathways were computed. The DFT results for the reactions with C(3)H(8) are consistent with the observed reactions and the different products observed for Th(2+) and U(2+); however, several exothermic products which emerge from energetically favorable PEPs were not experimentally observed. The comparison between experiment and theory reveals that DFT can effectively exclude unfavorable reaction pathways, due to energetic barriers and/or endothermic products, and can predict energetic differences in similar reaction pathways for different ions. However, and not surprisingly, a simple evaluation of the PEP features is insufficient to reliably exclude energetically favorable pathways. The computed PEPs, which all proceed by insertion, were used to evaluate the relationship between the energetics of the bare Th(2+) and U(2+) ions and the energies for C-H and C-C activation. It was found that the computed energetics for insertion are entirely consistent with the empirical model which relates insertion efficiency to the

  20. Initiation precursors and initiators in laser-induced copolymerization of styrene and maleic anhydride in acetone

    NASA Technical Reports Server (NTRS)

    Miner, Gilda A.; Meador, Willard E.; Chang, C. Ken

    1990-01-01

    The initiation step of photopolymerized styrene/maleic anhydride copolymer was investigated at 365 nm. UV absorption measurements provide decisive evidence that the styrene/maleic anhydride charge transfer complex is the sole absorbing species; however, key laser experiments suggest intermediate reactions lead to a monoradical initiating species. A mechanism for the photoinitiation step of the copolymer is proposed.

  1. Experimental and theoretical study of the {sup 2}H(d-vector{gamma}){sup 4}He reaction below E{sub c.m.}=60 keV

    SciTech Connect

    Sabourov, K.; Ahmed, M.W.; Canon, S.R.; Crowley, B.; Joshi, K.; Kelley, J.H.; Nelson, S.O.; Perdue, B.A.; Schreiber, E.C.; Sabourov, A.; Tonchev, A.; Weller, H.R.; Wulf, E.A.; Prior, R.M.; Spraker, M.C.; Hofmann, H.M.; Trini, M.

    2004-12-01

    New measurements of the analyzing powers A{sub y} and T{sub 20} have been obtained for the {sup 2}H(d,{gamma}){sup 4}He reaction at a laboratory beam energy of 115 keV. A transition matrix element analysis results in a unique solution which indicates that the reaction proceeds by 55% E2, 29% E1, and 16% M2 radiation. These results are shown to be in good agreement with the results of a new refined resonating group model calculation. The impact of these results on the extrapolated value of the astrophysical S factor for this reaction is discussed.

  2. Unravelling Mechanistic Aspects of the Gas-Phase Ethanol Conversion: An Experimental and Computational Study on the Thermal Reactions of MO2 (+) (M=Mo, W) with Ethanol.

    PubMed

    González-Navarrete, Patricio; Schlangen, Maria; Wu, Xiao-Nan; Schwarz, Helmut

    2016-02-24

    The ion/molecule reactions of molybdenum and tungsten dioxide cations with ethanol have been studied by Fourier transform ion-cyclotron resonance mass spectrometry (FT-ICR MS) and density functional theory (DFT) calculations. Dehydration of ethanol has been found as the dominant reaction channel, while generation of the ethyl cation corresponds to a minor product. Cleary, the reactions are mainly governed by the Lewis acidity of the metal center. Computational results, together with isotopic labeling experiments, show that the dehydration of ethanol can proceed either through a conventional concerted [1,2]-elimination mechanism or a step-wise process; the latter occurs via a hydroxyethoxy intermediate. Formation of C2 H5 (+) takes place by transfer of OH(-) from ethanol to the metal center of MO2 (+) . The molybdenum and tungsten dioxide cations exhibit comparable reactivities toward ethanol, and this is reflected in similar reaction rate constants and branching ratios. PMID:26834042

  3. Experimental cross-sections of deuteron-induced reaction on 89Y up to 20 MeV; comparison of natTi(d,x)48V and 27Al(d,x)24Na monitor reactions

    NASA Astrophysics Data System (ADS)

    Lebeda, Ondřej; Štursa, Jan; Ráliš, Jan

    2015-10-01

    We measured cross-sections of the deuteron-induced reactions on 89Y in the energy range of 3.9-19.5 MeV. Excitation functions for formation of 88Zr, 89mZr, 89Zr, 88Y, 90mY and 87mSr were determined and compared with previously published data and prediction of the TALYS code. Thick target yields for production of 88Zr, 89Zrcum, 88Y, 90mY and 87mSr were calculated from the measured cross-sections. Achievable activity versus radionuclidic purity of medically relevant 89Zr is discussed and compared with the production via the 89Y(p,n) reaction. Parallel use of titanium and aluminium beam monitors revealed systematic difference between the recommended cross-sections of both monitoring reactions and provided new cross-section data for formation of 24Na, 27Mg, 43Sc, 44mSc, 44Sc, 46Sc, 47Sc and 48Sc. The cross-sections for the natTi(d,x)46Sc reactions agree very well with recently proposed recommended values.

  4. Experimental evidence for chair-like transition states in aldol reactions of methyl ketone lithium enolates: stereoselective synthesis and utilization of a deuterium-labeled enolate as a probe of reaction stereochemistry.

    PubMed

    Liu, Christopher M; Smith, William J; Gustin, Darin J; Roush, William R

    2005-04-27

    Aldol reactions of methyl ketone lithium enolates proceed via chairlike Zimmerman-Traxler transition states with 7:1 to 50:1 preference over alternative, boatlike transition structures, as determined by studies involving the configurationally stable deuterium-labeled enol silane 18 as the lithium enolate precursor.

  5. Experimental study of neutron-rich nuclei near the N = 82 closed shell using the {sub 40}{sup 96}Zr+{sub 50}{sup 124}Sn reaction with GASP and PRISMA-CLARA arrays

    SciTech Connect

    Rodríguez, W.; Torres, D. A.; Cristancho, F.; Medina, N. H.; Chapman, R.; Smith, J. F.; Mengoni, D.; Truesdale, V.; Grocutt, L.; Mulholland, K.; Kumar, V.; Hadinia, B.; Labiche, M.; Liang, X.; O'Donell, D.; Ollier, J.; Orlandi, R.; Smith, J. F.; Spohr, K. M.; Wady, P.; and others

    2014-11-11

    In this contribution an experimental study of the deep-inelastic reaction {sub 40}{sup 96}Zr+{sub 50}{sup 124}Sn at 530 MeV, using the GASP and PRISMA-CLARA arrays, is presented. The experiments populate a wealth of projectile-like and target-like binary fragments, in a large neutron-rich region around N ≥ 50 and Z ≈ 40. Preliminary results on the study of the yrast and near-yrast states for {sup 95}Nb will be shown, along with a comparison of the experimental yields obtained in the experiments.

  6. A combined experimental, theoretical, and Van't Hoff model study for identity methyl, proton, hydrogen atom, and hydride exchange reactions. Correlation with three-center four-, three-, and two-electron systems

    NASA Astrophysics Data System (ADS)

    Buck, Henk M.

    We have studied carbon transfer reactions following an SN2 reaction profile. With ab initio calculations and experimental geometries concerning the nature of the various complexes indicated as stable, intermediate, and transition state we were able to show the additional value of van't Hoff's tetrahedral configuration by changing its geometry via a trigonal pyramid into a trigonal bipyramid. The ratio of the apical bond and corresponding tetrahedral bond distances is then nearly 1.333. The relevance of this approach has also been shown for identity proton-(hydrogen atom-, and hydride-) in-line reactions. The use of this geometrical transmission will be demonstrated for the hydrogen bonding distances in e.g., DNA duplexes and other biological (supra) molecular systems.

  7. Experimental determination of the kerma factors for the reaction /sup 12/C(n,n'3. cap alpha. ) at E/sub n/ = 10-35 MeV

    SciTech Connect

    Antolkovic, B.; Slaus, I.; Plenkovic, D.

    1984-02-01

    Kerma factors for the reaction /sup 12/C(n,n'3..cap alpha..) have been experimentally determined performing kinematically complete measurement and using a continuous energy neutron beam up to 35 MeV. The results are compared with only one existing experiment at E/sub n/ = 27.4, 39.7, and 60.7 MeV and with a number of various model calculations.

  8. Preparation of Syndiotactic Poly(vinyl alcohol)/Poly(vinyl pivalate/vinyl acetate) Microspheres with Radiopacity Using Suspension Copolymerization and Saponification

    NASA Astrophysics Data System (ADS)

    Seok Lyoo, Won; Wook Cha, Jin; Young Kwak, Kun; Jae Lee, Young; Yong Jeon, Han; Sik Chung, Yong; Kyun Noh, Seok

    2010-06-01

    To prepare Poly(vinyl pivalate/vinyl acetate) [P(VPi/VAc)] microspheres with radiopacity, the suspension copolymerization approach in the presence of aqueous radiopaque nanoparticles was used. After, The P(VPi/VAc) microspheres with radiopacity were saponified in heterogeneous system, and then P(VPi/VAc) microspheres without aggregates were converted to s-PVA/P(VPi/VAc) microspheres of skin/core structure through the heterogeneous surface saponification. Radiopacity of microspheres was confirmed with Computed tomography (CT).

  9. Copolymerization and terpolymerization of carbon dioxide/propylene oxide/phthalic anhydride using a (salen)Co(III) complex tethering four quaternary ammonium salts

    PubMed Central

    Jeon, Jong Yeob; Eo, Seong Chan; Varghese, Jobi Kodiyan

    2014-01-01

    Summary The (salen)Co(III) complex 1 tethering four quaternary ammonium salts, which is a highly active catalyst in CO2/epoxide copolymerizations, shows high activity for propylene oxide/phthalic anhydride (PO/PA) copolymerizations and PO/CO2/PA terpolymerizations. In the PO/PA copolymerizations, full conversion of PA was achieved within 5 h, and strictly alternating copolymers of poly(1,2-propylene phthalate)s were afforded without any formation of ether linkages. In the PO/CO2/PA terpolymerizations, full conversion of PA was also achieved within 4 h. The resulting polymers were gradient poly(1,2-propylene carbonate-co-phthalate)s because of the drift in the PA concentration during the terpolymerization. Both polymerizations showed immortal polymerization character; therefore, the molecular weights were determined by the activity (g/mol-1) and the number of chain-growing sites per 1 [anions in 1 (5) + water (present as impurity) + ethanol (deliberately fed)], and the molecular weight distributions were narrow (M w/M n, 1.05–1.5). Because of the extremely high activity of 1, high-molecular-weight polymers were generated (M n up to 170,000 and 350,000 for the PO/PA copolymerization and PO/CO2/PA terpolymerization, respectively). The terpolymers bearing a substantial number of PA units (f PA, 0.23) showed a higher glass-transition temperature (48 °C) than the CO2/PO alternating copolymer (40 °C). PMID:25161738

  10. Concerted HO2 Elimination from α-Aminoalkylperoxyl Free Radicals: Experimental and Theoretical Evidence from the Gas-Phase NH2(•)CHCO2(-) + O2 Reaction.

    PubMed

    da Silva, Gabriel; Kirk, Benjamin B; Lloyd, Celli; Trevitt, Adam J; Blanksby, Stephen J

    2012-04-01

    We have investigated the gas-phase reaction of the α-aminoacetate (glycyl) radical anion (NH2(•)CHCO2(-)) with O2 using ion trap mass spectrometry, quantum chemistry, and statistical reaction rate theory. This radical is found to undergo a remarkably rapid reaction with O2 to form the hydroperoxyl radical (HO2(•)) and an even-electron imine (NHCHCO2(-)), with experiments and master equation simulations revealing that reaction proceeds at the ion-molecule collision rate. This reaction is facilitated by a low-energy concerted HO2(•) elimination mechanism in the NH2CH(OO(•))CO2(-) peroxyl radical. These findings can explain the widely observed free-radical-mediated oxidation of simple amino acids to amides plus α-keto acids (their imine hydrolysis products). This work also suggests that imines will be the main intermediates in the atmospheric oxidation of primary and secondary amines, including amine carbon capture solvents such as 2-aminoethanol (commonly known as monoethanolamine, or MEA), in a process that avoids the ozone-promoting conversion of (•)NO to (•)NO2 commonly encountered in peroxyl radical chemistry. PMID:26286401

  11. In vitro drug release behavior, mechanism and antimicrobial activity of rifampicin loaded low molecular weight PLGA-PEG-PLGA triblock copolymeric nanospheres.

    PubMed

    Gajendiran, M; Divakar, S; Raaman, N; Balasubramanian, S

    2013-12-01

    Poly (lactic-co-glycolic acid) (PLGA (92:8)) and a series of PLGA-PEG-PLGA tri block copolymers were synthesized by direct melt polycondensation. The copolymers were characterized by FTIR, and 1HNMR spectroscopic techniques, viscosity, gel permeation chromatography (GPC) and powder x-ray diffraction (XRD). The rifampicin (RIF) loaded polymeric nanospheres (NPs) were prepared by ultrasonication-W/O emulsification technique. The NPs have been characterized by field emission scanning electron microscopy (FESEM), TEM, powder X-ray diffraction (XRD), UVvisible spectroscopy and DLS measurements. The drug loaded triblock copolymeric NPs have five folds higher drug content and drug loading efficiency than that of PLGA microspheres (MPs). The in vitro drug release study shows that the drug loaded NPs showed an initial burst release after that sustained release up to 72 h. All the triblock copolymeric NPs follow anomalous drug diffusion mechanism while the PLGA MPs follow non-Fickian super case-II mechanism up to 12 h. The overall in-vitro release follows second order polynomial kinetics up to 72 h. The antimicrobial activity of the RIF loaded polymer NPs was compared with that of pure RIF and tetracycline (TA). The RIF loaded triblock copolymeric NPs inhibited the bacterial growth more effectively than the pure RIF and TA.

  12. Functional and surface-active membranes from poly(vinylidene fluoride)-graft-poly(acrylic acid) prepared via RAFT-mediated graft copolymerization.

    PubMed

    Ying, L; Yu, W H; Kang, E T; Neoh, K G

    2004-07-01

    Poly (vinylidene fluoride) (PVDF) with "living" poly (acrylic acid) (PAAc) side chains (PVDF-g-PAAc) was prepared by reversible addition-fragmentation chain transfer (RAFT)-mediated graft copolymerization of acrylic acid (AAc) with the ozone-pretreated PVDF. The chemical composition and structure of the copolymers were characterized by elemental analysis, Fourier transform infrared spectroscopy, and thermogravimetric analysis. The copolymer could be readily cast into pH-sensitive microfiltration (MF) membranes with enriched living PAAc graft chains on the surface (including the pore surfaces) by phase inversion in an aqueous medium. The surface composition of the membranes was determined by X-ray photoelectron spectroscopy. The morphology of the membranes was characterized by scanning electron microscopy. The pore size distribution of the membranes was found to be much more uniform than that of the corresponding membranes cast from PVDF-g-PAAc prepared by the "conventional" free-radical graft copolymerization process. Most important of all, the MF membranes with surface-tethered PAAc macro chain transfer agents, or the living membrane surfaces, could be further functionalized via surface-initiated block copolymerization with N-isopropylacrylamide (NIPAAM) to obtain the PVDF-g-PAAc-b-PNIPAAM MF membranes, which exhibited both pH- and temperature-dependent permeability to aqueous media. PMID:16459627

  13. Ion-neutral reaction of the C2H2N+ cation with C2H2: An experimental and theoretical study

    NASA Astrophysics Data System (ADS)

    Fathi, P.; Geppert, W. D.; Kaiser, A.; Ascenzi, D.

    2016-03-01

    The ion-neutral reactions of the C2H2N+ cation with C2H2 have been investigated using a Guided Ion Beam Mass Spectrometer (GIB-MS). The following ionic products were observed: CH3+, C2H2+, C2H3+, HNC+ /HCN+ , HCNH+, C3H+ , C2N+ , C3H3+, HCCN+ and C4H2N+ . Theoretical calculations have been carried out to propose reaction pathways leading to the observed products. These processes are of relevance for the generation of long chain nitrogen-containing species and they may be of interest for the chemistry of Titan's ionosphere or circumstellar envelopes.

  14. Experimental and Numerical Investigation of the Dependency of Reaction Dynamics on the Plasma Gas Temperature in He/N2 Cryoplasmas

    NASA Astrophysics Data System (ADS)

    Muneoka, Hitoshi; Urabe, Keiichiro; Stauss, Sven; Terashima, Kazuo

    2014-10-01

    The plasma gas temperature (Tg) is one of the essential parameters in plasma science and technology, but so far, the effect of Tg on low-temperature high-gas-density plasma chemistry has not been investigated in detail yet. Cryoplasmas, which are defined as plasmas whose Tg can be controlled below room temperature (RT), have the potential for various applications. In this study, to investigate the effect of Tg on the reaction dynamics in He/N2 cryoplasmas, we developed a new 0D reaction model and also investigated the cryoplasmas by time-resolved laser absorption spectroscopy (LAS) and optical emission spectroscopy (OES). LAS measurements in He cryoplasmas at the same gas density as at RT and 1 atm, showed a longer lifetime (>50 times) of metastable helium atom (Hem) at cryogenic temperature (CT) compared to those at RT. OES revealed a time delay of the N2+ emission peak relative to the He emission peak of a few microseconds, and the delay decreased with increasing Tg. The simulation using our reaction model suggested that the long lifetime of Hem at CT are due to the change of the reaction dynamics related to Hem as a function of Tg.

  15. Holographic polymer dispersed liquid crystal system utilizing the co-polymerizations with siloxane compounds and polypropylene glycol derivatives

    NASA Astrophysics Data System (ADS)

    Takanokura, Tomoe; Kurashige, Makio; Ishida, Kazutoshi; Ohyagi, Yasuyuki; Watanabe, Masachika; Cho, Yeong Hee

    2011-03-01

    Holographic polymer dispersed liquid crystal (HPDLC) has a feature that can control diffraction of light by applying electric field. HPDLC can be used for optical elements such as an optical switch, or a polarized beam splitter etc. One of the reactive systems for making HPDLC is well known photopolymerization-induced phase separation (PIPS). The performance of HPDLC by PIPS is dependent on distribution of oriented liquid crystal (LC) molecules, or size and shape of LC droplets. These are controlled by chemical structure or functional group of polymer matrix. In this report, Organic-inorganic hybrid materials having sensitivity at 532 nm were synthesized. Polymer matrix was formed with co-polymerization of siloxane-containing materials and poly (propylene glycol) derivatives functionalized with methacrylate groups. Siloxane chain was introduced in polymer matrix to encourage phase separation of LC and stabilize grating structure. In addition, poly (propylene glycol) derivatives were designed to control polymerization rate and extent of phase separation of LC. The characterization of HPDLC was evaluated in terms of diffraction efficiency, contrast between diffraction and transparency modes by applying voltage, and switch speed. As a result, the separation ratio of p-polarized light and s-polarized light was 100:1. The value of ▵n was 0.075, and the index matching of both polymer-rich layer and LC-rich layer was completed at voltage of 17V/μm.

  16. Furfuralcohol Co-Polymerized Urea Formaldehyde Resin-derived N-Doped Microporous Carbon for CO2 Capture

    NASA Astrophysics Data System (ADS)

    Liu, Zhen; Yang, Yi; Du, Zhenyu; Xing, Wei; Komarneni, Sridhar; Zhang, Zhongdong; Gao, Xionghou; Yan, Zifeng

    2015-08-01

    Carbon-based adsorbent is considered to be one of the most promising adsorbents for CO2 capture form flue gases. In this study, a series of N-doped microporous carbon materials were synthesized from low cost and widely available urea formaldehyde resin co-polymerized with furfuralcohol. These N-doped microporous carbons showed tunable surface area in the range of 416-2273 m2 g-1 with narrow pore size distribution within less than 1 nm and a high density of the basic N functional groups (2.93-13.92 %). Compared with the carbon obtained from urea resin, the addition of furfuralcohol apparently changed the surface chemical composition and pore size distribution, especially ultramicropores as can be deduced from the X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FT-IR), and pore size distribution measurements and led to remarkable improvement on CO2 adsorption capacity. At 1 atm, N-doped carbons activated at 600 °C with KOH/UFFC weight ratio of 2 (UFFA-2-600) showed the highest CO2 uptake of 3.76 and 1.57 mmol g-1 at 25 and 75 °C, respectively.

  17. Radiation-induced graft copolymerization of poly(ethylene glycol) monomethacrylate onto deoxycholate-chitosan nanoparticles as a drug carrier

    NASA Astrophysics Data System (ADS)

    Pasanphan, Wanvimol; Rattanawongwiboon, Thitirat; Rimdusit, Pakjira; Piroonpan, Thananchai

    2014-01-01

    Poly(ethylene glycol) monomethacrylate-grafted-deoxycholate chitosan nanoparticles (PEGMA-g-DCCSNPs) were successfully prepared by radiation-induced graft copolymerization. The hydrophilic poly(ethylene glycol) monomethacrylate was grafted onto deoxycholate-chitosan in an aqueous system. The radiation-absorbed dose is an important parameter on degree of grafting, shell thickness and particle size of PEGMA-g-DCCSNPs. Owing to their amphiphilic architecture, PEGMA-g-DCCSNPs self-assembled into spherical core-shell nanoparticles in aqueous media. The particle size of PEGMA-g-DCCSNPs measured by TEM varied in the range of 70-130 nm depending on the degree of grafting as well as the irradiation dose. Berberine (BBR) as a model drug was encapsulated into the PEGMA-g-DCCSNPs. Drug release study revealed that the BBR drug was slowly released from PEGMA-g-DCCSNPs at a mostly constant rate of 10-20% in PBS buffer (pH 7.4) at 37 °C over a period of 23 days.

  18. High-energy radiation monitoring based on radio-fluorogenic co-polymerization. I: Small volume in situ probe.

    PubMed

    Warman, J M; de Haas, M P; Luthjens, L H

    2009-05-21

    A method of radiation dosimetry is described which is based on the radiation-induced initiation of polymerization of a bulk monomer (e.g. methyl methacrylate) containing a small concentration (about 100 ppm) of a compound which is non-fluorescent but which becomes highly fluorescent when it is incorporated into a growing polymer chain of the bulk monomer. We call the overall process 'radio-fluorogenic co-polymerization' or RFCP for short. The method is illustrated by results on the in situ monitoring of the accumulated dose within the irradiation chamber of a cobalt-60 gamma-ray source using a small plastic capsule containing about 0.2 ml of an RFCP solution. Remote monitoring of the fluorescence is carried out on a timescale of seconds using optical fibres connecting the probe to a 360 nm LED excitation source and a miniature spectrophotometer. The fluorescence is permanent and the intensity is linearly proportional to the accumulated dose from a few tenths of a gray up to hundreds of gray. The sensitivity to dose depends on the polymerizable monomer used and obeys a square root dependence on dose rate over the range studied, 0.27-3.76 Gy min(-1). The polymeric nature of the fluorescent product suggests that the RFCP effect could be used to provide fixed two- or three-dimensional fluorescent images of dose deposition in gel films or phantoms. PMID:19420430

  19. Fabrication of Fluoropolymer Microtubes via RAFT Copolymerization of N,N'-Methylene Bisacrylamide Gel Fibers and Fluoromonomer.

    PubMed

    Li, Qi; Wang, Yi; Tang, Liming

    2015-06-01

    Fluoropolymer microtubes with a smooth surface were fabricated in more than 70 % yield via reversible addition fragmentation chain transfer (RAFT) co-polymerization of N,N'-methylene bisacrylamide (MBA) gel fibers as both template and monomer, 2-(perfluoro-3-methylbutyl)ethyl acrylate (R-3420) as co-monomer, and pentaerythritol tetraacrylate (PET4A) as cross-linker. The resulting fluoropolymer microtubes were characterized fully by SEM, TEM, EDS, XPS, and FT-IR. The influence of the monomer composition on the yields and morphologies of the tubes were investigated in detail. The results indicated that polymer microtubes with a smooth surface were obtained at suitable amounts of R-3420 and PET4A. Because of the decreased solubility of MBA gel fibers, the wall thickness increased as more R-3420 was used. In the presence of PET4A, the solution polymerization could be facilitated and more R-3420 could be attached onto the tubes based on FT-IR analysis. The water contact angle and swelling ratio measurements both revealed the low hydrophilicity and high lipophilicity of the fluoropolymer microtubes, which made the sample able to absorb toluene selectively in a water/toluene two-phase system. PMID:25786386

  20. Homogeneous graft copolymerization of styrene onto cellulose in a sulfur dioxide-diethylamine-dimethyl sulfoxide cellulose solvent

    SciTech Connect

    Tsuzuki, M.; Hagiwara, I.; Shiraishi, N.; Yokota, T.

    1980-12-01

    Graft copolymerization of styrene onto cellulose was studied in a homogeneous system (SO/sub 2/(liquid)- diethylamine (DEA)-dimethyl sulfoxide (DMSO) medium)) by ..gamma..-ray mutual irradiation technique. At the same time, homopolymerization of styrene was also examined separately in DMSO, SO/sub 2/-DMSO, DEA-DMSO, and SO/sub 2/-DEA-DMSO media by the same technique. Polymerization of styrene hardly occurs on concentrations above 10 mole SO/sub 2/-DEA complex per mole glucose unit. Maximum percent grafting was obtained in concentrations of 4 mole, after which it decreased rapidly. Total conversion and percent grafting increased with the irradiation time. The value (=0.55) of the slope of the total conversion rate plotted against the dose was only a little higher than the 1/2 which was expected from normal kinetics. No retardation in homopolymerization of styrene in DMSO, SO/sub 2/-DMSO, and DEA-DMSO was evident, while the retardation of homopolymerization in the SO/sub 2/-DEA-DMSO medium was measurable. Sulfur atoms were detected in the polymers obtained in both of SO/sub 2/-DMSO and SO/sub 2/-DEA-DMSO solutions. All of the molecular weights of polymers obtained in the present experiment were very low (3.9 x 10/sup 3/-1.75 x 10/sup 4/).

  1. Experimental and theoretical studies of the O(3P) + C2H4 reaction dynamics: Collision energy dependence of branching ratios and extent of intersystem crossing

    NASA Astrophysics Data System (ADS)

    Fu, Bina; Han, Yong-Chang; Bowman, Joel M.; Leonori, Francesca; Balucani, Nadia; Angelucci, Luca; Occhiogrosso, Angela; Petrucci, Raffaele; Casavecchia, Piergiorgio

    2012-12-01

    The reaction of O(3P) with C2H4, of importance in combustion and atmospheric chemistry, stands out as paradigm reaction involving not only the indicated triplet state potential energy surface (PES) but also an interleaved singlet PES that is coupled to the triplet surface. This reaction poses great challenges for theory and experiment, owing to the ruggedness and high dimensionality of these potentials, as well as the long lifetimes of the collision complexes. Crossed molecular beam (CMB) scattering experiments with soft electron ionization detection are used to disentangle the dynamics of this polyatomic multichannel reaction at a collision energy Ec of 8.4 kcal/mol. Five different primary products have been identified and characterized, which correspond to the five exothermic competing channels leading to H + CH2CHO, H + CH3CO, CH3 + HCO, CH2 + H2CO, and H2 + CH2CO. These experiments extend our previous CMB work at higher collision energy (Ec ˜ 13 kcal/mol) and when the results are combined with the literature branching ratios from kinetics experiments at room temperature (Ec ˜ 1 kcal/mol), permit to explore the variation of the branching ratios over a wide range of collision energies. In a synergistic fashion, full-dimensional, QCT surface hopping calculations of the O(3P) + C2H4 reaction using ab initio PESs for the singlet and triplet states and their coupling, are reported at collision energies corresponding to the CMB and the kinetics ones. Both theory and experiment find almost an equal contribution from the triplet and singlet surfaces to the reaction, as seen from the collision energy dependence of branching ratios of product channels and extent of intersystem crossing (ISC). Further detailed comparisons at the level of angular distributions and translational energy distributions are made between theory and experiment for the three primary radical channel products, H + CH2CHO, CH3 + HCO, and CH2 + H2CO. The very good agreement between theory and

  2. Gas-phase reactions of OH with methyl amines in the presence or absence of molecular oxygen. An experimental and theoretical study.

    PubMed

    Onel, L; Thonger, L; Blitz, M A; Seakins, P W; Bunkan, A J C; Solimannejad, M; Nielsen, C J

    2013-10-17

    The rate coefficients for the reaction of OH with the alkyl amines: methylamine (MA), dimethylamine (DMA), trimethylamine (TMA), and ethylamine (EA) have been determined using the technique of pulsed laser photolysis with detection of OH by laser-induced fluorescence as a function of temperature from 298 K to ∼600 K. The rate coefficients (10(11) × k/cm(3) molecule(-1) s(-1)) at 298 K in nitrogen bath gas (typically 5-25 Torr) are: k(OH+MA) = 1.97 ± 0.11, k(OH+DMA) = 6.27 ± 0.63, k(OH+TMA) = 5.78 ± 0.48, k(OH+EA) = 2.50 ± 0.13. The reactions all show a negative temperature dependence which can be characterized as: k(OH+MA) = (1.889 ± 0.053) × 10(-11)(T/298 K)(-(0.56±0.10)), k(OH+DMA) = (6.39 ± 0.35) × 10(-11)(T/298 K)(-(0.75±0.18)), k(OH+TMA) = (5.73 ± 0.15) × 10(-11)(T/298 K)(-(0.71±0.10)), and k(OH+EA) = (2.54 ± 0.08) × 10(-11)(T/298 K)(-(0.68±0.10)). OH and OD reactions have very similar kinetics. Potential energy surfaces (PES) for the reactions have been characterized at the MP2/aug-cc-pVTZ level and improved single point energies of stationary points obtained in CCSD(T) and CCSD(T*)-F12a calculations. The PES for all reactions are characterized by the formation of pre- and post-reaction complexes and submerged barriers. The calculated rate coefficients are in good agreement with experiment; the overall rate coefficients are relatively insensitive to variations of the barrier heights within typical chemical accuracy, but the branching ratios vary significantly. The rate coefficients for the reactions of OH/OD with MA, DMA, and EA do not vary with added oxygen, but for TMA a significant reduction in the rate coefficient is observed consistent with OH recycling from a chemically activated peroxy radical. OH regeneration is pressure-dependent and is not significant at 298 K and atmospheric pressure, but the efficiency of recycling increases strongly with temperature. The PES for OH recycling have been calculated. There is evidence that the

  3. Application of fluid-rock reaction studies to in situ recovery from oil sand deposits, Alberta, Canada - I. Aqueous phase results for an experimental-statistical study of water-bitumen-shale reactions

    NASA Astrophysics Data System (ADS)

    Boon, J. A.; Hitchon, Brian

    1983-02-01

    In situ recovery operations in oil sand deposits effectively represent man-imposed low to intermediate temperature metamorphism of the sediments in the deposit. In order to evaluate some of the reactions which occur, a factorial experiment was earned out in which a shale from the Lower Cretaceous McMurray Formation in the Athabasca oil sand deposit of Alberta, in the presence or absence of bitumen, was subjected to hydrothermal treatment with aqueous fluids of varying pH and salinity, at two different temperatures, for periods up to 92 hours. The aqueous fluid was analyzed and the analytical data subjected to statistical factor analysis and analysis of variance, which enabled identification of the main processes, namely, cation exchange, the production of two types of colloidal material, and the dissolution of quartz There is also saturation of the aqueous phase by. as yet unidentified, "total organic carbon" and complete conversion and removal of all nitrogen in the shale to the aqueous phase. These reactions have implications with regards to the economics of the in situ recovery process, specifically with respect to the reuse and/or disposal of the produced water and the plugging of the pore space and hence of reduction of permeability between the injection and production wells. As a result of these experiments it is suggested that monitoring of the composition of the produced water from in situ recovery operations in oil sand deposits would be advisable.

  4. Intramolecular cycloadditions of cyclobutadiene with dienes: experimental and computational studies of the competing (2 + 2) and (4 + 2) modes of reaction.

    PubMed

    Limanto, John; Khuong, Kelli S; Houk, K N; Snapper, Marc L

    2003-12-31

    Highly functionalized, cyclobutene-containing adducts are afforded through intramolecular cycloadditions between cyclobutadiene and tethered dienes. The cycloaddition displays the following reactivity trend: cyclobutadiene serves as a dienophile in intramolecular reactions when it is connected to the diene through a four-atom tether. In cases where a three-atom linker separates the two reaction partners, the cyclobutadiene can function as both a diene and dienophile, affording a mixture of vinylcyclobutane (2 + 2) and cyclohexene-containing cycloadducts (4 + 2). Theoretical studies provide insight into the factors influencing the various pericyclic pathways operative in this system. In cases where cyclobutadiene functions as a diene to generate vinylcyclobutanes, these (2 + 2) adducts can be converted into the corresponding (4 + 2) cyclohexenyl products through a [3,3]-sigmatropic rearrangement.

  5. Experimental and theoretical angular and translational energy distributions for the reaction CN+D{sub 2}{r_arrow}DCN+D

    SciTech Connect

    Wang, J.; Liu, K.; Schatz, G.C.; ter Horst, M.

    1997-11-01

    This paper presents new measurements of angular and translational energy distributions for the title reaction at a reagent kinetic energy of 5.8 kcal/mol, and compares them with the corresponding results from quasiclassical trajectory calculations based on an accurate global potential energy surface. The comparison of theory and experiment is generally good; however, the minor deviations that we find provide valuable information concerning errors in the potential energy surface. Both experiment and theory indicate that CN+D{sub 2} is a simple abstraction reaction, with predominantly backward-scattered angular distributions and about 37{percent} of the available energy ending up in product translation. Strong dependence of the calculated angular and translational energy distributions on reagent kinetic energy is noted. {copyright} {ital 1997 American Institute of Physics.}

  6. Experimental cross section of the 71Ga(n,γ)72Ga reaction at 0.0334 eV energy

    NASA Astrophysics Data System (ADS)

    Afroze, N.; Uddin, M. S.; Hossain, S. M.; Islam, M. A.; Shariff, M. A.; Zakaria, A. K. M.; Datta, T. K.; Azharul Islam, S. M.

    2014-10-01

    The cross section of the 71Ga(n,γ)72Ga reaction at 0.0334 eV was measured for the first time using monochromatic neutrons from powder diffractometer at TRIGA Mark II nuclear reactor. The 197Au(n,γ)198Au reaction was used to monitor the neutron beam intensity. The HPGe γ-ray spectrometry was used to determine the radioactivity of the product radionuclides. The obtained cross section value amounted 3.42 ± 0.27 b is about 95% consistent with JENDL-4, but about 17% and 14% lower than that of the ENDF/B-VII and TENDL-2012 data libraries, respectively. The measured value at 0.0334 eV and the previous measured value at 0.0536 eV would be useful to confirm the reliability of the data evaluated by 1/v relation in the above libraries.

  7. Pretreatment with antilymphocyte globulin and donor cells on graft prolongation in an experimental model and some observations on graft-versus-host reaction.

    PubMed

    Pegrum, G D; Williams, G; Markwick, J; Barnes, R M

    1976-01-01

    Survival of Lewis X Brown Norway F1 renal allografts was prolonged in Lewis recipients by pretreatment with small numbers of donor marrow cells and low dose antilymphocyte globulin(ALG)in combination. Either marrow cells or ALG alone were ineffective at these doses. It was also shown that pretreatment with marrow cells and antilymphocyte serum (ALS) considerably suppressed the local graft-versus-host reaction.

  8. Herbert P. Broida Prize Talk: Experimental realization of coherent control of molecular dynamics and chemical reactions with feedback-optimized laser pulses--Quantum Control of Femtochemistry

    NASA Astrophysics Data System (ADS)

    Gerber, Gustav

    2009-05-01

    By using coherent control techniques we control the behavior of quantum systems on their natural fs-time scale by applying ultrashort coherent light fields in the wavelength range from the IR to the UV. These laser pulses can be variably shaped in space and time using a laser pulse shaper consisting of a liquid-crystal display. [1] Laser-optimized femtochemistry in the gas phase and liquid phase is one field in which this new technique is successfully employed. Automated optimization of branching ratios and total product yields of gas phase photodissociation reactions as well as chemically selective molecular excitation in the liquid phase is performed [2][3]. Structural changes of a molecule in the liquid phase have been controlled by laser-optimized photoisomerization of a cyanine dye molecule [4] and of retinal in bacteriorhodopsin [5]. So far, optimal control techniques have been restricted to gas phase and condensed phase optimization experiments. Recently we have demonstrated femtosecond laser-assisted catalytic reactions on a Pd(100) single crystal surface. By applying a closed-loop optimal control scheme, we manipulate these reactions and selectively optimize the ratio of different bond-forming reaction channels, in contrast to previous quantum control experiments aiming at bond-cleavage. The results represent a first step towards selective photocatalysis of molecules. [4pt] [1] T. Baumert et al, Appl. Phys. B 65, 779 (1997)[0pt] [2] A. Assion et al, Science 282, 919(1998); T. Brixner et al, J. Mod. Opt. 50, 539 (2003)[0pt] [3] T. Brixner et al, Nature, Vol. 414, 57 (2001) and J. Chem. Phys. 118, 3692 (2003)[0pt] [4] G. Krampert et al, Phys. Rev. Lett. 94, 068305 (2005)[0pt] [5] G. Vogt et al, Chem. Phys. Lett. 433, 211 (2006) P. Nuernberger et al, Phys. Chem. Chem. Phys. 9, 2470 (2007)

  9. The fluorine destruction in stars: First experimental study of the {sup 19}F(p,{alpha}){sup 16}O reaction at astrophysical energies

    SciTech Connect

    La Cognata, M.; Mukhamedzhanov, A.; Spitaleri, C.; Indelicato, I.; Aliotta, M.; Burjan, V.; Cherubini, S.; Coc, A.; Gulino, M.; Hons, Z.; Kiss, G. G.; Kroha, V.; Lamia, L.; Mrazek, J.; Palmerini, S.; Piskor, S.; Pizzone, R. G.; Puglia, S. M. R.; Rapisarda, G. G.; Romano, S.; and others

    2012-11-12

    The {sup 19}F(p,{alpha}){sup 16}O reaction is an important fluorine destruction channel in the proton-rich outer layers of asymptotic giant branch (AGB) stars and it might also play a role in hydrogendeficient post-AGB star nucleosynthesis. So far, available direct measurements do not reach the energy region of astrophysical interest (E{sub cm}{approx} 300 keV), because of the hindrance effect of the Coulomb barrier. The Trojan Horse (TH) method was thus used to access this energy region, by extracting the quasi-free contribution to the {sup 2}H({sup 19}F,{alpha}{sup 16}O)n reaction. The TH measurement of the {alpha}{sub 0} channel, which is the dominant one at such energies, shows the presence of resonant structures not observed before that cause an increase of the reaction rate at astrophysical temperatures up to a factor of 1.7, with potential important consequences for stellar nucleosynthesis.

  10. Theoretical Analyses and Experimental Investigations of Selective Carbothermal Reactions of Vanadium-Bearing Titanomagnetite Concentrates for Preparation of Iron-Based Wear-Resistant Material

    NASA Astrophysics Data System (ADS)

    Zhang, Guangming; Feng, Keqin; Yue, Huifang

    2016-09-01

    Based on FACTSage® software, this paper focuses on the thermodynamic calculations of selective carbothermal reactions of vanadium-bearing titanomagnetite concentrates for preparing iron-based wear-resistant material directly from vanadium-bearing titanomagnetite concentrates. The calculations show that it was most likely to generate metallic iron, titanium carbide and vanadium carbide among all possible carbothermal reactions of vanadium-bearing titanomagnetite concentrates in a vacuum of 10 Pa. The equilibrium composition calculations indicate that Fe3O4 can be reduced to metallic iron by carbon above 400°C, FeTiO3 can be converted into TiC by carbon above 800°C and V2O5 can be converted into VC by carbon above 600°C in a vacuum of 10 Pa. The investigations demonstrated that the percentage of ferrous oxides reduced to metallic iron was about 96%, the conversion percentage of FeTiO3 into TiC was about 75% and the conversion percentage of V2O5 into VC was about 94% after the selective carbothermal reactions of vanadium-bearing titanomagnetite concentrates at 1300°C for 3 h in a vacuum of 10 Pa.

  11. Theoretical Analyses and Experimental Investigations of Selective Carbothermal Reactions of Vanadium-Bearing Titanomagnetite Concentrates for Preparation of Iron-Based Wear-Resistant Material

    NASA Astrophysics Data System (ADS)

    Zhang, Guangming; Feng, Keqin; Yue, Huifang

    2016-07-01

    Based on FACTSage® software, this paper focuses on the thermodynamic calculations of selective carbothermal reactions of vanadium-bearing titanomagnetite concentrates for preparing iron-based wear-resistant material directly from vanadium-bearing titanomagnetite concentrates. The calculations show that it was most likely to generate metallic iron, titanium carbide and vanadium carbide among all possible carbothermal reactions of vanadium-bearing titanomagnetite concentrates in a vacuum of 10 Pa. The equilibrium composition calculations indicate that Fe3O4 can be reduced to metallic iron by carbon above 400°C, FeTiO3 can be converted into TiC by carbon above 800°C and V2O5 can be converted into VC by carbon above 600°C in a vacuum of 10 Pa. The investigations demonstrated that the percentage of ferrous oxides reduced to metallic iron was about 96%, the conversion percentage of FeTiO3 into TiC was about 75% and the conversion percentage of V2O5 into VC was about 94% after the selective carbothermal reactions of vanadium-bearing titanomagnetite concentrates at 1300°C for 3 h in a vacuum of 10 Pa.

  12. Experimental determination of the {sup 17}O(p,{alpha}){sup 14}N and {sup 17}O(p,{gamma}){sup 18}F reaction rates

    SciTech Connect

    Chafa, A.; Ouichaoui, S.; Tatischeff, V.; Coc, A.; Garrido, F.; Kiener, J.; Lefebvre-Schuhl, A.; Thibaud, J.-P.; Aguer, P.; Barhoumi, S.; Hernanz, M.; Jose, J.; Sereville, N. de

    2007-03-15

    The {sup 17}O(p,{alpha}){sup 14}N and {sup 17}O(p,{gamma}){sup 18}F reactions are of major importance to hydrogen-burning nucleosynthesis in a number of different stellar sites. In particular, {sup 17}O and {sup 18}F nucleosynthesis in classical novae is strongly dependent on the thermonuclear rates of these two reactions. The previously estimated rate for {sup 17}O(p,{alpha}){sup 14}N carries very large uncertainties in the temperature range of classical novae (T=0.01-0.4 GK), whereas a recent measurement has reduced the uncertainty of the {sup 17}O(p,{gamma}){sup 18}F rate. We report on the observation of a previously undiscovered resonance at E{sub c.m.}=183.3 keV in the {sup 17}O(p,{alpha}){sup 14}N reaction, with a measured resonance strength {omega}{gamma}{sub p{alpha}}=(1.6{+-}0.2)x10{sup -3} eV. We studied in the same experiment the {sup 17}O(p,{gamma}){sup 18}F reaction by an activation method, and the resonance strength was found to amount to {omega}{gamma}{sub p{gamma}}=(2.2{+-}0.4)x10{sup -6} eV. The excitation energy of the corresponding level in {sup 18}F was determined to be 5789.8{+-}0.3 keV in a Doppler shift attenuation method measurement, which yielded a value of {tau}<2.6 fs for the level lifetime. The {sup 17}O(p,{alpha}){sup 14}N and {sup 17}O(p,{gamma}){sup 18}F reaction rates were calculated using the measured resonance properties and reconsidering some previous analyses of the contributions of other levels or processes. The {sup 17}O(p,{alpha}){sup 14}N rate is now well established below T=1.5 GK, with uncertainties reduced by orders of magnitude in the temperature range T=0.1-0.4 GK. The uncertainty in the {sup 17}O(p,{gamma}){sup 18}F rate is somewhat larger because of remaining obscurities in the knowledge of the direct capture process. These new resonance properties have important consequences for {sup 17}O nucleosynthesis and {gamma}-ray emission of classical novae.

  13. Swelling, ion uptake and biodegradation studies of PE film modified through radiation induced graft copolymerization

    NASA Astrophysics Data System (ADS)

    Kaur, Inderjeet; Gupta, Nitika; Kumari, Vandna

    2011-09-01

    An attempt to develop biodegradable polyethylene film grafting of mixture of hydrophilic monomers methacrylic acid (MAAc) and acrylamide (AAm) onto PE film has been carried out by preirradiation method using benzoyl peroxide as the radical initiator. Since ether linkages are susceptible to easy cleavage during degradation process, PE film was irradiated before the grafting reactions by γ-rays to introduce peroxidic linkages (PE-OO-PE) that offer sites for grafting. The effect of irradiation dose, monomer concentration, initiator concentration, temperature, time and amount of water on the grafting percent was determined. Maximum percentage of grafting of binary mixture (MAAc+AAm), (1792%) was obtained at a total concentration of binary monomer mixture=204.6×10 -2 mol/L ([MAAc]=176.5×10 -2 mol/L, [AAm]=28.1×10 -2 mol/L), [BPO]=8.3×10 -2 mol/L at 100 °C in 70 min. The grafted PE film was characterized by the Fourier Transform Infrared Spectroscopy (FTIR), Thermogravimetric Analysis (TGA) and Scanning Electron Microscopic (SEM) methods. Some selective properties of grafted films such as swelling studies, ion uptake and biodegradation studies have been investigated. The grafted films show good swelling in water, ion uptake studies shows promising results for desalination of brackish water and the soil burial test shows that PE film grafted with binary monomer mixture degrades up to 47% within 50 days.

  14. Luminescent Nanocellulose Platform: From Controlled Graft Block Copolymerization to Biomarker Sensing.

    PubMed

    Navarro, Julien R G; Wennmalm, Stefan; Godfrey, Jamie; Breitholtz, Magnus; Edlund, Ulrica

    2016-03-14

    A strategy is devised for the conversion of cellulose nanofibrils (CNF) into fluorescently labeled probes involving the synthesis of CNF-based macroinitiators that initiate radical polymerization of methyl acrylate and acrylic acid N-hydroxysuccinimide ester producing a graft block copolymer modified CNF. Finally, a luminescent probe (Lucifer yellow derivative) was labeled onto the modified CNF through an amidation reaction. The surface modification steps were verified with solid-state (13)C nuclear magnetic resonance (NMR) and Fourier transform infrared spectroscopy. Fluorescence correlation spectroscopy (FCS) confirmed the successful labeling of the CNF; the CNF have a hydrodynamic radius of about 700 nm with an average number of dye molecules per fibril of at least 6600. The modified CNF was also imaged with confocal laser scanning microscopy. Luminescent CNF proved to be viable biomarkers and allow for fluorescence-based optical detection of CNF uptake and distribution in organisms such as crustaceans. The luminescent CNF were exposed to live juvenile daphnids and microscopy analysis revealed the presence of the luminescent CNF all over D. magna's alimentary canal tissues without any toxicity effect leading to the death of the specimen. PMID:26789648

  15. Asking for work adjustments or initiating behavioural changes - what makes a 'problematic co-worker' score Brownie points? An experimental study on the reactions towards colleagues with a personality disorder.

    PubMed

    Muschalla, Beate; Fay, Doris; Seemann, Anne

    2016-10-01

    People with mental disorders, especially personality disorders, often face low acceptance at work. This is particularly problematic when returning to work after sick leave, because it impedes reintegration into the former workplace. This study explores colleagues' reactions towards a problematic worker dependent on the returning person's reintegration strategy: The returning person undertaking changes in their behaviour is compared with the person requesting adjustments of the workplace. In an experimental study, 188 employed persons read one of four vignettes that described a return-to-work-situation of a problematic co-worker. Across all vignettes, the co-worker was depicted as having previously caused problems in the work team. In the first vignette, the co-worker did not change anything (control condition) when she returned to work; in the second, she asked for workplace adjustments; in the third vignette she initiated efforts to change her own behaviour; and the fourth vignette combined both workplace adjustments and behavioural change. Study participants were asked for their reactions towards the problematic co-worker. Vignettes that included a behavioural change evoked more positive reactions towards the co-worker than vignettes without any behavioural change. Asking for workplace adjustments alone did not yield more positive reactions compared to not initiating any change. When preparing employees with interactional problems for their return to work, it is not effective to only instruct them on their statutory entitlement for workplace adjustments. Instead, it is advisable to encourage them to proactively strive for behaviour changes.

  16. A review on the radiation synthesis of copolymeric hydrogels for adsorption and separation purposes1

    NASA Astrophysics Data System (ADS)

    Güven, Olgun; Şen, Murat; Karadağ, Erdener; Saraydın, Dursun

    1999-10-01

    Recent theoretical and experimental work on the radiation synthesis, characterization and the use of hydrogels containing diprotic acid moieties have been reviewed. It is shown that upon incorporating vinyl monomers carrying diprotic acid groups randomly in the main chain, non-ionic hydrogels like poly(acryl amide) and poly(n-vinyl 2-pyrrolidone) acquired stimuli-responsive behaviours. The swelling behaviours of these hydrogels are shown to be predictable reliably under varying solution conditions by a theoretical expression derived recently. Examples are given for the utilization of these hydrogels in the adsorption and separation of biomolecules, dyes and metal ions in aqueous media and their ability to release drugs in stepwise manner in response to pH of the environment.

  17. Reactions of laser-ablated Nb and Ta atoms with N2: experimental and theoretical study of M(NN)x (M = Nb, Ta; x = 1-4) in solid neon.

    PubMed

    Lu, Zhang-Hui; Jiang, Ling; Xu, Qiang

    2010-07-01

    Reactions of laser-ablated niobium and tantalum atoms with dinitrogen in solid neon have been investigated using matrix-isolation infrared spectroscopy. The Nb(NN)(x) and Ta(NN)(x) (x = 1-4) molecules formed during sample deposition or on annealing are the major products. The products are characterized on the basis of isotopic shifts, mixed isotopic splitting patterns, stepwise annealing, and change of reagent concentration and laser energy. Density functional theory calculations have been performed to understand the structures, ground electronic states, and bonding characteristics of niobium and tantalum dinitrogen complexes. The overall agreement between the experimental and calculated vibrational frequencies, relative absorption intensities, and isotopic shifts supports the identification of these species from the matrix infrared spectra. The molecular orbital analyses and plausible reaction pathways for the formation of the products are also discussed.

  18. Experimental and theoretical investigation of the reaction NH(X3Sigma-) + H(2S)-->N(4S) + H2(X1)Sigmag +).

    PubMed

    Adam, L; Hack, W; Zhu, H; Qu, Z-W; Schinke, R

    2005-03-15

    The rate coefficient of the reaction NH(X (3)Sigma(-)) + H((2)S)-->(k(1a) )N((4)S) + H(2)(X (1)Sigma(g) (+)) is determined in a quasistatic laser-flash photolysis, laser-induced fluorescence system at low pressures (2 mbar< or =p< or =10 mbar). The NH(X) radicals are produced via the quenching of NH(a(1)Delta) (obtained by photolyzing HN(3)) with Xe whereas the H atoms are generated in a H(2)He microwave discharge. The NH(X) concentration profile is measured under pseudo-first-order condition, i.e., in the presence of a large excess of H atoms. The room temperature rate coefficient is determined to be k(1a) = (1.9 +/- 0.5) x 10(12) cm(3) mol(-1) s(-1). It is found to be independent of the pressure in the range considered in the present experiment. A global potential energy surface for the (4)A(") state is calculated with the internally contracted multireference configuration interaction method and the augmented correlation consistent polarized valence quadruple zeta atomic basis. The title reaction is investigated by classical trajectory calculations on this surface. The theoretical room temperature rate coefficient is k(1a) = 0.92 x 10(12)cm(3) mol(-1) s(-1). Using the thermodynamical data for the atoms and molecules involved, the rate coefficient for the reverse reaction, k(-1a), is also calculated. At high temperatures it agrees well with the measured k(-1a).

  19. Experimental study of the p+{sup 6}Li{yields}{eta}+{sup 7}Be reaction 11.3 MeV above threshold

    SciTech Connect

    Budzanowski, A.; Kliczewski, S.; Siudak, R.; Chatterjee, A.; Jha, V.; Roy, B. J.; Hawranek, P.; Magiera, A.; Jahn, R.; Kilian, K.; Maier, R.; Protic, D.; Ritman, J.; Rossen, P. von; Kirillov, Da.; Machner, H.; Kirillov, Di.; Piskunov, N.; Sitnik, I.; Kolev, D.

    2010-10-15

    The cross section for the reaction p+{sup 6}Li{yields}{eta}+{sup 7}Be was measured at an excess energy of 11.28 MeV above threshold by detecting the recoiling {sup 7}Be nuclei. A dedicated set of focal plane detectors was built for the magnetic spectrograph Big Karl and was used for identification and four-momentum measurement of {sup 7}Be. A differential cross section of nb/(d{sigma}/d{Omega})=[0.69{+-}0.20(stat.){+-}0.20(syst.)] sr for the ground state plus 1/2{sup -} was measured. The result is compared to model calculations.

  20. Experimental and Theoretical Study on the OH-Reaction Kinetics and Photochemistry of Acetyl Fluoride (CH3C(O)F), an Atmospheric Degradation Intermediate of HFC-161 (C2H5F).

    PubMed

    Song, Xinli; Zügner, Gábor L; Farkas, Mária; Illés, Ádám; Sarzyński, Dariusz; Rozgonyi, Tamás; Wang, Baoshan; Dóbé, Sándor

    2015-07-16

    The direct reaction kinetic method of low pressure fast discharge flow (DF) with resonance fluorescence monitoring of OH (RF) has been applied to determine rate coefficients for the overall reactions OH + C2H5F (EtF) (1) and OH + CH3C(O)F (AcF) (2). Acetyl fluoride reacts slowly with the hydroxyl radical, the rate coefficient at laboratory temperature is k2(300 K) = (0.74 ± 0.05) × 10(-14) cm(3) molecule(-1) s(-1) (given with 2σ statistical uncertainty). The temperature dependence of the reaction does not obey the Arrhenius law and it is described well by the two-exponential rate expression of k2(300-410 K) = 3.60 × 10(-3) exp(-10500/T) + 1.56 × 10(-13) exp(-910/T) cm(3) molecule(-1) s(-1). The rate coefficient of k1 = (1.90 ± 0.19) × 10(-13) cm(3) molecule(-1) s(-1) has been determined for the EtF-reaction at room temperature (T = 298 K). Microscopic mechanisms for the OH + CH3C(O)F reaction have also been studied theoretically using the ab initio CBS-QB3 and G4 methods. Variational transition state theory was employed to obtain rate coefficients for the OH + CH3C(O)F reaction as a function of temperature on the basis of the ab initio data. The calculated rate coefficients are in good agreement with the experimental data. It is revealed that the reaction takes place predominantly via the indirect H-abstraction mechanism involving H-bonded prereactive complexes and forming the nascent products of H2O and the CH2CFO radical. The non-Arrhenius behavior of the rate coefficient at temperatures below 500 K is ascribed to the significant tunneling effect of the in-the-plane H-abstraction dynamic bottleneck. The production of FC(O)OH + CH3 via the addition/elimination mechanism is hardly competitive due to the significant barriers along the reaction routes. Photochemical experiments of AcF were performed at 248 nm by using exciplex lasers. The total photodissociation quantum yield for CH3C(O)F has been found significantly less than unity; among the primary

  1. Oxidation-Responsive and "Clickable" Poly(ethylene glycol) via Copolymerization of 2-(Methylthio)ethyl Glycidyl Ether.

    PubMed

    Herzberger, Jana; Fischer, Karl; Leibig, Daniel; Bros, Matthias; Thiermann, Raphael; Frey, Holger

    2016-07-27

    Poly(ethylene glycol) (PEG) is a widely used biocompatible polymer. We describe a novel epoxide monomer with methyl-thioether moiety, 2-(methylthio)ethyl glycidyl ether (MTEGE), which enables the synthesis of well-defined thioether-functional poly(ethylene glycol). Random and block mPEG-b-PMTEGE copolymers (Mw/Mn = 1.05-1.17) were obtained via anionic ring opening polymerization (AROP) with molecular weights ranging from 5 600 to 12 000 g·mol(-1). The statistical copolymerization of MTEGE with ethylene oxide results in a random microstructure (rEO = 0.92 ± 0.02 and rMTEG E = 1.06 ± 0.02), which was confirmed by in situ (1)H NMR kinetic studies. The random copolymers are thermoresponsive in aqueous solution, with a wide range of tunable transition temperatures of 88 to 28 °C. In contrast, mPEG-b-PMTEGE block copolymers formed well-defined micelles (Rh ≈ 9-15 nm) in water, studied by detailed light scattering (DLS and SLS). Intriguingly, the thioether moieties of MTEGE can be selectively oxidized into sulfoxide units, leading to full disassembly of the micelles, as confirmed by detection of pure unimers (DLS and SLS). Oxidation-responsive release of encapsulated Nile Red demonstrates the potential of these micelles as redox-responsive nanocarriers. MTT assays showed only minor effects of the thioethers and their oxidized derivatives on the cellular metabolism of WEHI-164 and HEK-293T cell lines (1-1000 μg·mL(-1)). Further, sulfonium PEG polyelectrolytes can be obtained via alkylation or alkoxylation of MTEGE, providing access to a large variety of functional groups at the charged sulfur atom. PMID:27375132

  2. A Combined Experimental and Computational Investigation on the Unusual Molecular Mechanism of the Lossen Rearrangement Reaction Activated by Carcinogenic Halogenated Quinones

    PubMed Central

    2015-01-01

    The classic Lossen rearrangement is a well-known reaction describing the transformation of an O-activated hydroxamic acid into the corresponding isocyanate. In this study, we found that chlorinated benzoquinones (CnBQ) serve as a new class of agents for the activation of benzohydroxamic acid (BHA), leading to Lossen rearrangement. Compared to the classic one, this new kind of CnBQ-activated Lossen rearrangement has the following unique characteristics: (1) The stability of CnBQ-activated BHA intermediates was found to depend not only on the degree but also on the position of Cl-substitution on CnBQs, which can be divided into two subgroups. (2) It is the relative energy of the anionic CnBQ–BHA intermediates that determine the rate of this CnBQ-activated rearrangement, which is the rate-limiting step, and the Cl or H ortho to the reaction site at CnBQ is crucial for the stability of the anionic intermediates. (3) A pKa–activation energy correlation was observed, which can explain why the correlation exists between the rate of the rearrangement and the acidity of the conjugate acid of the anionic leaving group, the hydroxlated quinones. These findings may have broad implications for future research on halogenated quinoid carcinogens and hydroxamate biomedical agents. PMID:25470188

  3. Experimental studies of the 249Bk + 48Ca reaction including decay properties and excitation function for isotopes of element 117, and discovery of the new isotope 277Mt

    NASA Astrophysics Data System (ADS)

    Oganessian, Yu. Ts.; Abdullin, F. Sh.; Alexander, C.; Binder, J.; Boll, R. A.; Dmitriev, S. N.; Ezold, J.; Felker, K.; Gostic, J. M.; Grzywacz, R. K.; Hamilton, J. H.; Henderson, R. A.; Itkis, M. G.; Miernik, K.; Miller, D.; Moody, K. J.; Polyakov, A. N.; Ramayya, A. V.; Roberto, J. B.; Ryabinin, M. A.; Rykaczewski, K. P.; Sagaidak, R. N.; Shaughnessy, D. A.; Shirokovsky, I. V.; Shumeiko, M. V.; Stoyer, M. A.; Stoyer, N. J.; Subbotin, V. G.; Sukhov, A. M.; Tsyganov, Yu. S.; Utyonkov, V. K.; Voinov, A. A.; Vostokin, G. K.

    2013-05-01

    Studies of superheavy nuclei produced in the 249Bk + 48Ca reaction were performed using the Dubna Gas Filled Recoil Separator. The cross section for the production of 293117 and 294117 isotopes was measured at five excitation energies of the 297117 compound nucleus ranging from 30 to 48 MeV and yielding maximum values of 1.1-0.6+1.2 pb for the 3n and 2.4-1.4+3.3 pb for the 4n reaction channels. Alpha emission from 281Rg competing with spontaneous fission (α/SF decay probability 1:9) was observed for the first time leading to the identification of the new isotope 277Mt (TSF≈5 ms). The measured decay properties are in good agreement with those expected based on the properties of neighboring even-Z and odd-Z nuclei. The α energies and half-lives of odd-Z isotopes observed in the 293117 and 294117 decay chains together with results obtained for lower-Z superheavy nuclei demonstrate enhanced stability with increasing neutron number toward the predicted new magic number N=184.

  4. Experimental investigations of certain side reactions and the initial voltage transient for FeS/sub 2/ cathodes in thermal batteries

    SciTech Connect

    Searcy, J. Q.; Delnick, F. M.; D'Angelo, J. C.

    1981-02-01

    The direct reaction of FeS/sub 2/ with stainless steel current collectors reduces the coulombic efficiency of thermal cell cathodes. When single cells are discharged in air, the reduction of O/sub 2/ at the FeS/sub 2/ cathode represents a significant fraction of the discharge current. At least five separate phenomena contribute to the initial voltage transient observed in thermal batteries which use FeS/sub 2/ for the cathode material. These five phenomena are: (1) a thermodynamic increase in the potential caused by the initial temperature peak which results from the heat pellets when ignited, (2) electrochemical participation of surface contaminants on the FeS/sub 2/, (3) electrochemical reduction of oxygen or reaction products of oxygen with FeS/sub 2/, (4) electrochemical reduction of elemental sulfur produced by the thermal decomposition of FeS/sub 2/, and (5) the voltage decrease which accompanies the saturation of the electrolyte with the electrochemical reduction product, or products. Mitigative techniques for the observed phenomena include: (1) performing single cell tests under an inert atmosphere, (2) using a nonreactive material for current collectors, (3) using an additive with the cathode to suppress the initial voltage transient, and (4) predischarging the cathodes.

  5. Experimental verification of proton beam monitoring in a human body by use of activity image of positron-emitting nuclei generated by nuclear fragmentation reaction.

    PubMed

    Nishio, Teiji; Miyatake, Aya; Inoue, Kazumasa; Gomi-Miyagishi, Tomoko; Kohno, Ryosuke; Kameoka, Satoru; Nakagawa, Keiichi; Ogino, Takashi

    2008-01-01

    Proton therapy is a form of radiotherapy that enables concentration of dose on a tumor by use of a scanned or modulated Bragg peak. Therefore, it is very important to evaluate the proton-irradiated volume accurately. The proton-irradiated volume can be confirmed by detection of pair-annihilation gamma rays from positron-emitting nuclei generated by the nuclear fragmentation reaction of the incident protons on target nuclei using a PET apparatus. The activity of the positron-emitting nuclei generated in a patient was measured with a PET-CT apparatus after proton beam irradiation of the patient. Activity measurement was performed in patients with tumors of the brain, head and neck, liver, lungs, and sacrum. The 3-D PET image obtained on the CT image showed the visual correspondence with the irradiation area of the proton beam. Moreover, it was confirmed that there were differences in the strength of activity from the PET-CT images obtained at each irradiation site. The values of activity obtained from both measurement and calculation based on the reaction cross section were compared, and it was confirmed that the intensity and the distribution of the activity changed with the start time of the PET imaging after proton beam irradiation. The clinical use of this information about the positron-emitting nuclei will be important for promoting proton treatment with higher accuracy in the future.

  6. Application Of Phenol/Amine Copolymerized Film Modified Magnesium Alloys: Anticorrosion And Surface Biofunctionalization.

    PubMed

    Chen, Si; Zhang, Jiang; Chen, Yingqi; Zhao, Sheng; Chen, Meiyun; Li, Xin; Maitz, Manfred F; Wang, Jin; Huang, Nan

    2015-11-11

    Magnesium metal as degradable metallic material is one of the most researched areas, but its rapid degradation rate restricts its development. The current anticorrosion surface modification methods require expensive equipment and complicated operation processes and cannot continue to introduce biofunction on modified surface. In this study, the GAHD conversion coatings were fabricated on the surface of magnesium alloys (MZM) by incubating in the mixture solution of gallic acid (GA) and hexamethylenediamine (HD) to decrease the corrosion rate and provide primary amines (-NH2), carboxyl (-COOH), and quinone groups, which is supposed to introduce biomolecules on MZM. Chemical structures of the MZM-GAHD and MZM-HEP-GAHD were explored by analyzing the results of FTIR and XPS comprehensively. Furthermore, it was proved that the heparin (HEP) molecules were successfully immobilized on MZM-GAHD surface through carbodiimide method. The evaluation of platelet adhesion and clotting time test showed that MZM-HEP-GAHD had higher anticoagulation than MZM-GAHD. Through electrochemical detection (polarization curves and electrochemical impedance spectroscopy Nyquist spectrum) and immersion test (Mg(2+) concentration and weight loss), it was proved that compared to MZM, both the MZM-GAHD and MZM-HEP-GAHD significantly improved the corrosion resistance. Finally, in vivo experimentation indicated that mass loss had no significant difference between MZM-1:1, MZM-HEP-1:1, and MZM. However, the trend still suggested that MZM-1:1 and MZM-HEP-1:1 possessed corrosion resistance property.

  7. Application Of Phenol/Amine Copolymerized Film Modified Magnesium Alloys: Anticorrosion And Surface Biofunctionalization.

    PubMed

    Chen, Si; Zhang, Jiang; Chen, Yingqi; Zhao, Sheng; Chen, Meiyun; Li, Xin; Maitz, Manfred F; Wang, Jin; Huang, Nan

    2015-11-11

    Magnesium metal as degradable metallic material is one of the most researched areas, but its rapid degradation rate restricts its development. The current anticorrosion surface modification methods require expensive equipment and complicated operation processes and cannot continue to introduce biofunction on modified surface. In this study, the GAHD conversion coatings were fabricated on the surface of magnesium alloys (MZM) by incubating in the mixture solution of gallic acid (GA) and hexamethylenediamine (HD) to decrease the corrosion rate and provide primary amines (-NH2), carboxyl (-COOH), and quinone groups, which is supposed to introduce biomolecules on MZM. Chemical structures of the MZM-GAHD and MZM-HEP-GAHD were explored by analyzing the results of FTIR and XPS comprehensively. Furthermore, it was proved that the heparin (HEP) molecules were successfully immobilized on MZM-GAHD surface through carbodiimide method. The evaluation of platelet adhesion and clotting time test showed that MZM-HEP-GAHD had higher anticoagulation than MZM-GAHD. Through electrochemical detection (polarization curves and electrochemical impedance spectroscopy Nyquist spectrum) and immersion test (Mg(2+) concentration and weight loss), it was proved that compared to MZM, both the MZM-GAHD and MZM-HEP-GAHD significantly improved the corrosion resistance. Finally, in vivo experimentation indicated that mass loss had no significant difference between MZM-1:1, MZM-HEP-1:1, and MZM. However, the trend still suggested that MZM-1:1 and MZM-HEP-1:1 possessed corrosion resistance property. PMID:26479205

  8. Analysis of the kinetics and yields of OH radical production from the CH3OCH2 + O2 reaction in the temperature range 195-650 K: an experimental and computational study.

    PubMed

    Eskola, A J; Carr, S A; Shannon, R J; Wang, B; Blitz, M A; Pilling, M J; Seakins, P W; Robertson, S H

    2014-08-28

    The methoxymethyl radical, CH3OCH2, is an important intermediate in the low temperature combustion of dimethyl ether. The kinetics and yields of OH from the reaction of the methoxymethyl radical with O2 have been measured over the temperature and pressure ranges of 195-650 K and 5-500 Torr by detecting the hydroxyl radical using laser-induced fluorescence following the excimer laser photolysis (248 nm) of CH3OCH2Br. The reaction proceeds via the formation of an energized CH3OCH2O2 adduct, which either dissociates to OH + 2 H2CO or is collisionally stabilized by the buffer gas. At temperatures above 550 K, a secondary source of OH was observed consistent with thermal decomposition of stabilized CH3OCH2O2 radicals. In order to quantify OH production from the CH3OCH2 + O2 reaction, extensive relative and absolute OH yield measurements were performed over the same (T, P) conditions as the kinetic experiments. The reaction was studied at sufficiently low radical concentrations (∼10(11) cm(-3)) that secondary (radical + radical) reactions were unimportant and the rate coefficients could be extracted from simple bi- or triexponential analysis. Ab initio (CBS-GB3)/master equation calculations (using the program MESMER) of the CH3OCH2 + O2 system were also performed to better understand this combustion-related reaction as well as be able to extrapolate experimental results to higher temperatures and pressures. To obtain agreement with experimental results (both kinetics and yield data), energies of the key transition states were substantially reduced (by 20-40 kJ mol(-1)) from their ab initio values and the effect of hindered rotations in the CH3OCH2 and CH3OCH2OO intermediates were taken into account. The optimized master equation model was used to generate a set of pressure and temperature dependent rate coefficients for the component nine phenomenological reactions that describe the CH3OCH2 + O2 system, including four well-skipping reactions. The rate coefficients were

  9. Enzymatic copolymerization alters the structure of unpolymerized mixtures of the biomimetic monomers: the amphiphilic decyl ester of L-tyrosine and L-tyrosineamide--an AFM investigation of nano- to micrometer-scale structure differences.

    PubMed

    Marx, Kenneth A; Lee, Jun S; Sung, Changmo

    2004-01-01

    Previously, we have shown that the amphiphilic decyl esters of both D- and L-tyrosine (DELT) self-assemble in aqueous solution above their critical micelle concentration values to form long rodlike structures that can be enzymatically polymerized. In the current study, we have examined the self-assembled structures of unpolymerized and enzymatically (horseradish peroxidase) copolymerized 1:1 molar mixtures of DELT with the nonamphiphilic comonomer L-tyrosineamide. The structures were examined following adsorption to gold-coated mica surfaces using optical microscopy and scanning electron microscopy, but primarily noncontact atomic force microscopy. Both unpolymerized and copolymerized 1:1 comonomer mixture aggregates produced amorphous to spherical shaped structures, exhibiting increased flexibility that contrasted with our previous observations of the more highly ordered long rodlike structures seen with the pure DELT. The unpolymerized comonomer aggregates were amorphous and of varying size. Interestingly, they contained occasional novel structures-smooth, sharp, nipplelike features that rose hundreds of nanometers above the smooth aggregate surface. However, upon enzymatic copolymerization, the structures are altered, forming nearly hemispherical aggregates in contact with each other on the surface. These structures possessed diameters of 1.51 +/- 0.24 microm. The copolymerized structures lacked any evidence of the sharp nipplelike features observed in the unpolymerized sample, but they did exhibit nanometer-scale detailed surface features, indicative of a higher degree of internal organization. The measured surface roughness of the copolymerized comonomer mixture was more than 10 times greater than the surface roughness of the unpolymerized comonomer mixture.

  10. Experimental evaluation of in situ CO2-water-rock reactions during CO2 injection in basaltic rocks: Implications for geological CO2 sequestration

    NASA Astrophysics Data System (ADS)

    Matter, Juerg M.; Takahashi, Taro; Goldberg, David

    2007-02-01

    Deep aquifers are potential long-term storage sites for anthropogenic CO2 emissions. The retention time and environmental safety of the injected CO2 depend on geologic and physical factors and on the chemical reactions between the CO2, the aquifer water, and the host rocks. The pH buffer capacity of the aquifer water and the acid neutralization potential of the host rocks are important factors for the permanent stabilization of the injected CO2. Mafic rocks, such as basalt, which primarily consists of Ca, Mg silicate minerals, have a high acid neutralization capacity by providing alkaline earth elements that form stable carbonate minerals. The carbonate minerals formed thus sequester CO2 in a chemically stable and environmentally benign form. In this study, we present results from a small-scale CO2 injection test in mafic and metasedimentary rocks. The injection test was conducted using a single-well push-pull test strategy. CO2 saturated water (pH = 3.5) was injected into a hydraulically isolated and permeable aquifer interval to study the acid neutralization capacity of Ca, Mg silicate rocks and to estimate in situ cation release rates. Release rates for Ca, Mg, and Na were calculated by use of solute compositions of water samples retrieved after the CO2 injection, the incubation time of the injected solution within the aquifer, and geometric estimates of the reactive surface area of the host rocks. Our results confirm rapid acid neutralization rates and water-rock reactions sufficient for safe and permanent storage of CO2. Carbonic acid was neutralized within hours of injection into a permeable mafic aquifer by two processes: mixing between the injected solution and the aquifer water, and water-rock reactions. Calculated cation release rates decrease with increasing pH that is confirmed by laboratory-based experiments. Large differences between release rates obtained from the field and laboratory experiments may be mainly due to uncertainties in the estimation

  11. Experimental study of sediment-CO2 reactions with application to changes in groundwater quality due to leakage of sequestered CO2

    NASA Astrophysics Data System (ADS)

    Carey, J. W.; Williams, M. R.; Hakala, A.; Fessenden, J. E.; Keating, E. H.

    2009-12-01

    Geologic sequestration of CO2 requires storage of buoyant, immiscible supercritical CO2 in the subsurface for long periods of time. In the viability assessment of sequestration, one of the most significant risk concerns is damage of shallow drinking water aquifers from potential CO2 leakage. The groundwater quality concerns are primarily due to acidification, increase in total dissolved solids (TDS), and the potential mobilization of hazardous trace metals. Previous studies of this issue include natural analogs of CO2-groundwater interactions where there can be uncertainty as to whether observations reflect variations in groundwater quality unrelated to CO2 and numerical studies of CO2-brine interactions with shallow aquifers where there is uncertainty as to the geochemical mechanisms of trace element mobilization. In this study, we conduct experiments of CO2-water-sediment interactions from the Chimayo region in north-central New Mexico. This region includes a natural CO2 seep which we have used in natural analog studies (Keating et al. 2009) and the presence of elevated arsenic and uranium concentrations. The experiments were designed to address the question of whether CO2 reactions with aquifer sediments could account for the observed water quality problems in Chimayo and to consider the more general question of the nature of trace element mobilization by CO2-induced reactions. The experiments consisted of periodically sampled batch reactions of water and sediment reacted with a continuous source of 1-atm CO2. The sediments are quartz-rich alluvial fan deposits that include feldspars and clays and were characterized by XRD, XRF, and by sequential extraction to determine trace metal content. The water was created to represent the background major ion chemistry of groundwater in the region. The sediments were initially equilibrated with the synthetic water prior to introduction of CO2. Reaction with CO2 was monitored over 10 days with periodic fluid sampling. The

  12. Swelling properties of copolymeric hydrogels of poly(ethylene glycol) monomethacrylate and monoesters of itaconic acid for use in drug delivery.

    PubMed

    Teijón, César; Guerrero, Sandra; Olmo, Rosa; Teijón, José M; Blanco, M Dolores

    2009-11-01

    Copolymeric hydrogels of poly(ethylene glycol) monomethacrylate (PEGMA) (P) have been synthesized for use in drug-delivery. New copolymeric hydrogels were prepared by free radical solution polymerization of PEGMA and monomethyl itaconate (MMI) or monoethyl itaconate (MEI), using ethyleneglycol dimethacrylate and tetraethyleneglycol dimethacrylate, respectively, as cross-linkers. The effect of copolymer composition on swelling behavior, thermal decomposition and drug release was studied. Three compositions of each copolymer were studied: 70P/30MMI (or MEI), 80P/20MMI (or MEI) and 90P/10MMI (or MEI). The largest equilibrium swelling degree was observed in gels containing the highest content of MMI or MEI (84.22 +/- 0.22 wt % for 70P/30MEI; 79.56 +/- 0.64 wt % for 70P/30MMI). The swelling process was in accordance with Fick's Second Law. Methotrexate (MTX), an anticancer agent used in the treatment of different hyperproliferative epithelial diseases, was chosen to be loaded in the gels. The drug was included by immersion of the copolymeric disks in an aqueous solution of the drug. The amount of MTX in the xerogels was between 5.34 +/- 0.06 mg MTX/g (90P/10MMI) and 14.94 +/- 0.91 mg MTX/g (80P/20MEI). Two stages of thermal degradation for unloaded and MTX-loaded gels were determined; the presence of the drug in the polymeric matrices decreased the temperature of the first stage of thermal degradation. MTX release was also in accordance with Fick's Second Law. The length of total drug release (340 +/- 30 min-1502 +/- 81 min) could be modulated as a function of the comonomer composition of the hydrogel.

  13. CO2/ethylene oxide copolymerization and ligand variation for a highly active salen-cobalt(III) complex tethering 4 quaternary ammonium salts.

    PubMed

    Jeon, Jong Yeob; Lee, Jung Jae; Varghese, Jobi Kodiyan; Na, Sung Jae; Sujith, S; Go, Min Jeong; Lee, Junseong; Ok, Myung-Ahn; Lee, Bun Yeoul

    2013-07-01

    A cobalt(III) complex (1) of a salcy-type ligand tethering 4 quaternary ammonium salts, which is thought to act as a highly active catalyst for CO2/propylene oxide (PO) copolymerization, also shows high activity (TOF, 25,900 h(-1); TON, 518,000; 2.72 kg polymer per g cat) and selectivity (>98%) for CO2/ethylene oxide (EO) copolymerization that results in high-molecular-weight polymers (M(n), 200,000-300,000) that have strictly alternating repeating units. The related cobalt(III) complexes 11-14 were prepared through variations of the ligand framework of 1 by replacing the trans-1,2-diaminocyclohexane unit with 2,2-dimethyl-1,3-propanediamine, trans-1,2-diaminocyclopentane, or 1,1'-binaphthyl-2,2'-diamine or by replacing the aldimine bond with ketimine. These ligand frameworks are thought to favour the formation of the cis-β configuration in complexation, and the formation of the cis-β configuration in 11-14 was confirmed through NMR studies or X-ray crystallographic studies of model complexes not bearing the quaternary ammonium salts. Complexes 11, 13, and 14, which adopt the cis-β configuration even in DMSO did not show any activity for CO2/PO copolymerization. Complex 12, which was constructed with trans-1,2-diaminocyclopentane and fluctuated in DMSO between the coordination and de-coordination of the acetate ligand as observed for 1, showed fairly high activity (TOF, 12,400 h(-1)). This fluctuating behaviour may play a role in polymerization. However, complex 12 did not compete with 1 in terms of activity, selectivity, and the catalyst cost.

  14. Experimental colitis.

    PubMed

    MacPherson, B; Pfeiffer, C J

    1976-01-01

    Ulcerative colitis and Crohn's disease are complex, problematic diseases of unknown etiology in man, and appropriate experimental models would be useful in elucidating their pathogenesis and treatment. Although there have been numerous attempts to produce inflammatory ulcerative colonic disease in laboratory animals resembling those human disease forms, none has been entirely successful. Investigators have conducted experiments involving almost every etiological factor suggested for initiation of these diseases. The methods reviewed in this paper include production of experimental colitis by vascular impairment, and immunological methods such as bacterial infection, allergic reactions, direct and indirect hypersensitivity reactions, as well as autoimmune mechanisms. The results of carrageenan-induced colitis, irradiation, dietary, and drug-induced techniques are also discussed and the frequency and nature of spontaneous colonic lesions in animals is summarized.

  15. Sterically (un)encumbered mer-tridentate N-heterocyclic carbene complexes of titanium(iv) for the copolymerization of cyclohexene oxide with CO2.

    PubMed

    Hessevik, Julie; Lalrempuia, Ralte; Nsiri, Hajar; Törnroos, Karl W; Jensen, Vidar R; Le Roux, Erwan

    2016-10-01

    Titanium(iv) complexes bearing an unsubstituted tridentate bis(phenolate) N-heterocyclic carbene (NHC) were synthesized and structurally identified. While sterically unencumbered NHC-Ti(iv) complexes bearing chloro and alkoxy co-ligands tend to dimerize in solution and in solid-state, the use of a bulky aryloxy as co-ligand favors the monomeric species. Upon activation by onium salts, all these complexes were found to be highly selective towards the copolymerization of cyclohexene oxide (CHO) with CO2 under mild conditions (PCO2 < 1 bar), albeit the sterically unencumbered NHC-Ti(iv) complexes are less stable and active than their structural analogues bearing bulkier substituents.

  16. Designing artificial enzymes from scratch: Experimental study and mesoscale simulation

    NASA Astrophysics Data System (ADS)

    Komarov, Pavel V.; Zaborina, Olga E.; Klimova, Tamara P.; Lozinsky, Vladimir I.; Khalatur, Pavel G.; Khokhlov, Alexey R.

    2016-09-01

    We present a new concept for designing biomimetic analogs of enzymatic proteins; these analogs are based on the synthetic protein-like copolymers. α-Chymotrypsin is used as a prototype of the artificial catalyst. Our experimental study shows that in the course of free radical copolymerization of hydrophobic and hydrophilic monomers the target globular nanostructures of a "core-shell" morphology appear in a selective solvent. Using a mesoscale computer simulation, we show that the protein-like globules can have a large number of catalytic centers located at the hydrophobic core/hydrophilic shell interface.

  17. First experimental determination of the absolute gas-phase rate coefficient for the reaction of OH with 4-hydroxy-2-butanone (4H2B) at 294 K by vapor pressure measurements of 4H2B.

    PubMed

    El Dib, Gisèle; Sleiman, Chantal; Canosa, André; Travers, Daniel; Courbe, Jonathan; Sawaya, Terufat; Mokbel, Ilham; Chakir, Abdelkhaleq

    2013-01-10

    The reaction of the OH radicals with 4-hydroxy-2-butanone was investigated in the gas phase using an absolute rate method at room temperature and over the pressure range 10-330 Torr in He and air as diluent gases. The rate coefficients were measured using pulsed laser photolysis (PLP) of H(2)O(2) to produce OH and laser induced fluorescence (LIF) to measure the OH temporal profile. An average value of (4.8 ± 1.2) × 10(-12) cm(3) molecule(-1) s(-1) was obtained. The OH quantum yield following the 266 nm pulsed laser photolysis of 4-hydroxy-2-butanone was measured for the first time and found to be about 0.3%. The investigated kinetic study required accurate measurements of the vapor pressure of 4-hydroxy-2-butanone, which was measured using a static apparatus. The vapor pressure was found to range from 0.056 to 7.11 Torr between 254 and 323 K. This work provides the first absolute rate coefficients for the reaction of 4-hydroxy-2-butanone with OH and the first experimental saturated vapor pressures of the studied compound below 311 K. The obtained results are compared to those of the literature and the effects of the experimental conditions on the reactivity are examined. The calculated tropospheric lifetime obtained in this work suggests that once emitted into the atmosphere, 4H2B may contribute to the photochemical pollution in a local or regional scale.

  18. Atmospheric fate of nitramines: an experimental and theoretical study of the OH reactions with CH3NHNO2 and (CH3)2NNO2.

    PubMed

    Maguta, Mihayo Musabila; Aursnes, Marius; Bunkan, Arne Joakim Coldevin; Edelen, Katie; Mikoviny, Tomáš; Nielsen, Claus Jørgen; Stenstrøm, Yngve; Tang, Yizhen; Wisthaler, Armin

    2014-05-15

    The rates of CH3NHNO2 and (CH3)2NNO2 reaction with OH radicals were determined relative to CH3OCH3 and CH3OH at 298 ± 2 K and 1013 ± 10 hPa in purified air by long path FTIR spectroscopy, and the rate coefficients were determined to be k(OH+CH3NHNO2) = (9.5 ± 1.9) × 10(-13) and k(OH+(CH3)2NNO2) = (3.5 ± 0.7) × 10(-12) (2σ) cm(3) molecule(-1) s(-1). Ozone was found to react very slowly with the two nitramines, k(O3+nitramine) < 10(-21) cm(3) molecule(-1) s(-1). Product formation in the photo-oxidation of CH3NHNO2 and (CH3)2NNO2 was studied by FTIR, PTR-ToF-MS, and quantum chemistry calculations; the major products in the OH-initiated degradation are the corresponding imines, CH2═NH and CH3N═CH2, and N-nitro amides, CHONHNO2 and CHON(CH3)NO2. Atmospheric degradation mechanisms are presented. PMID:24766577

  19. Mushroom tyrosinase: A model system to combine experimental investigation of enzyme-catalyzed reactions, data handling using R, and enzyme-inhibitor structural studies.

    PubMed

    Nairn, Robert; Cresswell, Will; Nairn, Jacqueline

    2015-01-01

    The activity of mushroom tyrosinase can be measured by monitoring the conversion of phenolic compounds into quinone derivatives using spectrophotometry. This article describes a series of experiments which characterize the functional properties of tyrosinase, the analysis of the resulting data using R to determine the kinetic parameters, and the exploration of the structural properties of tyrosinase-inhibitor complexes. Tyrosinase assay development and subsequent activity measurements, in the presence of varying pH, substrate concentration and inhibitors, offers the opportunity to learn the enzyme characterization skills relevant to a research laboratory setting. Combining the activity studies with an exploration of the nature of the tyrosinase-inhibitor interactions enables a structural understanding of the experimental observations.

  20. The 18Ne(α,p)21Na breakout reaction in x-ray bursts: Experimental determination of spin-parities for α resonances in 22Mg via resonant elastic scattering of 21Na+p

    NASA Astrophysics Data System (ADS)

    He, J. J.; Zhang, L. Y.; Parikh, A.; Xu, S. W.; Yamaguchi, H.; Kahl, D.; Kubono, S.; Hu, J.; Ma, P.; Chen, S. Z.; Wakabayashi, Y.; Sun, B. H.; Wang, H. W.; Tian, W. D.; Chen, R. F.; Guo, B.; Hashimoto, T.; Togano, Y.; Hayakawa, S.; Teranishi, T.; Iwasa, N.; Yamada, T.; Komatsubara, T.

    2013-07-01

    The 18Ne(α,p)21Na reaction provides a pathway for breakout from the hot CNO cycles to the rp process in type-I x-ray bursts. To better determine this astrophysical reaction rate, the resonance parameters of the compound nucleus 22Mg have been investigated by measuring the resonant elastic scattering of 21Na+p. An 89 MeV 21Na radioactive ion beam was produced at the CNS Radioactive Ion Beam Separator and bombarded an 8.8 mg/cm2 thick polyethylene target. The recoiled protons were measured at scattering angles of θc.m.≈175∘ and 152∘ by three ΔE-E silicon telescopes. The excitation function was obtained with a thick-target method over energies Ex(22Mg) = 5.5-9.2 MeV. The resonance parameters have been determined through an R-matrix analysis. For the first time, the Jπ values for ten states above the α threshold in 22Mg have been experimentally determined in a single consistent measurement. We have made three new Jπ assignments and confirmed seven of the ten tentative assignments in the previous work. The 18Ne(α,p)21Na reaction rate has been recalculated, and the astrophysical impact of our new rate has been investigated through one-zone postprocessing x-ray burst calculations. We find that the 18Ne(α,p)21Na rate significantly affects the peak nuclear energy generation rate and the onset temperature of this breakout reaction in these phenomena.

  1. Drug Reactions

    MedlinePlus

    ... or diabetes. But medicines can also cause unwanted reactions. One problem is interactions, which may occur between ... more serious. Drug allergies are another type of reaction. They can be mild or life-threatening. Skin ...

  2. Zwitterionic sulfobetaine-grafted poly(vinylidene fluoride) membrane with highly effective blood compatibility via atmospheric plasma-induced surface copolymerization.

    PubMed

    Chang, Yung; Chang, Wan-Ju; Shih, Yu-Ju; Wei, Ta-Chin; Hsiue, Ging-Ho

    2011-04-01

    Development of nonfouling membranes to prevent nonspecific protein adsorption and platelet adhesion is critical for many biomedical applications. It is always a challenge to control the surface graft copolymerization of a highly polar monomer from the highly hydrophobic surface of a fluoropolymer membrane. In this work, the blood compatibility of poly(vinylidene fluoride) (PVDF) membranes with surface-grafted electrically neutral zwitterionic poly(sulfobetaine methacrylate) (PSBMA), from atmospheric plasma-induced surface copolymerization, was studied. The effect of surface composition and graft morphology, electrical neutrality, hydrophilicity and hydration capability on blood compatibility of the membranes were determined. Blood compatibility of the zwitterionic PVDF membranes was systematically evaluated by plasma protein adsorption, platelet adhesion, plasma-clotting time, and blood cell hemolysis. It was found that the nonfouling nature and hydration capability of grafted PSBMA polymers can be effectively controlled by regulating the grafting coverage and charge balance of the PSBMA layer on the PVDF membrane surface. Even a slight charge bias in the grafted zwitterionic PSBMA layer can induce electrostatic interactions between proteins and the membrane surfaces, leading to surface protein adsorption, platelet activation, plasma clotting and blood cell hemolysis. Thus, the optimized PSBMA surface graft layer in overall charge neutrality has a high hydration capability and the best antifouling, anticoagulant, and antihemolytic activities when comes into contact with human blood. PMID:21388227

  3. Copolymeric hexyl acrylate-methacrylic acid microspheres - surface vs. bulk reactive carboxyl groups. Coulometric and colorimetric determination and analytical applications for heterogeneous microtitration.

    PubMed

    Stelmach, Emilia; Maksymiuk, Krzysztof; Michalska, Agata

    2016-10-01

    Copolymeric acrylate microspheres were prepared from hexyl acrylate using different amounts of methacrylic acid, resulting in a series of microspheres of gradually changing properties. The distribution of carboxyl groups - between surface and bulk of microspheres was evaluated. Bulk reactive carboxyl groups were determined using reverse coulometric titration with H(+) ions, following hydroxide ions have been generated and allowed to react with microspheres in the first step. It was found that the number of reactive carboxyl groups available in copolymeric microspheres is lower compared to number of methacrylic acid units used for polymerization process. Moreover, there is correlation between the number of groups introduced and found to be reactive in microspheres. On the other hand, the number of surface reactive groups was proportional to the number of groups introduced in course of polymerization. Thus, the surface reactive groups can be used as reagent, in novel heterogeneous microtitration procedure, in which a constant number of microspheres of different carboxyl groups contents is introduced to the sample to react with the analyte. The applicability of novel proposed method was tested on the example of Ni(2+) determination. PMID:27474305

  4. Experimental study of excitation functions for the deuteron induced reactions 64Zn(d,2p)64Cu and 64Zn(d,alphan)61Cu using the stacked-foil technique.

    PubMed

    Daraban, L; Abbas, K; Simonelli, F; Adam-Rebeles, R; Gibson, N

    2008-02-01

    There is considerable, and growing, interest in the 64Cu radioisotope for application in Nuclear Medicine for PET imaging and targeted radiotherapy of tumours. We are investigating the cyclotron production of this isotope by way of deuteron bombardment of enriched 64Zn target material. In this study, experimental excitation functions for both the 64Zn(d,2p)64Cu and 64Zn(d,alphan)61Cu reactions up to 18.2 MeV deuteron energy have been measured using the stacked-foil technique. The deuteron energies in the various foils were calculated with the SRIM 2003 code and gamma-ray spectrometry was used to measure the activities of the various radioisotopes produced. Monitor foils were used to determine the deuteron beam current on the target stack. Theoretical excitation functions, calculated both with the Empire II code and with an updated version of the Alice code, were compared with the experimental results and a reasonable agreement was found. The experimental work was performed at the MC40 Cyclotron at the European Commission's Joint Research Centre at Ispra, Italy.

  5. Proposal for New Experimental Tests of the Bose-Einstein Condensation Mechanism for Low-Energy Nuclear Reaction and Transmutation Processes in Deuterium Loaded - and Nano-Scale Cavities

    NASA Astrophysics Data System (ADS)

    Kim, Yeong E.; Koltick, David S.; Reifenberger, Ronald G.; Zubarev, Alexander L.

    2006-02-01

    Most of experimental results of low-energy nuclear reaction (LENR) reported so far cannot be reproduced on demand. There have been persistent experimental results indicating that the LENR and transmutation processes in condensed matters (LENRTPCM) are surface phenomena rather than bulk phenomena. Recently proposed Bose-Einstein condensation (BEC) mechanism may provide a suitable theoretical description of the surface phenomena. New experiments are proposed and described for testing the BEC mechanism for LENR and transmutation processes in micro- and nano-scale traps. (1) We propose the use of micro- or nano-porous conducting materials as a cathode in electrolysis experiments with heavy water with or without Li in order to stabilize the active surface spots and to enhance the effect for the purpose of improving the reproducibility of excess heat generation and nuclear emission. (2) We propose new experimental tests of the BEC mechanism by measuring the pressure and temperature dependence of LENR events using deuterium gas and these deuterated metals with or without Li. If the LENRTPCM are surface phenomena, the proposed use of micro-/nano-scale porous materials is expected to enhance and scale up the LENRTPCM effects by many order of magnitude, and thus may lead to better reproductivity and theoretical understanding of the phenomena.

  6. Low-dose benznidazole treatment results in parasite clearance and attenuates heart inflammatory reaction in an experimental model of infection with a highly virulent Trypanosoma cruzi strain

    PubMed Central

    Cevey, Ágata Carolina; Mirkin, Gerardo Ariel; Penas, Federico Nicolás; Goren, Nora Beatriz

    2015-01-01

    Chagas disease, caused by Trypanosoma cruzi, is the main cause of dilated cardiomyopathy in the Americas. Antiparasitic treatment mostly relies on benznidazole (Bzl) due to Nifurtimox shortage or unavailability. Both induce adverse drug effects (ADE) of varied severity in many patients, leading to treatment discontinuation or abandonment. Since dosage may influence ADE, we aimed to assess Bzl efficacy in terms of parasiticidal and anti-inflammatory activity, using doses lower than those previously reported. BALB/c mice infected with the T. cruzi RA strain were treated with different doses of Bzl. Parasitaemia, mortality and weight change were assessed. Parasite load, tissue infiltrates and inflammatory mediators were studied in the heart. Serum creatine kinase (CK) activity was determined as a marker of heart damage. The infection-independent anti-inflammatory properties of Bzl were studied in an in vitro model of LPS-treated cardiomyocyte culture. Treatment with 25 mg/kg/day Bzl turned negative the parasitological parameters, induced a significant decrease in IL-1β, IL-6 and NOS2 in the heart and CK activity in serum, to normal levels. No mortality was observed in infected treated mice. Primary cultured cardiomyocytes treated with Bzl showed that inflammatory mediators were reduced via inhibition of the NF-κB pathway. A Bzl dose lower than that previously reported for treatment of experimental Chagas disease exerts adequate antiparasitic and anti-inflammatory effects leading to parasite clearance and tissue healing. This may be relevant to reassess the dose currently used for the treatment of human Chagas disease, aiming to minimize ADE. PMID:26862474

  7. Low-dose benznidazole treatment results in parasite clearance and attenuates heart inflammatory reaction in an experimental model of infection with a highly virulent Trypanosoma cruzi strain.

    PubMed

    Cevey, Ágata Carolina; Mirkin, Gerardo Ariel; Penas, Federico Nicolás; Goren, Nora Beatriz

    2016-04-01

    Chagas disease, caused by Trypanosoma cruzi, is the main cause of dilated cardiomyopathy in the Americas. Antiparasitic treatment mostly relies on benznidazole (Bzl) due to Nifurtimox shortage or unavailability. Both induce adverse drug effects (ADE) of varied severity in many patients, leading to treatment discontinuation or abandonment. Since dosage may influence ADE, we aimed to assess Bzl efficacy in terms of parasiticidal and anti-inflammatory activity, using doses lower than those previously reported. BALB/c mice infected with the T. cruzi RA strain were treated with different doses of Bzl. Parasitaemia, mortality and weight change were assessed. Parasite load, tissue infiltrates and inflammatory mediators were studied in the heart. Serum creatine kinase (CK) activity was determined as a marker of heart damage. The infection-independent anti-inflammatory properties of Bzl were studied in an in vitro model of LPS-treated cardiomyocyte culture. Treatment with 25 mg/kg/day Bzl turned negative the parasitological parameters, induced a significant decrease in IL-1β, IL-6 and NOS2 in the heart and CK activity in serum, to normal levels. No mortality was observed in infected treated mice. Primary cultured cardiomyocytes treated with Bzl showed that inflammatory mediators were reduced via inhibition of the NF-κB pathway. A Bzl dose lower than that previously reported for treatment of experimental Chagas disease exerts adequate antiparasitic and anti-inflammatory effects leading to parasite clearance and tissue healing. This may be relevant to reassess the dose currently used for the treatment of human Chagas disease, aiming to minimize ADE. PMID:26862474

  8. Experimental study of the dynamics of the H+D2 --> HD+D reaction at collision energies of 0.55 and 1.30 eV

    NASA Astrophysics Data System (ADS)

    Gerrity, Daniel P.; Valentini, James J.

    1984-08-01

    We report here experimental measurement of the nascent HD product quantum state distributions for the H+D2 → HD+D reaction. Pulsed laser photolysis of HI in an HI/D2 gas mixture produces hydrogen atoms giving H+D2 collision energies of 0.55 and 1.30 eV. Nanosecond-time-resolved coherent anti-Stokes Raman scattering (CARS) spectroscopy is used to record rotationally and vibrationally resolved spectra of the HD reaction product under nearly single-collision conditions. The spectra are analyzed to determine the nascent, single-collision HD product quantum state distributions. These distributions are compared to the results of related experiments by E. E. Marinero, C. T. Rettner, and R. N. Zare and to the results of recent quasiclassical trajectory calculations of N. C. Blais and D. G. Truhlar. Our results are in qualitative agreement with those of Marinero et al., but there are some quantitative differences. The trajectory calculations yield HD quantum state distributions which are very close to those we have measured. We find that our HD product quantum state distributions are fairly well summarized by a linear surprisal analysis with a rotational surprisal of 3.0 and a vibrational surprisal of 2.6. The quantum state distributions indicate that 71%±1% of the energy available to the products appears in translation, while 19%±2% is in HD rotation, and 10%±2% is in vibration. These results are discussed in terms of the dynamics of the reaction.

  9. Regioselective construction of 1,3-diazaheterocycle fused [1,2-a][1,8]naphthyridine derivatives via cascade reaction of quinolines with heterocyclic ketene aminals: a joint experimental-computational approach.

    PubMed

    Zhang, Yi-Chuan; Liu, Zhi-Cheng; Yang, Rui; Zhang, Ji-Hong; Yan, Sheng-Jiao; Lin, Jun

    2013-11-14

    A one-step, transition-metal-free protocol, involving facile post-treatment, for the regioselective synthesis of 1,3-diazaheterocycle fused [1,2-a][1,8]naphthyridine derivatives (3) from 2-chloroquinoline-3-carbaldehydes (ClQuAlds) (1) and heterocyclic ketene aminals (HKAs) (2) was developed via a joint experimental-computational approach. The computational prediction of the reactivity of two series of synthons was applied in the process of optimizing the reaction conditions, which relied on density functional theory (DFT) calculations together with concepts of frontier molecular orbital (FMO) theory and quantitative structure-reactivity relationship (QSRR) presumptions. The combined results enabled the proposal of a pre-synthetic prediction of global reactivity. The fully consistent results of the synthetic experiments with the in silico evaluation confirmed the rationality, effectiveness, and practicability of the new strategy. Notably, the joint method is not limited to the laboratory, but has applications ranging from routine to industry. This approach is likely to yield numerous insights to accelerate HKA-related synthetic chemistry that can be extended to numerous heterocycles. It thus opens up a novel entry towards rapidly investigating the reactivity of novel synthons with unique properties, a further step towards exploiting cascade reactions by avoiding the futile waste of time and resources. PMID:24057033

  10. An experimental guided-ion-beam and ab initio study of the ion-molecule gas-phase reactions between Li{sup +} ions and iso-C{sub 3}H{sub 7}Cl in their ground electronic state

    SciTech Connect

    Lucas, J. M.; Andres, J. de; Sogas, J.; Alberti, M.; Aguilar, A.; Bofill, J. M.; Bassi, D.; Ascenzi, D.; Tosi, P.

    2009-07-14

    Reactive collisions between Li{sup +} ions and i-C{sub 3}H{sub 7}Cl molecules have been studied in the 0.20-12.00 eV center-of-mass energy range using an octopole radio frequency guided-ion beam apparatus recently developed in our laboratory. At low collision energies, dehydrohalogenation reactions giving rise to Li(C{sub 3}H{sub 6}){sup +} and Li(HCl){sup +} are the main reaction channels, while at higher ones C{sub 3}H{sub 7}{sup +} and C{sub 2}H{sub 3}{sup +} become dominant, all their reactive cross sections having been measured as a function of the collision energy. To obtain information about the potential energy surfaces (PESs) on which the reactive processes take place, ab initio calculations at the MP2 level have been performed. For dehydrohalogenations, the reactive ground singlet PES shows ion-molecule adduct formation in both the reactant and product sides of the surface. Following the minimum energy path connecting both minima, an unstable intermediate and the corresponding barriers, both lying below the reactant's energy, have been characterized. The entrance channel ion-molecule adduct is also involved in the formation of C{sub 3}H{sub 7}{sup +}, which then generates C{sub 2}H{sub 3}{sup +} via an CH{sub 4} unimolecular elimination. A qualitative interpretation of the experimental results based on ab initio calculations is also included.

  11. Experimental and theoretical studies of the reaction of the OH radical with alkyl sulfides: 3. Kinetics and mechanism of the OH initiated oxidation of dimethyl, dipropyl, and dibutyl sulfides: reactivity trends in the alkyl sulfides and development of a predictive expression for the reaction of OH with DMS.

    PubMed

    Williams, M B; Campuzano-Jost, P; Hynes, A J; Pounds, A J

    2009-06-18

    A pulsed laser photolysis-pulsed laser-induced fluorescence technique has been employed to measure rate coefficients for the OH-initiated oxidation of dimethyl sulfide (DMS), its deuterated analog (DMS-d(6)), dipropyl sulfide (DPS), and dibutyl sulfide (DBS). Effective rate coefficients have been measured as a function of the partial pressure of O(2) over the temperature range of 240-295 K and at 200 and 600 Torr total pressure. We report the first observations of an O(2) enhancement in the effective rate coefficients for the reactions of OH with DPS and DBS. All observations are consistent with oxidation proceeding via a two-channel oxidation mechanism involving abstraction and addition channels. Structures and thermochemistry of the DPSOH and DBSOH adducts were calculated. Calculated bond strengths of adducts increase with alkyl substitution but are comparable to that of the DMSOH adduct and are consistent with experimental observations. Reactivity trends across the series of alkyl sulfide (C(2)-C(8)) reactions are analyzed. All reactions proceed via a two-channel mechanism involving either an H-atom abstraction or the formation of an OH adduct that can then react with O(2). Measurements presented in this work, in conjunction with previous measurements, have been used to develop a predictive expression for the OH-initiated oxidation of DMS. This expression is based on the elementary rate coefficients in the two-channel mechanism. The expression can calculate the effective rate coefficient for the reaction of OH with DMS over the range of 200-300 K, 0-760 Torr, and 0-100% partial pressure of O(2). This expression expands on previously published work but is applicable to DMS oxidation throughout the troposphere.

  12. Reactions of Phenolphthalein at Various pH Values.

    ERIC Educational Resources Information Center

    Wittke, Georg

    1983-01-01

    Reactions of phenolphthalein with sodium hydroxide and sulfuric are discussed. Also discusses the sulfonation of phenolphthalein, listing experimental results related to the sulfonation reaction. (JN)

  13. Radiative capture reactions in astrophysics

    SciTech Connect

    Brune, Carl R.; Davids, Barry

    2015-08-07

    Here, the radiative capture reactions of greatest importance in nuclear astrophysics are identified and placed in their stellar contexts. Recent experimental efforts to estimate their thermally averaged rates are surveyed.

  14. Code System to Calculate Integral Parameters with Reaction Rates from WIMS Output.

    1994-10-25

    Version 00 REACTION calculates different integral parameters related to neutron reactions on reactor lattices, from reaction rates calculated with WIMSD4 code, and comparisons with experimental values.

  15. Sympathetic reaction tests and analyses

    NASA Technical Reports Server (NTRS)

    Ricardson, D. E.; Bowman, A. L.

    1980-01-01

    The critical separation distances for explosive reactions of a solid rocket propellant were measured. Explosive reactions included low order explosion, low order detonation, and high order detonation. The effects of sample size, shape, damage and temperature on sympathetic reaction were determined experimentally. The sympathetic detonation of small cubes of solid rocket propellant was modelled numerically, using the Eulerian reactive hydrodynamic code 2DE with Forest Fire burn rates. The model was applied to cubes of 2.54 - 7.62 cm (1 - 3 in.), with agreement between calculated and experimental results.

  16. Proposed mechanism for the reaction catalyzed by a diterpene cyclase, aphidicolan-16beta-ol synthase: experimental results on biomimetic cyclization and examination of the cyclization pathway by ab initio calculations.

    PubMed

    Oikawa, Hideaki; Nakamura, Kensuke; Toshima, Hiroaki; Toyomasu, Tomonobu; Sassa, Takeshi

    2002-08-01

    To examine the mechanism of the cyclization reaction catalyzed by aphidicolan-16beta-ol synthase (ACS), which is a key enzyme in the biosynthesis of diterpene aphidicolin, a specific inhibitor of DNA polymerase alpha, skeletal rearrangement of 2a and biomimetic cyclization of 4b were employed. The structures of the reaction products, which reflect penultimate cation intermediates, allowed us to propose a detailed reaction pathway for the Lewis acid-catalyzed cyclizations and rearrangements. Isolation of these products in an aphidicolin-producing fungus led us to speculate that the mechanism of the ACS-catalyzed cyclization reaction is the same as that of a nonenzymatic reaction. Ab initio calculations of the acid-catalyzed reaction intermediates and the transition states indicate that the overall reaction catalyzed by ACS is an exothermic process though the reaction proceeds via an energetically disfavored secondary cation-like transition state. In conjunction with the solvent effect in the acid-catalyzed reactions, this indicates that the actual role of ACS is to provide a template which enforces conformations of the intermediate cations leading to the productive cyclization although it has been believed that the cation-pi interaction between cation intermediates and aromatic amino acid residues in the active site is important for the enzymatic catalysis. This study provided important information on the role of various cationic species, especially secondary cation-like structures, in both nonenzymatic and enzymatic reactions.

  17. A Mechanism of O-Demethylation of Aristolochic Acid I by Cytochromes P450 and Their Contributions to This Reaction in Human and Rat Livers: Experimental and Theoretical Approaches.

    PubMed

    Stiborová, Marie; Bárta, František; Levová, Kateřina; Hodek, Petr; Schmeiser, Heinz H; Arlt, Volker M; Martínek, Václav

    2015-11-18

    Aristolochic acid I (AAI) is a plant alkaloid causing aristolochic acid nephropathy, Balkan endemic nephropathy and their associated urothelial malignancies. AAI is detoxified by cytochrome P450 (CYP)-mediated O-demethylation to 8-hydroxyaristolochic acid I (aristolochic acid Ia, AAIa). We previously investigated the efficiencies of human and rat CYPs in the presence of two other components of the mixed-functions-oxidase system, NADPH:CYP oxidoreductase and cytochrome b₅, to oxidize AAI. Human and rat CYP1A are the major enzymes oxidizing AAI. Other CYPs such as CYP2C, 3A4, 2D6, 2E1, and 1B1, also form AAIa, but with much lower efficiency than CYP1A. Based on velocities of AAIa formation by examined CYPs and their expression levels in human and rat livers, here we determined the contributions of individual CYPs to AAI oxidation in these organs. Human CYP1A2 followed by CYP2C9, 3A4 and 1A1 were the major enzymes contributing to AAI oxidation in human liver, while CYP2C and 1A were most important in rat liver. We employed flexible in silico docking methods to explain the differences in AAI oxidation in the liver by human CYP1A1, 1A2, 2C9, and 3A4, the enzymes that all O-demethylate AAI, but with different effectiveness. We found that the binding orientations of the methoxy group of AAI in binding centers of the CYP enzymes and the energies of AAI binding to the CYP active sites dictate the efficiency of AAI oxidation. Our results indicate that utilization of experimental and theoretical methods is an appropriate study design to examine the CYP-catalyzed reaction mechanisms of AAI oxidation and contributions of human hepatic CYPs to this metabolism.

  18. A Mechanism of O-Demethylation of Aristolochic Acid I by Cytochromes P450 and Their Contributions to This Reaction in Human and Rat Livers: Experimental and Theoretical Approaches

    PubMed Central

    Stiborová, Marie; Bárta, František; Levová, Kateřina; Hodek, Petr; Schmeiser, Heinz H.; Arlt, Volker M.; Martínek, Václav

    2015-01-01

    Aristolochic acid I (AAI) is a plant alkaloid causing aristolochic acid nephropathy, Balkan endemic nephropathy and their associated urothelial malignancies. AAI is detoxified by cytochrome P450 (CYP)-mediated O-demethylation to 8-hydroxyaristolochic acid I (aristolochic acid Ia, AAIa). We previously investigated the efficiencies of human and rat CYPs in the presence of two other components of the mixed-functions-oxidase system, NADPH:CYP oxidoreductase and cytochrome b5, to oxidize AAI. Human and rat CYP1A are the major enzymes oxidizing AAI. Other CYPs such as CYP2C, 3A4, 2D6, 2E1, and 1B1, also form AAIa, but with much lower efficiency than CYP1A. Based on velocities of AAIa formation by examined CYPs and their expression levels in human and rat livers, here we determined the contributions of individual CYPs to AAI oxidation in these organs. Human CYP1A2 followed by CYP2C9, 3A4 and 1A1 were the major enzymes contributing to AAI oxidation in human liver, while CYP2C and 1A were most important in rat liver. We employed flexible in silico docking methods to explain the differences in AAI oxidation in the liver by human CYP1A1, 1A2, 2C9, and 3A4, the enzymes that all O-demethylate AAI, but with different effectiveness. We found that the binding orientations of the methoxy group of AAI in binding centers of the CYP enzymes and the energies of AAI binding to the CYP active sites dictate the efficiency of AAI oxidation. Our results indicate that utilization of experimental and theoretical methods is an appropriate study design to examine the CYP-catalyzed reaction mechanisms of AAI oxidation and contributions of human hepatic CYPs to this metabolism. PMID:26593908

  19. Radiation-induced reactions in polymer films

    NASA Astrophysics Data System (ADS)

    Biscoglio, Michael Benedict

    photophysically characterized so that they can be easily identified in future experiments where they may be important reactants. Alternatively, photophysical probes are attached to polymer chains by radical copolymerization of pyrene acrylic acid and methyl acrylate with the underivatized monomer. These probes did not inhibit the polymerization reaction, and were found to be useful in monitoring polymerization rates during the early stages of polymerization.

  20. Formaldehyde reactions in dark clouds.

    PubMed

    Sen, A D; Anicich, V G; Federman, S R

    1992-05-20

    The low-pressure reactions of formaldehyde (H2CO) with D+, D2+, D3+, and He+ have been studied by the ion cyclotron resonance technique. These reactions are potential loss processes for formaldehyde in cores of dark interstellar clouds. The deuterated reactants, which are easier to study experimentally, represent direct analogs for protons. Rate coefficients and branching ratios of product channels have been measured. Charge transfer is observed to be the dominant reaction of H2CO with D+, D2+, and He+ ions. Only the D3+ reaction exhibits a proton transfer channel. All reactions proceed at rate coefficients near the collision limit. Proton-deuteron exchange reactions were found to be inefficient processes in the formaldehyde system.

  1. Cationic Copolymerization of 3,3-Bis(hydroxymethyl)oxetane and Glycidol: Biocompatible Hyperbranched Polyether Polyols with High Content of Primary Hydroxyl Groups.

    PubMed

    Christ, Eva-Maria; Hobernik, Dominika; Bros, Matthias; Wagner, Manfred; Frey, Holger

    2015-10-12

    The cationic ring-opening copolymerization of 3,3-bis(hydroxymethyl)oxetane (BHMO) with glycidol using different comonomer ratios (BHMO content from 25 to 90%) and BF3OEt2 as an initiator has been studied. Apparent molecular weights of the resulting hyperbranched polyether copolymers ranged from 1400 to 3300 g mol(-1) (PDI: 1.21-1.48; method: SEC, linear PEG standards). Incorporation of both comonomers is evidenced by MALDI-TOF mass spectroscopy. All hyperbranched polyether polyols with high content of primary hydroxyl groups portray good solubility in water, which correlates with an increasing content of glycerol units. Detailed NMR characterization was employed to elucidate the copolymer microstructures. Kinetic studies via FTIR demonstrated a weak gradient-type character of the copolymers. MTT assays of the copolymers (up to 100 μg mL(-1)) on HEK and fibroblast cell lines (3T3, L929, WEHI) as well as viability tests on the fibroblast cells were carried out to assess the biocompatibility of the materials, confirming excellent biocompatibility. Transfection efficiency characterization by flow cytometry and confocal laser microscopy demonstrated cellular uptake of the copolymers. Antiadhesive properties of the materials on surfaces were assessed by adhesion assays with fibroblast cells.

  2. Cationic Copolymerization of 3,3-Bis(hydroxymethyl)oxetane and Glycidol: Biocompatible Hyperbranched Polyether Polyols with High Content of Primary Hydroxyl Groups.

    PubMed

    Christ, Eva-Maria; Hobernik, Dominika; Bros, Matthias; Wagner, Manfred; Frey, Holger

    2015-10-12

    The cationic ring-opening copolymerization of 3,3-bis(hydroxymethyl)oxetane (BHMO) with glycidol using different comonomer ratios (BHMO content from 25 to 90%) and BF3OEt2 as an initiator has been studied. Apparent molecular weights of the resulting hyperbranched polyether copolymers ranged from 1400 to 3300 g mol(-1) (PDI: 1.21-1.48; method: SEC, linear PEG standards). Incorporation of both comonomers is evidenced by MALDI-TOF mass spectroscopy. All hyperbranched polyether polyols with high content of primary hydroxyl groups portray good solubility in water, which correlates with an increasing content of glycerol units. Detailed NMR characterization was employed to elucidate the copolymer microstructures. Kinetic studies via FTIR demonstrated a weak gradient-type character of the copolymers. MTT assays of the copolymers (up to 100 μg mL(-1)) on HEK and fibroblast cell lines (3T3, L929, WEHI) as well as viability tests on the fibroblast cells were carried out to assess the biocompatibility of the materials, confirming excellent biocompatibility. Transfection efficiency characterization by flow cytometry and confocal laser microscopy demonstrated cellular uptake of the copolymers. Antiadhesive properties of the materials on surfaces were assessed by adhesion assays with fibroblast cells. PMID:26355352

  3. Acidity-promoted cellular uptake and drug release mediated by amine-functionalized block polycarbonates prepared via one-shot ring-opening copolymerization.

    PubMed

    Wang, Hua-Fen; Jia, Hui-Zhen; Chu, Yan-Feng; Feng, Jun; Zhang, Xian-Zheng; Zhuo, Ren-Xi

    2014-04-01

    This paper reports a drug nanovehicle self-assembled from an amine-functionalized block copolymer poly(6,14-dimethyl-1,3,9,11-tetraoxa-6,14-diaza-cyclohexadecane-2,10-dione)-block-poly(1,3-dioxepan-2-one) (PADMC-b-PTeMC), which is prepared by controlable ring-opening block copolymerization attractively in a "one-shot feeding" pathway. The copolymers display high cell-biocompatibility with no apparent cytotoxicities detected in 293T and HeLa cells. Due to their amphiphilic nature, PADMC-b-PTeMC copolymers can self-assemble into nanosized micelles capable of loading anticancer drugs such as camptothecin (CPT) and doxorubicin (DOX). In particular, the outer PADMC shell endows the PADMC-b-PTeMC nanomicelles with pH-dependent control over the micellar morphology, cell uptake efficiency, and the drug release pattern. Confocal inspection reveals the remarkably enhanced cellular internalization of drug loaded micelles by cancerous HeLa cells at relatively lower pH 5.8 simulating the mildly acid microenvironment in tumors. Along with the acidity-triggered volume expansion of micelles, an accelerated CPT release in vitro occurs. The obtained results adumbrate the possibility of completely biodegradable PADMC-b-PTeMC as pH-sensitive drug carriers for tumor chemotherapy.

  4. Electrophoretic analysis of proteinases in sodium dodecyl sulfate-polyacrylamide gels containing copolymerized radiolabeled protein substrates: Application to proenkephalin processing enzymes

    SciTech Connect

    Irvine, J.W.; Roberts, S.F.; Lindberg, I. )

    1990-10-01

    A novel method is described for the zymographic analysis of proteinases in sodium dodecyl sulfate-polyacrylamide gels containing copolymerized radiolabeled protein substrates such as ({sup 35}S)methionine-labeled proenkephalin or {sup 125}I-labeled proinsulin. After electrophoresis the enzyme is reactivated and cleaves the radiolabeled in situ substrate into smaller peptides. These small peptides are able to diffuse out of the gel, leaving clear areas against a dark background when visualized by autoradiography. The technique can be used to detect as little as 200 fg of trypsin using only 50 ng (1.25 microCi) of ({sup 35}S)proenkephalin. Soluble- and membrane-bound adrenal trypsin-like enzyme were isolated from bovine adrenal chromaffin granules. Both proteinases cleaved ({sup 35}S)methionine-labeled proenkephalin but not {sup 125}I-labeled proinsulin. Moreover, both had a Mr of approximately 30,000. The potential of this technique for general use is discussed. An additional method using the synthetic fluorogenic substrate t-butoxycarbonyl Glu-Lys-Lys aminomethylcoumarin is also described.

  5. Synthesis of a novel supermagnetic iron oxide nanocomposite hydrogel based on graft copolymerization of poly((2-dimethylamino)ethyl methacrylate) onto salep for controlled release of drug.

    PubMed

    Bardajee, Ghasem Rezanejade; Hooshyar, Zari; Asli, Maryam Jahanbakhsh; Shahidi, Fatemeh Emamjome; Dianatnejad, Nastaran

    2014-03-01

    In this research, a novel supermagnetic iron oxide nanocomposite hydrogel was prepared using simultaneous in situ formation of iron oxide nanoparticles (IONs) and three-dimensional cross-linked polymer networks based on graft copolymerization of poly((2-dimethylamino)ethyl methacrylate) (PDMA) onto salep (PDMA-g-salep). The prepared ION-PDMA-g-salep hydrogel was systematically characterized by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy with energy dispersive X-ray analysis (SEM-EDAX), transmission electron microscopy (TEM), thermal gravimetric analysis (TGA), X-ray diffraction (XRD), and vibrating sample magnetometer (VSM). In addition, the ION-PDMA-g-salep hydrogel exhibits favorable swelling properties that are sensitive to temperature, pH, and external magnetic field (EMF). The drug release behavior of the prepared hydrogel under EMF, different temperatures and pHs was also studied for the evaluation of the release mechanism and determination of diffusion coefficients. Finally, the antibacterial activity and cytotoxicity studies of the prepared hydrogel were examined. These results suggested that the ION-PDMA-g-salep hydrogel could be a promising candidate for biological dressing applications. PMID:24433913

  6. Oxygen and carbon dioxide dual gas-responsive and switchable microgels prepared from emulsion copolymerization of fluoro- and amino-containing monomers.

    PubMed

    Lei, Lei; Zhang, Qi; Shi, Shuxian; Zhu, Shiping

    2015-02-24

    We report herein the design and preparation of microgels that are responsive to both O2 and CO2 gases. The microgels were synthesized through soap-free emulsion copolymerization of O2-responsive monomer 2,3,4,5,6-pentafluorostyrene (FS) and CO2-responsive monomer 2-(diethylamino)ethyl methacrylate (DEA) with N,N'-methylenebis(acrylamide) (BisAM) as the cross-linker. The P(DEA-co-FS) microgels dispersed in aqueous solution could undergo volume phase transitions triggered by O2 and/or CO2 aeration. The particles were very responsive to CO2, while their responsivity to O2 was moderate. Microgels having different levels of the responsivity could be designed and prepared by varying the FS content in the copolymer. The phase transitions were also highly reversible, and the initial states of microgels could be easily recovered by "washing off" the trigger gases with N2. Multicycle O2, CO2, and N2 aerations were applied, and no loss in the dual gas responsivity and switchability was observed. PMID:25643178

  7. Kinetic studies of elementary chemical reactions

    SciTech Connect

    Durant, J.L. Jr.

    1993-12-01

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

  8. Nuclear Structure and Reaction Mechanism Studies with Multinucleon Reactions

    SciTech Connect

    Regan, P. H.; Jones, G. A.; Podolyak, Zs.; Abdullah, M.; Gelletly, W.; Langdown, S. D.; Wollel, G.; De Angelis, G.; Gadea, A.; Kroell, Th.; Marginean, N.; Martinez, T.; Napoli, D. R.; Rusu, C.; Tonev, D.; Zhang, Y. H.; Ur, C. A.; Axiotis, M.; Bazzacco, D.; Farnea, E.

    2006-08-14

    This contribution reports on the results of an experiment to study the near-yrast states in selenium- and osmium-like nuclei, following their population in thick-target, multinucleon transfer reactions between an 82Se beam and a 192Os target. The experimental results for the level scheme for 84Se are presented together with investigations into the use of multi-dimensional gamma-ray energy gating to investigate angular momentum population in such heavy-ion binary reactions.

  9. Chemical Reactions in DSMC

    SciTech Connect

    Bird, G. A.

    2011-05-20

    DSMC simulations of chemically reacting gas flows have generally employed procedures that convert the macroscopic chemical rate equations to reaction cross-sections at the microscopic level. They therefore depend on the availability of experimental data that has been fitted to equations of the Arrhenius form. This paper presents a physical model for dissociation and recombination reactions and a phenomenological model for exchange and chain reactions. These are based on the vibrational states of the colliding molecules and do not require any experimentally-based data. The simplicity of the models allows the corresponding rate equations to be written down and, while these are not required for the implementation of the models, they facilitate their validation. The model is applied to a typical hypersonic atmospheric entry problem and the results are compared with the corresponding results from the traditional method. It is also used to investigate both spontaneous and forced ignition as well as the structure of a deflagration wave in an oxygen-hydrogen mixture.

  10. Experimental study of the {sup 238}U({sup 36}S,3-5n){sup 269-271}Hs reaction leading to the observation of {sup 270}Hs

    SciTech Connect

    Graeger, R.; Gorshkov, A.; Tuerler, A.; Yakushev, A.; Ackermann, D.; Duellmann, Ch. E.; Hessberger, F. P.; Huebner, A.; Jaeger, E.; Khuyagbaatar, J.; Kindler, B.; Krier, J.; Lommel, B.; Schaedel, M.; Schausten, B.; Chelnokov, M.; Chepigin, V.; Kuznetsov, A.; Petrushkin, O.; Dvorak, J.

    2010-06-15

    The deformed doubly magic nucleus {sup 270}Hs has so far only been observed as the four-neutron (4n) evaporation residue of the reaction {sup 26}Mg+{sup 248}Cm, where a maximum cross section of 3 pb was measured. Theoretical studies on the formation of {sup 270}Hs in the 4n evaporation channel of fusion reactions with different entrance channel asymmetry in the framework of a two-parameter Smoluchowski equation predict that the reactions {sup 48}Ca+{sup 226}Ra and {sup 36}S+{sup 238}U result in higher cross sections due to lower reaction Q values, in contrast to simple arguments based on the reaction asymmetry, which predict opposite trends. Calculations using hivap predict cross sections for the reaction {sup 36}S+{sup 238}U that are similar to those of the {sup 26}Mg+{sup 248}Cm reaction. Here, we report on the first measurement of evaporation residues formed in the complete nuclear fusion reaction {sup 36}S+{sup 238}U and the observation of {sup 270}Hs, which is produced in the 4n evaporation channel, with a measured cross section of 0.8{sub -0.7}{sup +2.6} pb at 51-MeV excitation energy. The one-event cross-section limits (68% confidence level) for the 3n, 4n, and 5n evaporation channels at 39-MeV excitation energy are 2.9 pb, while the cross-section limits of the 3n and 5n channel at 51 MeV are 1.5 pb. This is significantly lower than the 5n cross section of the {sup 26}Mg+{sup 248}Cm reaction at similar excitation energy.

  11. Modeling the complex bromate-iodine reaction.

    PubMed

    Machado, Priscilla B; Faria, Roberto B

    2009-05-01

    In this article, it is shown that the FLEK model (ref 5 ) is able to model the experimental results of the bromate-iodine clock reaction. Five different complex chemical systems, the bromate-iodide clock and oscillating reactions, the bromite-iodide clock and oscillating reactions, and now the bromate-iodine clock reaction are adequately accounted for by the FLEK model. PMID:19361181

  12. Indirect techniques for astrophysical reaction rates determinations

    NASA Astrophysics Data System (ADS)

    Hammache, F.; Oulebsir, N.; Benamara, S.; De Séréville, N.; Coc, A.; Laird, A.; Stefan, I.; Roussel, P.

    2016-05-01

    Direct measurements of nuclear reactions of astrophysical interest can be challenging. Alternative experimental techniques such as transfer reactions and inelastic scattering reactions offer the possibility to study these reactions by using stable beams. In this context, I will present recent results that were obtained in Orsay using indirect techniques. The examples will concern various astrophysical sites, from the Big-Bang nucleo synthesis to the production of radioisotopes in massive stars.

  13. Nuclear reactions at intermediate energies

    NASA Astrophysics Data System (ADS)

    Shyam, Radhey

    2016-05-01

    In the domain of Nuclear reactions at intermediate energies, the QCD coupling constant αs is large enough (~ 0.3 - 0.5) to render the perturbative calculational techniques inapplicable. In this regime the quarks are confined into colorless hadrons and it is expected that effective field theories of hadron interactions via exchange of hadrons, provide useful tools to describe such reactions. In this contribution we discuss the application of one such theory, the effective Lagrangian model, in describing the hadronic reactions at intermediate energies whose measurements are the focus of a vast international experimental program.

  14. Coarctate cyclization reactions: a primer.

    PubMed

    Young, Brian S; Herges, Rainer; Haley, Michael M

    2012-10-01

    The cleavage of five-membered heterocycles possessing an exocyclic carbene or nitrene to form conjugated ene-ene-yne systems has been documented for over 40 years; however, the reverse reaction, using a conjugated "ene-ene-yne" precursor to form a heterocycle is a relatively new approach. Over the past decade, the Haley and Herges groups have studied computationally and experimentally the cyclization of the "hetero-ene-ene-yne" motif via an unusual class of concerted reactions known as coarctate reactions. This feature article details our synthetic and mechanistic work involving triazene-arene-alkynes and structurally-related systems to generate heterocycles using coarctate chemistry.

  15. Photoneutron reactions in astrophysics

    SciTech Connect

    Varlamov, V. V. Ishkhanov, B. S.; Orlin, V. N.; Peskov, N. N.; Stopani, K. A.

    2014-12-15

    Among key problems in nuclear astrophysics, that of obtaining deeper insight into the mechanism of synthesis of chemical elements is of paramount importance. The majority of heavy elements existing in nature are produced in stars via radiative neutron capture in so-called s- and r processes, which are, respectively, slow and fast, in relation to competing β{sup −}-decay processes. At the same time, we know 35 neutron-deficient so-called bypassed p-nuclei that lie between {sup 74}Se and {sup 196}Hg and which cannot originate from the aforementioned s- and r-processes. Their production is possible in (γ, n), (γ, p), or (γ, α) photonuclear reactions. In view of this, data on photoneutron reactions play an important role in predicting and describing processes leading to the production of p-nuclei. Interest in determining cross sections for photoneutron reactions in the threshold energy region, which is of particular importance for astrophysics, has grown substantially in recent years. The use of modern sources of quasimonoenergetic photons obtained in processes of inverse Compton laser-radiation scattering on relativistic electronsmakes it possible to reveal rather interesting special features of respective cross sections, manifestations of pygmy E1 and M1 resonances, or the production of nuclei in isomeric states, on one hand, and to revisit the problem of systematic discrepancies between data on reaction cross sections from experiments of different types, on the other hand. Data obtained on the basis of our new experimental-theoretical approach to evaluating cross sections for partial photoneutron reactions are invoked in considering these problems.

  16. qPCR (quantitative polymerase chain reaction) for the quantification of bacteriophages in stream water samples to investigate hydrological processes: a proof-of-concept study in the Huewelerbach experimental catchment (Luxembourg)

    NASA Astrophysics Data System (ADS)

    Antonelli, Marta; Narayanan Balasubramanian, Mukundh; Ogorzaly, Leslie; Pfister, Laurent

    2016-04-01

    Albeit recent technological developments (e.g. field deployable instruments operating at high temporal frequencies), experimental hydrology is a discipline that remains measurement limited. From this perspective, trans-disciplinary approaches may create valuable opportunities to enlarge the amount of tools available for investigating hydrological processes. Bacteriophages have been widely used in hydrology as biological tracer for investigating colloid transport and contamination of ground water systems. However, there are only a few studies focusing on the employability of bacteriophages as surface water tracers (i.e. phage transport, system functioning). Here, we present a proof-of-concept study carried out in the Huewelerbach catchment in Luxembourg in December 2015. The aim of this study was to investigate how viral particles can be used to detect hydrological connectivity between the riparian zone/river bank and the stream during rainfall events. Moreover, this study is one of the first attempts for applying the qPCR (quantitative polymerase chain reaction) technique for the quantification of bacteriophages in stream water samples to investigate hydrological processes. This technique is very sensitive and has a large dynamic range - enhancing ease and speed of phage detection. We used two different male-specific coliphages (GA phage, genogroup II and SP phage, genogroup IV). Two litres of GA phage were injected directly in the stream as a slug injection and two litres of SP phage were poured next to the river bank (alluvial deposition) close to the injection point. We also added NaCl (200 g) to both phage suspensions. We collected stream water samples 100 m and 500 m downstream (i.e. catchment outlet) of the injection point for one week. Phages were concentrated through ultracentrifugation of 100 ml of water sample followed by quantification via qPCR. Conductivity in stream water was monitored for the entire duration of the experiment. Discharge was monitored

  17. Magnetic hydrophilic methacrylate-based polymer microspheres designed for polymerase chain reactions applications.

    PubMed

    Spanová, Alena; Horák, Daniel; Soudková, Eva; Rittich, Bohuslav

    2004-02-01

    Magnetic hydrophilic non-porous P(HEMA-co-EDMA), P(HEMA-co-GMA) and PGMA microspheres were prepared by dispersion (co)polymerization of 2-hydroxyethyl methacrylate (HEMA) and ethylene dimethacrylate (EDMA) or glycidyl methacrylate (GMA) in the presence of several kinds of magnetite. It was found that some components used in the preparation of magnetic carriers interfered with polymerase chain reaction (PCR). Influence of non-magnetic and magnetic microspheres, including magnetite nanoparticles and various components used in their synthesis, on the PCR course was thus investigated. DNA isolated from bacterial cells of Bifidobacterium longum was used in PCR evaluation of non-interfering magnetic microspheres. The method enabled verification of the incorporation of magnetite nanoparticles in the particular methacrylate-based polymer microspheres and evaluation of suitability of their application in PCR. Preferably, electrostatically stabilized colloidal magnetite (ferrofluid) should be used in the design of new magnetic methacrylate-based microspheres by dispersion polymerization. PMID:14698232

  18. Multifaceted and route-controlled "click" reactions based on vapor-deposited coatings.

    PubMed

    Sun, Ting-Pi; Tai, Ching-Heng; Wu, Jyun-Ting; Wu, Chih-Yu; Liang, Wei-Chieh; Chen, Hsien-Yeh

    2016-02-01

    "Click" reactions provide precise and reliable chemical transformations for the preparation of functional architectures for biomaterials and biointerfaces. The emergence of a multiple-click reaction strategy has paved the way for a multifunctional microenvironment with orthogonality and precise multitasking that mimics nature. We demonstrate a multifaceted and route-controlled click interface using vapor-deposited functionalized poly-para-xylylenes. Distinctly clickable moieties of ethynyl and maleimide were introduced into poly-para-xylylenes in one step via a chemical vapor deposition (CVD) copolymerization process. The advanced interface coating allows for a double-click route with concurrent copper(i)-catalyzed Huisgen 1,3-dipolar cycloaddition (CuAAC) and the thiol-maleimide click reaction. Additionally, double-click reactions can also be performed in a cascade manner by controlling the initiation route to enable the CuAAC and/or thiol-yne reaction using a mono-functional alkyne-functionalized poly-para-xylylene. The use of multifaceted coatings to create straightforward and orthogonal interface properties with respect to protein adsorption and cell attachment is demonstrated and characterized. PMID:26650976

  19. Transfer reactions in nuclear astrophysics

    NASA Astrophysics Data System (ADS)

    Bardayan, D. W.

    2016-08-01

    To a high degree many aspects of the large-scale behavior of objects in the Universe are governed by the underlying nuclear physics. In fact the shell structure of nuclear physics is directly imprinted into the chemical abundances of the elements. The tranquility of the night sky is a direct result of the relatively slow rate of nuclear reactions that control and determines a star’s fate. Understanding the nuclear structure and reaction rates between nuclei is vital to understanding our Universe. Nuclear-transfer reactions make accessible a wealth of knowledge from which we can extract much of the required nuclear physics information. A review of transfer reactions for nuclear astrophysics is presented with an emphasis on the experimental challenges and opportunities for future development.

  20. Effective radii of deuteron-induced reactions

    SciTech Connect

    Hashimoto, Shintaro; Chiba, Satoshi; Yahiro, Masanobu; Ogata, Kazuyuki; Minomo, Kosho

    2011-05-15

    The continuum-discretized coupled-channels method (CDCC) for exclusive reactions and the eikonal reaction theory (ERT) as an extension of CDCC to inclusive reactions are applied to deuteron-induced reactions. The CDCC result reproduces experimental data on the reaction cross section for d+{sup 58}Ni scattering at 200 MeV/nucleon, and ERT provides data on the neutron-stripping cross section for inclusive {sup 7}Li(d,n) reaction at 40 MeV. For deuteron-induced reactions at 200 MeV/nucleon, target-dependence of the reaction, elastic-breakup, nucleon-stripping, nucleon-removal, and complete- and incomplete-fusion cross sections is clearly explained by simple formulas. Accuracy of the Glauber model is also investigated.

  1. Oxidation reaction by xanthine oxidase: theoretical study of reaction mechanism.

    PubMed

    Amano, Tatsuo; Ochi, Noriaki; Sato, Hirofumi; Sakaki, Shigeyoshi

    2007-07-01

    The oxidation process by molybdenum-containing enzyme, xanthine oxidase, is theoretically studied with a model complex representing the reaction center and a typical benchmark substrate, formamide. Comparisons were systematically made among reaction mechanisms proposed previously. In the concerted and stepwise mechanisms that were theoretically discussed previously, the oxidation reaction takes place with a moderate activation barrier. However, the product is less stable than the reactant complex, which indicates that these mechanisms are unlikely. Moreover, the product of the concerted mechanism is not consistent with the isotope experimental result. In addition to those mechanisms, another mechanism initiated by the deprotonation of the active site was newly investigated here. In the transition state of this reaction, the carbon atom of formamide interacts with the oxo ligand of the Mo center and the hydrogen atom is moving from the carbon atom to the thioxo ligand. This reaction takes place with a moderate activation barrier and considerably large exothermicity. Furthermore, the product by this mechanism is consistent with the isotope experimental result. Also, our computations clearly show that the deprotonation of the active site occurs with considerable exothermicity in the presence of glutamic acid and substrate. The intermediate of the stepwise mechanism could not be optimized in the case of the deprotonated active site. From all these results, it should be concluded that the one-step mechanism with the deprotonated active site is the most plausible.

  2. Combined Experimental and Theoretical Study on the Formation of the Elusive 2-Methyl-1-silacycloprop-2-enylidene Molecule under Single Collision Conditions via Reactions of the Silylidyne Radical (SiH; X(2)Π) with Allene (H2CCCH2; X(1)A1) and D4-Allene (D2CCCD2; X(1)A1).

    PubMed

    Yang, Tao; Dangi, Beni B; Maksyutenko, Pavlo; Kaiser, Ralf I; Bertels, Luke W; Head-Gordon, Martin

    2015-12-17

    The crossed molecular beam reactions of the ground-state silylidyne radical (SiH; X(2)Π) with allene (H2CCCH2; X(1)A1) and D4-allene (D2CCCD2; X(1)A1) were carried out at collision energies of 30 kJ mol(-1). Electronic structure calculations propose that the reaction of silylidyne with allene has no entrance barrier and is initiated by silylidyne addition to the π electron density of allene either to one carbon atom (C1/C2) or to both carbon atoms simultaneously via indirect (complex forming) reaction dynamics. The initially formed addition complexes isomerize via two distinct reaction pathways, both leading eventually to a cyclic SiC3H5 intermediate. The latter decomposes through a loose exit transition state via an atomic hydrogen loss perpendicularly to the plane of the decomposing complex (sideways scattering) in an overall exoergic reaction (experimentally: -19 ± 13 kJ mol(-1); computationally: -5 ± 3 kJ mol(-1)). This hydrogen loss yields the hitherto elusive 2-methyl-1-silacycloprop-2-enylidene molecule (c-SiC3H4), which can be derived from the closed-shell cyclopropenylidene molecule (c-C3H2) by replacing a hydrogen atom with a methyl group and the carbene carbon atom by the isovalent silicon atom. The synthesis of the 2-methyl-1-silacycloprop-2-enylidene molecule in the bimolecular gas-phase reaction of silylidyne with allene enriches our understanding toward the formation of organosilicon species in the gas phase of the interstellar medium in particular via exoergic reactions of no entrance barrier. This facile route to 2-methyl-1-silacycloprop-2-enylidene via a silylidyne radical reaction with allene opens up a versatile approach to form hitherto poorly characterized silicon-bearing species in extraterrestrial environments; this reaction class might represent the missing link, leading from silicon-bearing radicals via organosilicon chemistry eventually to silicon-carbon-rich interstellar grains even in cold molecular clouds where temperatures are as

  3. Combined Experimental and Theoretical Study on the Formation of the Elusive 2-Methyl-1-silacycloprop-2-enylidene Molecule under Single Collision Conditions via Reactions of the Silylidyne Radical (SiH; X(2)Π) with Allene (H2CCCH2; X(1)A1) and D4-Allene (D2CCCD2; X(1)A1).

    PubMed

    Yang, Tao; Dangi, Beni B; Maksyutenko, Pavlo; Kaiser, Ralf I; Bertels, Luke W; Head-Gordon, Martin

    2015-12-17

    The crossed molecular beam reactions of the ground-state silylidyne radical (SiH; X(2)Π) with allene (H2CCCH2; X(1)A1) and D4-allene (D2CCCD2; X(1)A1) were carried out at collision energies of 30 kJ mol(-1). Electronic structure calculations propose that the reaction of silylidyne with allene has no entrance barrier and is initiated by silylidyne addition to the π electron density of allene either to one carbon atom (C1/C2) or to both carbon atoms simultaneously via indirect (complex forming) reaction dynamics. The initially formed addition complexes isomerize via two distinct reaction pathways, both leading eventually to a cyclic SiC3H5 intermediate. The latter decomposes through a loose exit transition state via an atomic hydrogen loss perpendicularly to the plane of the decomposing complex (sideways scattering) in an overall exoergic reaction (experimentally: -19 ± 13 kJ mol(-1); computationally: -5 ± 3 kJ mol(-1)). This hydrogen loss yields the hitherto elusive 2-methyl-1-silacycloprop-2-enylidene molecule (c-SiC3H4), which can be derived from the closed-shell cyclopropenylidene molecule (c-C3H2) by replacing a hydrogen atom with a methyl group and the carbene carbon atom by the isovalent silicon atom. The synthesis of the 2-methyl-1-silacycloprop-2-enylidene molecule in the bimolecular gas-phase reaction of silylidyne with allene enriches our understanding toward the formation of organosilicon species in the gas phase of the interstellar medium in particular via exoergic reactions of no entrance barrier. This facile route to 2-methyl-1-silacycloprop-2-enylidene via a silylidyne radical reaction with allene opens up a versatile approach to form hitherto poorly characterized silicon-bearing species in extraterrestrial environments; this reaction class might represent the missing link, leading from silicon-bearing radicals via organosilicon chemistry eventually to silicon-carbon-rich interstellar grains even in cold molecular clouds where temperatures are as

  4. Cu(II)-Gd(III) cryogenic magnetic refrigerants and Cu8Dy9 single-molecule magnet generated by in situ reactions of picolinaldehyde and acetylpyridine: experimental and theoretical study.

    PubMed

    Liu, Jun-Liang; Lin, Wei-Quan; Chen, Yan-Cong; Gómez-Coca, Silvia; Aravena, Daniel; Ruiz, Eliseo; Leng, Ji-Dong; Tong, Ming-Liang

    2013-12-16

    A series of heterometallic [Ln(III)(x)Cu(II)(y)] complexes, [Gd2Cu2]n (1), [Gd4Cu8] (2), [Ln9Cu8] (Ln=Gd, 3·Gd; Ln=Dy, 3·Dy), were successfully synthesized by a one-pot route at room temperature with three kinds of in situ carbonyl-related reactions: Cannizzaro reaction, aldol reaction, and oxidation. This strategy led to dysprosium analogues that behaved as single-molecule magnets (SMMs) and gadolinium analogues that showed significant magnetocaloric effect (MCE). In this study a numerical DFT approach is proposed by using pseudopotentials to calculate the exchange coupling constants in three polynuclear [Gd(x)Cu(y)] complexes; with these values exact diagonalization or quantum Monte Carlo simulations have been performed to calculate the variation of the magnetic entropy involved in the MCE. For the [Dy9Cu8] complexes, local magnetic properties of the Dy(III) centers have been determined by using the CASSCF+RASSI method.

  5. Surface treatment of poly(ethylene terephthalate) by gamma-ray induced graft copolymerization of methyl acrylate and its toughening effect on poly(ethylene terephthalate)/elastomer blend

    NASA Astrophysics Data System (ADS)

    Ma, Liang; Wang, Mozhen; Ge, Xuewu

    2013-09-01

    To improve the compatibility between ethylene-methyl acrylate-glycidyl methacrylate random terpolymer (E-MA-GMA) elastomer and poly(ethylene terephthalate) (PET), thereby enhance the toughening effect of E-MA-GMA on PET, γ-radiation-induced graft copolymerization technique was used to graft methyl acrylate (MA) monomer onto PET. The produced PET-g-PMA copolymer can be used as a self-compatibilizer in PET/E-MA-GMA blend since the copolymer contains the same segments, respectively, with PET and E-MA-GMA. The impact strength of PET/E-MA-GMA blend increased nearly by 30% in the presence of less than 0.1 wt% PET-g-PMA compared with that of the neat PET/elastomer blend, without loss of the tensile strength of the blends. This work proposed a potential application of radiation-induced grafting copolymerization technique on the in-situ compatibilization of PET/elastomer blends so as to improve the integral mechanical properties of PET based engineering plastic.

  6. Reactions of Monomeric [1,2,4-(Me3C)3C5H2]2CeH and CO with orwithout H2:An Experimental and Computational Study

    SciTech Connect

    Werkema, Evan L.; Maron, Laurent; Eisenstein, Odile; Andersen,Richard A.

    2006-09-07

    Addition of CO to [1,2,4-(Me3C)3C5H2]2CeH, Cp'2CeH, intoluene yields the cis (Cp'2Ce)2(mu-OCHCHO), in which the cis enediolategroup bridges the two metallocene fragments. The cis enediolatequantitatively isomerizes intramolecularly to the trans-enediolate inC6D6 at 100oC over seven months. When the solvent is pentane,Cp'2Ce(OCH2)CeCp'2 forms, in which the oxomethylene group or theformaldehyde dianion bridges the two metallocene fragments. The cisenediolate is suggested to form by insertion of CO into the Ce-C bond ofCp'2Ce(OCH2)CeCp'2 generating Cp'2CeOCH2COCeCp'2. The stereochemistry ofthe cis-enediolate is determined by a 1,2-hydrogen shift in the OCH2COfragment that has the OC(H2) bond anti periplanar relative to the carbenelone pair. The bridging oxomethylene complex reacts with H2, but not withCH4, to give Cp'2CeOMe, which is also the product of the reaction betweenCp'2CeH and a mixture of CO and H2. The oxomethylene complex reacts withCO to give the cis enediolate complex. DFT calculations on C5H5 modelmetallocenes show that the reaction of Cp2CeH with CO and H2 to giveCp2CeOMe is exoergic by 50 kcal mol-1. The net reaction proceeds by aseries of elementary reactions that occur after the formyl complex,Cp2Ce(eta-2 CHO), is formed by further reaction with H2. The key pointthat emerges from the calculated potential energy surface is thebifunctional nature of the metal formyl in which the carbon atom behavesas a donor and acceptor. Replacing H2 by CH4 increases the activationenergy barrier by 17 kcal mol-1.

  7. Copolymerization of dibenzofuran and dichloromethane

    SciTech Connect

    Rao, S.P.; Jones, M.B.; Baltisberger, R.J.; Brown, C.E.; Burger, V.T.

    1983-01-01

    As part of a project involving synthesis of model oligomers of coal derived asphaltenes and preasphaltenes, we required bis(2-dibenzofuranyl)methane (1). The successful preparation of 1 was carried out via coupling of 2-lithio-dibenzofuran with 2-formyldibenzofuran, followed by reduction of the resulting diaryl substituted methanol. Attempts to prepare 1 by Friedel-Crafts alkylation of dibenzofuran (DBF) with stoichiometric amounts of CH/sub 2/Cl/sub 2/ failed. However, when CH/sub 2/Cl/sub 2/ was present in excess (as solvent), alkylation of DBF proceeded smoothly at ambient temperature to yield an insoluble, infusible, yellow powder. We report herein preliminary observations on the characteristics and structural features of this new copolymer.

  8. Guidelines for measuring reaction time.

    PubMed

    Crabtree, D A; Antrim, L R

    1988-04-01

    Although reaction time is one of the most common measures of neurological function, protocols often do not take into consideration many of the extraneous factors that may invalidate such assessments. This paper discusses several issues related to matters of instrumentation, subject control, design of assessment, and interpretation. Twenty recommendations are provided as a guideline for those who assess reaction time of clients or patients. While these suggestions are not proposed as definitive or complete, the points should serve as a guide to young researchers as well as a checklist for more seasoned experimenters.

  9. Study of char gasification reactions

    SciTech Connect

    Ballal, G.D.

    1986-01-01

    A Texas lignite, an anthracite and two bituminous coals, Pittsburgh number8 and Illinois number6, were pyrolyzed in a nitrogen atmosphere to prepare chars. Optical microscopy, mercury porosimetry and gas adsorption techniques using nitrogen, CO/sub 2/ and CO, were employed for pore structure characterization. The lignite char exhibited the fastest rates of gaseous diffusion, followed in order of decreasing diffusivities by the Illinois number6, Pittsburgh number8 and anthracite chars. The changes in reactivities and pore structures of chars were measured experimentally during their reaction with oxygen (400-550C) and CO/sub 2/ (800-1000C). For a particular char-gas system, the normalized rate-conversion pattern was invariant with respect to temperature and gaseous concentration. In the case of lignite and Pittsburgh number8 chars, the rate-conversion pattern was similar during reaction with oxygen and CO/sub 2/. Adsorption experiments on partially reacted chars indicated that the micropores in the lignite char were accessible to both reactants. The micropores in the Illinois number6 char were, however, not accessible during its reaction with oxygen. The evolution of pore structure during reaction was modeled by using a probabilistic approach which accounts for overlapping pores with different shapes and sizes. The kinetics of gasification of the lignite and the Pittsburgh number8 chars was studied using a Langmuir-Hinshelwood type kinetic expression to correlate the experimental data. CO was found to inhibit the reaction substantially. The effect of a potassium carbonate catalyst on the reaction of these two chars was also investigated. Substantial increases in reaction rates were observed, and the enhancement was approximately proportional to the catalyst loading.

  10. A Combined Experimental and Theoretical Study on the Formation of the 2-Methyl-1-silacycloprop-2-enylidene Molecule via the Crossed Beam Reactions of the Silylidyne Radical (SiH; X(2)Π) with Methylacetylene (CH3CCH; X(1)A1) and D4-Methylacetylene (CD3CCD; X(1)A1).

    PubMed

    Yang, Tao; Dangi, Beni B; Kaiser, Ralf I; Bertels, Luke W; Head-Gordon, Martin

    2016-07-14

    The bimolecular gas-phase reactions of the ground-state silylidyne radical (SiH; X(2)Π) with methylacetylene (CH3CCH; X(1)A1) and D4-methylacetylene (CD3CCD; X(1)A1) were explored at collision energies of 30 kJ mol(-1) under single-collision conditions exploiting the crossed molecular beam technique and complemented by electronic structure calculations. These studies reveal that the reactions follow indirect scattering dynamics, have no entrance barriers, and are initiated by the addition of the silylidyne radical to the carbon-carbon triple bond of the methylacetylene molecule either to one carbon atom (C1; [i1]/[i2]) or to both carbon atoms concurrently (C1-C2; [i3]). The collision complexes [i1]/[i2] eventually isomerize via ring-closure to the c-SiC3H5 doublet radical intermediate [i3], which is identified as the decomposing reaction intermediate. The hydrogen atom is emitted almost perpendicularly to the rotational plane of the fragmenting complex resulting in a sideways scattering dynamics with the reaction being overall exoergic by -12 ± 11 kJ mol(-1) (experimental) and -1 ± 3 kJ mol(-1) (computational) to form the cyclic 2-methyl-1-silacycloprop-2-enylidene molecule (c-SiC3H4; p1). In line with computational data, experiments of silylidyne with D4-methylacetylene (CD3CCD; X(1)A1) depict that the hydrogen is emitted solely from the silylidyne moiety but not from methylacetylene. The dynamics are compared to those of the related D1-silylidyne (SiD; X(2)Π)-acetylene (HCCH; X(1)Σg(+)) reaction studied previously in our group, and from there, we discovered that the methyl group acts primarily as a spectator in the title reaction. The formation of 2-methyl-1-silacycloprop-2-enylidene under single-collision conditions via a bimolecular gas-phase reaction augments our knowledge of the hitherto poorly understood silylidyne (SiH; X(2)Π) radical reactions with small hydrocarbon molecules leading to the synthesis of organosilicon molecules in cold molecular

  11. Visualization of chemical reaction dynamics: Toward understanding complex polyatomic reactions

    PubMed Central

    SUZUKI, Toshinori

    2013-01-01

    Polyatomic molecules have several electronic states that have similar energies. Consequently, their chemical dynamics often involve nonadiabatic transitions between multiple potential energy surfaces. Elucidating the complex reactions of polyatomic molecules is one of the most important tasks of theoretical and experimental studies of chemical dynamics. This paper describes our recent experimental studies of the multidimensional multisurface dynamics of polyatomic molecules based on two-dimensional ion/electron imaging. It also discusses ultrafast photoelectron spectroscopy of liquids for elucidating nonadiabatic electronic dynamics in aqueous solutions. PMID:23318678

  12. Serpentinization reaction pathways: implications for modeling approach

    SciTech Connect

    Janecky, D.R.

    1986-01-01

    Experimental seawater-peridotite reaction pathways to form serpentinites at 300/sup 0/C, 500 bars, can be accurately modeled using the EQ3/6 codes in conjunction with thermodynamic and kinetic data from the literature and unpublished compilations. These models provide both confirmation of experimental interpretations and more detailed insight into hydrothermal reaction processes within the oceanic crust. The accuracy of these models depends on careful evaluation of the aqueous speciation model, use of mineral compositions that closely reproduce compositions in the experiments, and definition of realistic reactive components in terms of composition, thermodynamic data, and reaction rates.

  13. Catalysis of Photochemical Reactions.

    ERIC Educational Resources Information Center

    Albini, A.

    1986-01-01

    Offers a classification system of catalytic effects in photochemical reactions, contrasting characteristic properties of photochemical and thermal reactions. Discusses catalysis and sensitization, examples of catalyzed reactions of excepted states, complexing ground state substrates, and catalysis of primary photoproducts. (JM)

  14. Effects of small-scale chemical reactions between supercritical CO2 and arkosic sandstone on large-scale permeability fields: An experimental study with implications for geologic carbon sequestration

    NASA Astrophysics Data System (ADS)

    Luhmann, A. J.; Ding, K.; Saar, M. O.; Seyfried, W. E.

    2011-12-01

    During geologic carbon sequestration, small, pore-scale changes in mineralogy due to dissolution and precipitation reactions can modify bulk porosity. Porosity/permeability relationships are then typically used to infer large-scale permeability field changes. However, these relationships have limited use because they do not account for changes in pore geometry. Therefore, in connection with a DOE sponsored program, involving CO2 sequestration with geothermal energy usage, we constructed a novel hydrothermal flow system that allows simultaneous determination of changes in fluid chemistry and associated changes in permeability at elevated temperatures and high CO2 pressure. Initial experiments were conducted with an arkosic sandstone core of the Eau Claire Formation from southeastern Minnesota. The core was disaggregated and then wet sieved to yield a grain size distribution of 90-120 μm that was used to fill the Teflon sleeve held within the stainless steel pressure vessel. Initial water chemistry consisted of CO2 dissolved in deionized water. Outlet pressure was set to 11 MPa, and confinement pressure was 20 MPa. Flow rates produced inlet pressures between these two extremes, allowing CO2 solubility up to 1.1 mol/kg water. Rates of fluid flow ranged from 0.04 to 1.5 mL/min at a temperature of 21°C over the course of 33 days. Based on these data, the in-situ permeability of ~1E-14 to 9E-14 m2 for the arkosic sandstone was calculated. The reaction cell temperature was then increased to 50°C, and eventually 100°C. Each temperature step was associated with a sharp decrease in permeability, such that at 100°C the permeability had decreased by approximately three orders of magnitude from the starting condition. Fluid samples indicate release of dissolved Na, Ca, Mg, K, Al, SiO2, and Cl from minerals in the core, suggesting dissolution of primary mineral components. Charge balance constraints indicate a pH of approximately 4.2 at the highest temperature run condition

  15. Effect of reactions in small eddies on biomass gasification with eddy dissipation concept - Sub-grid scale reaction model.

    PubMed

    Chen, Juhui; Yin, Weijie; Wang, Shuai; Meng, Cheng; Li, Jiuru; Qin, Bai; Yu, Guangbin

    2016-07-01

    Large-eddy simulation (LES) approach is used for gas turbulence, and eddy dissipation concept (EDC)-sub-grid scale (SGS) reaction model is employed for reactions in small eddies. The simulated gas molar fractions are in better agreement with experimental data with EDC-SGS reaction model. The effect of reactions in small eddies on biomass gasification is emphatically analyzed with EDC-SGS reaction model. The distributions of the SGS reaction rates which represent the reactions in small eddies with particles concentration and temperature are analyzed. The distributions of SGS reaction rates have the similar trend with those of total reactions rates and the values account for about 15% of the total reactions rates. The heterogeneous reaction rates with EDC-SGS reaction model are also improved during the biomass gasification process in bubbling fluidized bed.

  16. Effect of reactions in small eddies on biomass gasification with eddy dissipation concept - Sub-grid scale reaction model.

    PubMed

    Chen, Juhui; Yin, Weijie; Wang, Shuai; Meng, Cheng; Li, Jiuru; Qin, Bai; Yu, Guangbin

    2016-07-01

    Large-eddy simulation (LES) approach is used for gas turbulence, and eddy dissipation concept (EDC)-sub-grid scale (SGS) reaction model is employed for reactions in small eddies. The simulated gas molar fractions are in better agreement with experimental data with EDC-SGS reaction model. The effect of reactions in small eddies on biomass gasification is emphatically analyzed with EDC-SGS reaction model. The distributions of the SGS reaction rates which represent the reactions in small eddies with particles concentration and temperature are analyzed. The distributions of SGS reaction rates have the similar trend with those of total reactions rates and the values account for about 15% of the total reactions rates. The heterogeneous reaction rates with EDC-SGS reaction model are also improved during the biomass gasification process in bubbling fluidized bed. PMID:27010338

  17. Vibrational excitation induces double reaction.

    PubMed

    Huang, Kai; Leung, Lydie; Lim, Tingbin; Ning, Zhanyu; Polanyi, John C

    2014-12-23

    Electron-induced reaction at metal surfaces is currently the subject of extensive study. Here, we broaden the range of experimentation to a comparison of vibrational excitation with electronic excitation, for reaction of the same molecule at the same clean metal surface. In a previous study of electron-induced reaction by scanning tunneling microscopy (STM), we examined the dynamics of the concurrent breaking of the two C-I bonds of ortho-diiodobenzene physisorbed on Cu(110). The energy of the incident electron was near the electronic excitation threshold of E0=1.0 eV required to induce this single-electron process. STM has been employed in the present work to study the reaction dynamics at the substantially lower incident electron energies of 0.3 eV, well below the electronic excitation threshold. The observed increase in reaction rate with current was found to be fourth-order, indicative of multistep reagent vibrational excitation, in contrast to the first-order rate dependence found earlier for electronic excitation. The change in mode of excitation was accompanied by altered reaction dynamics, evidenced by a different pattern of binding of the chemisorbed products to the copper surface. We have modeled these altered reaction dynamics by exciting normal modes of vibration that distort the C-I bonds of the physisorbed reagent. Using the same ab initio ground potential-energy surface as in the prior work on electronic excitation, but with only vibrational excitation of the physisorbed reagent in the asymmetric stretch mode of C-I bonds, we obtained the observed alteration in reaction dynamics.

  18. Photonuclear reactions on titanium isotopes

    SciTech Connect

    Belyshev, S. S.; Dzhilavyan, L. Z.; Ishkhanov, B. S.; Kapitonov, I. M.; Kuznetsov, A. A. Orlin, V. N.; Stopani, K. A.

    2015-03-15

    The photodisintegration of titanium isotopes in the giant-dipole-resonance energy region is studied by the photon-activation method. Bremsstrahlung photons whose spectrum has the endpoint energy of 55 MeV is used. The yields and integrated cross sections are determined for photoproton reactions on the titanium isotopes {sup 47,48,49,50}Ti. The respective experimental results are compared with their counterparts calculated on the basis of the TALYS code and a combined photonucleon-reaction model. The TALYS code disregards the isospin structure of the giant dipole resonance and is therefore unable to describe the yield of photoproton reactions on the heavy titanium isotopes {sup 49,50}Ti.

  19. An experimental and theoretical study on the formation of 2-methylnaphthalene (C11H10/C11H3D7) in the reactions of the para-tolyl (C7H7) and para-tolyl-d7 (C7D7) with vinylacetylene (C4H4).

    PubMed

    Parker, Dorian S N; Dangi, Beni B; Kaiser, Ralf I; Jamal, Adeel; Ryazantsev, Mikhail N; Morokuma, Keiji; Korte, André; Sander, Wolfram

    2014-04-17

    We present for the very first time single collision experimental evidence that a methyl-substituted polycyclic aromatic hydrocarbon (PAH)-2-methylnaphthalene-can be formed without an entrance barrier via indirect scattering dynamics through a bimolecular collision of two non-PAH reactants: the para-tolyl radical and vinylacetylene. Theory shows that this reaction is initiated by the addition of the para-tolyl radical to either the terminal acetylene carbon (C(4)) or a vinyl carbon (C(1)) leading eventually to two distinct radical intermediates. Importantly, addition at C(1) was found to be barrierless via a van der Waals complex implying this mechanism can play a key role in forming methyl substituted PAHs in low temperature extreme environments such as the interstellar medium and hydrocarbon-rich atmospheres of planets and their moons in the outer Solar System. Both reaction pathways involve a sequence of isomerizations via hydrogen transfer, ring closure, ring-opening and final hydrogen dissociation through tight exit transition states to form 2-methylnaphthalene in an overall exoergic process. Less favorable pathways leading to monocyclic products are also found. Our studies predict that reactions of substituted aromatic radicals can mechanistically deliver odd-numbered PAHs which are formed in significant quantities in the combustion of fossil fuels. PMID:24646186

  20. Experimental study on weathering of seafloor volcanic glass by bacteria (Pseudomonas fluorescens) - Implications for the contribution of bacteria to the wate-rock reaction at the Mid-Oceanic Ridge setting

    NASA Astrophysics Data System (ADS)

    Chen, Shun; Wu, Zijun; Peng, Xiaotong

    2014-08-01

    The biologically mediated weathering of the ocean crust has received increasing attention in recent decades, but the rates and the possible mechanism of elemental release during microbe-basalt interactions occurring below the seafloor have not been studied in detail. In this study, we established an experimental weathering study of seafloor natural basaltic glass comparing the effect of microbial activity (Pseudomonas fluorescens) in P-rich and P-poor media with parallel controls containing either nonviable cells or organic acid. The changes in the chemical parameters, including pH, bacterial densities, and ion concentrations (Ca, Mg, Si, Mn, Al, Fe, and P) in the solution, were examined during the different batch experiments. The results showed that the pH decreased from 7.0 to 3.5 and the bacterial density increased from 105 to 108 cells/ml during the first 120 h, and the cell numbers remained constant at 108 cells/ml and the pH increased from 3.5 to 6 between 120 h and 864 h in the P-bearing reactors containing bacteria. In contrast, during all the experimental time, the pH remained close to neutral condition in the abiotic control systems and the dissolution rates increased markedly with a decrease in pH and became minimal at near-neutral pH in P-bearing reactors containing bacteria, where Ca, Si, and Mg release rates were 2- to 4-fold higher than those obtained in chemical systems and biotic P-limited systems. Furthermore, the surfaces of the natural volcanic glass from the biotic systems were colonized by bacteria. Simultaneously, the etch pits were observed by Scanning Electron Microscope, which further indicate that the bacteria may promote the mineral dissolution for energy gain. Some elements (e.g., Fe, Mn, and Al) releasing from natural volcanic glass are likely an important source of the elemental budget in the ocean, and thus the element release and its possible mechanism conducted in this experimental study have potential implications on the

  1. Combustion kinetics and reaction pathways

    SciTech Connect

    Klemm, R.B.; Sutherland, J.W.

    1993-12-01

    This project is focused on the fundamental chemistry of combustion. The overall objectives are to determine rate constants for elementary reactions and to elucidate the pathways of multichannel reactions. A multitechnique approach that features three independent experiments provides unique capabilities in performing reliable kinetic measurements over an exceptionally wide range in temperature, 300 to 2500 K. Recent kinetic work has focused on experimental studies and theoretical calculations of the methane dissociation system (CH{sub 4} + Ar {yields} CH{sub 3} + H + Ar and H + CH{sub 4} {yields} CH{sub 3} + H{sub 2}). Additionally, a discharge flow-photoionization mass spectrometer (DF-PIMS) experiment is used to determine branching fractions for multichannel reactions and to measure ionization thresholds of free radicals. Thus, these photoionization experiments generate data that are relevant to both reaction pathways studies (reaction dynamics) and fundamental thermochemical research. Two distinct advantages of performing PIMS with high intensity, tunable vacuum ultraviolet light at the National Synchrotron Light Source are high detection sensitivity and exceptional selectivity in monitoring radical species.

  2. Nonlocality in deuteron stripping reactions.

    PubMed

    Timofeyuk, N K; Johnson, R C

    2013-03-15

    We propose a new method for the analysis of deuteron stripping reactions, A(d,p)B, in which the nonlocality of nucleon-nucleus interactions and three-body degrees of freedom are accounted for in a consistent way. The model deals with equivalent local nucleon potentials taken at an energy shifted by ∼40  MeV from the "E(d)/2" value frequently used in the analysis of experimental data, where E(d) is the incident deuteron energy. The "E(d)/2" rule lies at the heart of all three-body analyses of (d, p) reactions performed so far with the aim of obtaining nuclear structure properties such as spectroscopic factors and asymptotic normalization coefficients that are crucial for our understanding of nuclear shell evolution in neutron- and proton-rich regions of the nuclear periodic table and for predicting the cross sections of stellar reactions. The large predicted shift arises from the large relative kinetic energy of the neutron and proton in the incident deuteron in those components of the n+p+A wave function that dominate the (d, p) reaction amplitude. The large shift reduces the effective d-A potentials and leads to a change in predicted (d, p) cross sections, thus affecting the interpretation of these reactions in terms of nuclear structure. PMID:25166525

  3. Method of uranium reclamation from aqueous systems by reactive ion exchange. [US DOE patent application; anion exchange resin of copolymerized divinyl-benzene and styrene having quarternary ammonium groups and bicarbonate ligands

    DOEpatents

    Maya, L.

    1981-11-05

    A reactive ion exchange method for separation and recovery of values of uranium, neptunium, plutonium, or americium from substantially neutral aqueous systems of said metals comprises contacting said system with an effective amount of a basic anion exchange resin of copolymerized divinyl-benzene and styrene having quarternary ammonium groups and bicarbonate ligands to achieve nearly 100% sorption of said actinyl ion onto said resin and an aqueous system practically free of said actinyl ions. The method is operational over an extensive range of concentrations from about 10/sup -6/ M to 1.0 M actinyl ion and a pH range of about 4 to 7. The method has particulr application to treatment of waste streams from Purex-type nuclear fuel reprocessing facilities and hydrometallurgical processes involving U, Np, P, or Am.

  4. Clinical Pearls: Leprosy Reactions.

    PubMed

    Wu, Jane; Boggild, Andrea K

    2016-09-01

    Leprosy reactions are acute inflammatory episodes that occur in the setting of Mycobacterium leprae infection. Precipitants of reactions can be pharmacologic and nonpharmacologic. Both type 1 and type 2 reactions typically occur before and during leprosy treatment but may also occur after treatment has been completed. Reactions cause morbidity due to nerve damage, and prompt corticosteroid therapy is warranted to minimize nerve damage due to reactions.

  5. Multicomponent reactions of cyclobutanones.

    PubMed

    Pirrung, Michael C; Wang, Jianmei

    2009-04-17

    Cyclobutanones are essentially unknown as reactants in isonitrile-based multicomponent reactions. Ugi reactions of cyclobutanone and Passerini reactions of tetramethylcyclobutane-1,3-dione have been performed in this work. These reactions are significantly enhanced by being conducted in water, a subject of recent interest whose basis is still in question but whose effects are beyond doubt. The Ugi reaction of cyclobutanone has been used in a brief synthesis of an aspartame analogue.

  6. Reaction Coordinates and Mechanistic Hypothesis Tests.

    PubMed

    Peters, Baron

    2016-05-27

    Reaction coordinates are integral to several classic rate theories that can (a) predict kinetic trends across conditions and homologous reactions, (b) extract activation parameters with a clear physical interpretation from experimental rates, and (c) enable efficient calculations of free energy barriers and rates. New trajectory-based rare events methods can provide rates directly from dynamical trajectories without a reaction coordinate. Trajectory-based frameworks can also generate ideal (but abstract) reaction coordinates such as committors and eigenfunctions of the master equation. However, rates and mechanistic insights obtained from trajectory-based methods and abstract coordinates are not readily generalized across simulation conditions or reaction families. We discuss methods for identifying physically meaningful reaction coordinates, including committor analysis, variational transition state theory, Kramers-Langer-Berezhkovskii-Szabo theory, and statistical inference methods that can use path sampling data to screen, mix, and optimize thousands of trial coordinates. Special focus is given to likelihood maximization and inertial likelihood maximization approaches.

  7. Reaction Coordinates and Mechanistic Hypothesis Tests

    NASA Astrophysics Data System (ADS)

    Peters, Baron

    2016-05-01

    Reaction coordinates are integral to several classic rate theories that can (a) predict kinetic trends across conditions and homologous reactions, (b) extract activation parameters with a clear physical interpretation from experimental rates, and (c) enable efficient calculations of free energy barriers and rates. New trajectory-based rare events methods can provide rates directly from dynamical trajectories without a reaction coordinate. Trajectory-based frameworks can also generate ideal (but abstract) reaction coordinates such as committors and eigenfunctions of the master equation. However, rates and mechanistic insights obtained from trajectory-based methods and abstract coordinates are not readily generalized across simulation conditions or reaction families. We discuss methods for identifying physically meaningful reaction coordinates, including committor analysis, variational transition state theory, Kramers-Langer-Berezhkovskii-Szabo theory, and statistical inference methods that can use path sampling data to screen, mix, and optimize thousands of trial coordinates. Special focus is given to likelihood maximization and inertial likelihood maximization approaches.

  8. Resin-Immobilized Palladium Nanoparticle Catalysts for Organic Reactions in Aqueous Media: Morphological Aspects.

    PubMed

    Mastrorilli, Piero; Dell'Anna, Maria M; Rizzuti, Antonino; Mali, Matilda; Zapparoli, Mauro; Leonelli, Cristina

    2015-01-01

    An insight into the nano- and micro-structural morphology of a polymer supported Pd catalyst employed in different catalytic reactions under green conditions is reported. The pre-catalyst was obtained by copolymerization of the metal-containing monomer Pd(AAEMA)₂ [AAEMA-=deprotonated form of 2-(acetoacetoxy) ethyl methacrylate] with ethyl methacrylate as co-monomer, and ethylene glycol dimethacrylate as cross-linker. This material was used in water for the Suzuki-Miyaura cross-coupling of aryl bromides, and for the reduction of nitroarenes and quinolines using NaBH₄ or H₂, as reductants. TEM analyses showed that in all cases the pristine Pd(II) species were reduced in situ to Pd(0), which formed metal nanoparticles (NPs, the real active species). The dependence of their average size (2-10 nm) and morphology on different parameters (temperature, reducing agent, presence of a phase transfer agent) is discussed. TEM and micro-IR analyses showed that the polymeric support retained its porosity and stability for several catalytic cycles in all reactions and Pd NPs did not aggregate after reuse. The metal nanoparticle distribution throughout the polymer matrix after several recycles provided precious information about the catalytic mechanism, which was truly heterogeneous in the hydrogenation reactions and of the so-called "release and catch" type in the Suzuki coupling. PMID:26473823

  9. Resin-Immobilized Palladium Nanoparticle Catalysts for Organic Reactions in Aqueous Media: Morphological Aspects.

    PubMed

    Mastrorilli, Piero; Dell'Anna, Maria M; Rizzuti, Antonino; Mali, Matilda; Zapparoli, Mauro; Leonelli, Cristina

    2015-10-14

    An insight into the nano- and micro-structural morphology of a polymer supported Pd catalyst employed in different catalytic reactions under green conditions is reported. The pre-catalyst was obtained by copolymerization of the metal-containing monomer Pd(AAEMA)₂ [AAEMA-=deprotonated form of 2-(acetoacetoxy) ethyl methacrylate] with ethyl methacrylate as co-monomer, and ethylene glycol dimethacrylate as cross-linker. This material was used in water for the Suzuki-Miyaura cross-coupling of aryl bromides, and for the reduction of nitroarenes and quinolines using NaBH₄ or H₂, as reductants. TEM analyses showed that in all cases the pristine Pd(II) species were reduced in situ to Pd(0), which formed metal nanoparticles (NPs, the real active species). The dependence of their average size (2-10 nm) and morphology on different parameters (temperature, reducing agent, presence of a phase transfer agent) is discussed. TEM and micro-IR analyses showed that the polymeric support retained its porosity and stability for several catalytic cycles in all reactions and Pd NPs did not aggregate after reuse. The metal nanoparticle distribution throughout the polymer matrix after several recycles provided precious information about the catalytic mechanism, which was truly heterogeneous in the hydrogenation reactions and of the so-called "release and catch" type in the Suzuki coupling.

  10. A review of reaction rates in high temperature air

    NASA Technical Reports Server (NTRS)

    Park, Chul

    1989-01-01

    The existing experimental data on the rate coefficients for the chemical reactions in nonequilibrium high temperature air are reviewed and collated, and a selected set of such values is recommended for use in hypersonic flow calculations. For the reactions of neutral species, the recommended values are chosen from the experimental data that existed mostly prior to 1970, and are slightly different from those used previously. For the reactions involving ions, the recommended rate coefficients are newly chosen from the experimental data obtained more recently. The reacting environment is assumed to lack thermal equilibrium, and the rate coefficients are expressed as a function of the controlling temperature, incorporating the recent multitemperature reaction concept.

  11. A simple reaction-rate model for turbulent diffusion flames

    NASA Technical Reports Server (NTRS)

    Bangert, L. H.

    1975-01-01

    A simple reaction rate model is proposed for turbulent diffusion flames in which the reaction rate is proportional to the turbulence mixing rate. The reaction rate is also dependent on the mean mass fraction and the mean square fluctuation of mass fraction of each reactant. Calculations are compared with experimental data and are generally successful in predicting the measured quantities.

  12. A study of the Sabatier-methanation reaction kinetics

    NASA Technical Reports Server (NTRS)

    Verostko, C. E.; Forsythe, R. K.

    1974-01-01

    The kinetics of the Sabatier methanation reaction, the reduction of carbon dioxide with hydrogen to methane and water, was investigated for 58 percent nickel on kieselguhr catalyst and 20 percent ruthenium on alumina catalyst. Differential rate data from an experimental program were correlated with a power function rate equation both for forward and reverse reactions. The kinetic parameters of activation energy, frequency rate constant and reaction order were determined for the rate equation. The values of these parameters were obtained from an Arrhenius plot of the experimental differential rate data. Also the carbon monoxide side reaction effect was measured and included in the correlation of parameters. The reaction was found to fit the rate equation experimentally within the temperature range 421 K, where the reaction effectively begins, the 800 K where the reaction rate drops and departs from the rate equation form.

  13. Experimental Pi.

    ERIC Educational Resources Information Center

    Corris, G.

    1990-01-01

    Discusses the calculation of pi by means of experimental methods. Polygon circle ratios, Archimedes' method, Buffon's needles, a Monte Carlo method, and prime number approaches are used. Presents three BASIC programs for the calculations. (YP)

  14. Microscale Thermite Reactions.

    ERIC Educational Resources Information Center

    Arnaiz, Francisco J.; Aguado, Rafael; Arnaiz, Susana

    1998-01-01

    Describes the adaptation of thermite (aluminum with metal oxides) reactions from whole-class demonstrations to student-run micro-reactions. Lists detailed directions and possible variations of the experiment. (WRM)

  15. Allergic reactions (image)

    MedlinePlus

    Allergic reaction can be provoked by skin contact with poison plants, chemicals and animal scratches, as well as by ... dust, nuts and shellfish, may also cause allergic reaction. Medications such as penicillin and other antibiotics are ...

  16. Allergic reactions (image)

    MedlinePlus

    Allergic reaction is a sensitivity to a specific substance, called an allergen, that is contacted through the skin, inhaled into the lungs, swallowed or injected. The body's reaction to an allergen can be mild, such as ...

  17. Microfluidic chemical reaction circuits

    DOEpatents

    Lee, Chung-cheng; Sui, Guodong; Elizarov, Arkadij; Kolb, Hartmuth C.; Huang, Jiang; Heath, James R.; Phelps, Michael E.; Quake, Stephen R.; Tseng, Hsian-rong; Wyatt, Paul; Daridon, Antoine

    2012-06-26

    New microfluidic devices, useful for carrying out chemical reactions, are provided. The devices are adapted for on-chip solvent exchange, chemical processes requiring multiple chemical reactions, and rapid concentration of reagents.

  18. Continuous detonation reaction engine

    NASA Technical Reports Server (NTRS)

    Lange, O. H.; Stein, R. J.; Tubbs, H. E.

    1968-01-01

    Reaction engine operates on the principles of a controlled condensed detonation rather than on the principles of gas expansion. The detonation results in reaction products that are expelled at a much higher velocity.

  19. Special Relativity and Reactions with Unstable Nuclei

    SciTech Connect

    Bertulani, C.A.

    2005-10-14

    Dynamical relativistic effects are often neglected in the description of reactions with unstable nuclear beams at intermediate energies (ELab {approx_equal} 100 MeV/nucleon). Evidently, this introduces sizable errors in experimental analysis and theoretical descriptions of these reactions. This is particularly important for the experiments held in GANIL/France, MSU/USA, RIKEN/Japan and GSI/Germany. I review a few examples where relativistic effects have been studied in nucleus-nucleus scattering at intermediate energies.

  20. Catalytic diastereoselective petasis reactions.

    PubMed

    Muncipinto, Giovanni; Moquist, Philip N; Schreiber, Stuart L; Schaus, Scott E

    2011-08-22

    Multicomponent Petasis reactions: the first diastereoselective Petasis reaction catalyzed by chiral biphenols that enables the synthesis of syn and anti β-amino alcohols in pure form has been developed. The reaction exploits a multicomponent approach that involves boronates, α-hydroxy aldehydes, and amines. PMID:21751322

  1. Convenience experimentation.

    PubMed

    Krohs, Ulrich

    2012-03-01

    Systems biology aims at explaining life processes by means of detailed models of molecular networks, mainly on the whole-cell scale. The whole cell perspective distinguishes the new field of systems biology from earlier approaches within molecular cell biology. The shift was made possible by the high throughput methods that were developed for gathering 'omic' (genomic, proteomic, etc.) data. These new techniques are made commercially available as semi-automatic analytic equipment, ready-made analytic kits and probe arrays. There is a whole industry of supplies for what may be called convenience experimentation. My paper inquires some epistemic consequences of strong reliance on convenience experimentation in systems biology. In times when experimentation was automated to a lesser degree, modeling and in part even experimentation could be understood fairly well as either being driven by hypotheses, and thus proceed by the testing of hypothesis, or as being performed in an exploratory mode, intended to sharpen concepts or initially vague phenomena. In systems biology, the situation is dramatically different. Data collection became so easy (though not cheap) that experimentation is, to a high degree, driven by convenience equipment, and model building is driven by the vast amount of data that is produced by convenience experimentation. This results in a shift in the mode of science. The paper shows that convenience driven science is not primarily hypothesis-testing, nor is it in an exploratory mode. It rather proceeds in a gathering mode. This shift demands another shift in the mode of evaluation, which now becomes an exploratory endeavor, in response to the superabundance of gathered data.

  2. Curing behavior and reaction kinetics of binder resins for 3D-printing investigated by dielectric analysis (DEA)

    NASA Astrophysics Data System (ADS)

    Möginger, B.; Kehret, L.; Hausnerova, B.; Steinhaus, J.

    2016-05-01

    3D-Printing is an efficient method in the field of additive manufacturing. In order to optimize the properties of manufactured parts it is essential to adapt the curing behavior of the resin systems with respect to the requirements. Thus, effects of resin composition, e.g. due to different additives such as thickener and curing agents, on the curing behavior have to be known. As the resin transfers from a liquid to a solid glass the time dependent ion viscosity was measured using DEA with flat IDEX sensors. This allows for a sensitive measurement of resin changes as the ion viscosity changes two to four decades. The investigated resin systems are based on the monomers styrene and HEMA. To account for the effects of copolymerization in the calculation of the reaction kinetics it was assumed that the reaction can be considered as a homo-polymerization having a reaction order n≠1. Then the measured ion viscosity curves are fitted with the solution of the reactions kinetics - the time dependent degree of conversion (DC-function) - for times exceeding the initiation phase representing the primary curing. The measured ion viscosity curves can nicely be fitted with the DC-function and the determined fit parameters distinguish distinctly between the investigated resin compositions.

  3. Low-energy proton capture reactions

    SciTech Connect

    Lipoglavsek, M.; Cvetinovic, A.; Gajevic, J.; Likar, A.; Vavpetic, P.; Petrovic, T.

    2014-05-09

    An overview of experimental problems in measuring the cross sections for (p,γ) and (p,n) reactions at low energies is given with a specific emphasis on electron screening in metallic targets. Thick target γ-ray and neutron yields are compared for Ni and NiO targets, V and VO{sub 2} targets and Mn and MnO targets. The {sup 1}H({sup 7}Li,α){sup 4}He reaction was studied in inverse kinematics with hydrogen loaded into Pd and PdAg alloy foils from gas phase. Based on these results, a new approach to electron screening in nuclear reactions is suggested.

  4. On the Violence of High Explosive Reactions

    SciTech Connect

    Tarver, C M; Chidester, S K

    2004-02-09

    High explosive reactions can be caused by three general energy deposition processes: impact ignition by frictional and/or shear heating; bulk thermal heating; and shock compression. The violence of the subsequent reaction varies from benign slow combustion to catastrophic detonation of the entire charge. The degree of violence depends on many variables, including the rate of energy delivery, the physical and chemical properties of the explosive, and the strength of the confinement surrounding the explosive charge. The current state of experimental and computer modeling research on the violence of impact, thermal, and shock-induced reactions is reviewed.

  5. Experimental errors?

    NASA Astrophysics Data System (ADS)

    Downie, Neil; Turner, Jez

    2014-07-01

    In reply to Matin Durrani's article “Experimental mistake” (May p15, see also http://ow.ly/vDYlM) criticizing plans to base A-level science exams in England entirely on written tests, with practical skills noted as a separate grade.

  6. Integrating reaction and analysis: investigation of higher-order reactions by cryogenic trapping

    PubMed Central

    Stockinger, Skrollan

    2013-01-01

    Summary A new approach for the investigation of a higher-order reaction by on-column reaction gas chromatography is presented. The reaction and the analytical separation are combined in a single experiment to investigate the Diels–Alder reaction of benzenediazonium-2-carboxylate as a benzyne precursor with various anthracene derivatives, i.e. anthracene, 9-bromoanthracene, 9-anthracenecarboxaldehyde and 9-anthracenemethanol. To overcome limitations of short reaction contact times at elevated temperatures a novel experimental setup was developed involving a cooling trap to achieve focusing and mixing of the reactants at a defined spot in a fused-silica capillary. This trap functions as a reactor within the separation column in the oven of a gas chromatograph. The reactants are sequentially injected to avoid undefined mixing in the injection port. An experimental protocol was developed with optimized injection intervals and cooling times to achieve sufficient conversions at short reaction times. Reaction products were rapidly identified by mass spectrometric detection. This new approach represents a practical procedure to investigate higher-order reactions at an analytical level and it simultaneously provides valuable information for the optimization of the reaction conditions. PMID:24062850

  7. Charge separation in photoredox reactions

    SciTech Connect

    Kevan, L.

    1990-07-31

    The structural aspects controlling charge separation in molecular photoionization reactions in organized molecular assemblies involving micelles and vesicles are being studied by optical and electron magnetic resonance techniques including the time domain technique of electron spin echo modulation (ESEM). ESEM is particularly well adapted to the study of disordered systems as exemplified by micelles and vesicles. In addition to conventional studies by optical absorption and electron spin resonance, ESEM allows detection and analysis of extremely weak electron-nuclear dipolar interaction which gives structural information often not available by other experimental techniques. 32 refs., 2 figs.

  8. Animal experimentation.

    PubMed

    Kolar, Roman

    2006-01-01

    Millions of animals are used every year in often times extremely painful and distressing scientific procedures. Legislation of animal experimentation in modern societies is based on the supposition that this is ethically acceptable when certain more or less defined formal (e.g. logistical, technical) demands and ethical principles are met. The main parameters in this context correspond to the "3Rs" concept as defined by Russel and Burch in 1959, i.e. that all efforts to replace, reduce and refine experiments must be undertaken. The licensing of animal experiments normally requires an ethical evaluation process, often times undertaken by ethics committees. The serious problems in putting this idea into practice include inter alia unclear conditions and standards for ethical decisions, insufficient management of experiments undertaken for specific (e.g. regulatory) purposes, and conflicts of interest of ethics committees' members. There is an ongoing societal debate about ethical issues of animal use in science. Existing EU legislation on animal experimentation for cosmetics testing is an example of both the public will for setting clear limits to animal experiments and the need to further critically examine other fields and aspects of animal experimentation.

  9. Noncanonical reactions of flavoenzymes.

    PubMed

    Sobrado, Pablo

    2012-01-01

    Enzymes containing flavin cofactors are predominantly involved in redox reactions in numerous cellular processes where the protein environment modulates the chemical reactivity of the flavin to either transfer one or two electrons. Some flavoenzymes catalyze reactions with no net redox change. In these reactions, the protein environment modulates the reactivity of the flavin to perform novel chemistries. Recent mechanistic and structural data supporting novel flavin functionalities in reactions catalyzed by chorismate synthase, type II isopentenyl diphosphate isomerase, UDP-galactopyranose mutase, and alkyl-dihydroxyacetonephosphate synthase are presented in this review. In these enzymes, the flavin plays either a direct role in acid/base reactions or as a nucleophile or electrophile. In addition, the flavin cofactor is proposed to function as a "molecular scaffold" in the formation of UDP-galactofuranose and alkyl-dihydroxyacetonephosphate by forming a covalent adduct with reaction intermediates.

  10. Anaphylactic reactions to cinoxacin.

    PubMed Central

    Stricker, B. H.; Slagboom, G.; Demaeseneer, R.; Slootmaekers, V.; Thijs, I.; Olsson, S.

    1988-01-01

    During 1981 to mid-1988 three cases of anaphylactic shock after treatment with the quinolone derivative cinoxacin were reviewed by the Netherlands Centre for Monitoring of Adverse Reactions to Drugs and 17 cases of an anaphylactic type of reaction notified to the World Health Organisation Collaborating Centre for International Drug Monitoring. In five out of six patients for whom data were available the reaction began shortly after taking a single capsule of a second or next course of treatment. Cinoxacin is related to nalidixic acid, and one patient previously treated with that agent subsequently had an anaphylactoid reaction to cinoxacin and later developed a skin reaction to nalidixic acid. There were no deaths, and patients treated as an emergency with plasma expanders or with adrenaline and corticosteroids generally recovered promptly and uneventfully. In view of the potentially fatal consequences of anaphylactic reactions to cinoxacin and other quinolones doctors should take care when prescribing these drugs. PMID:3147004

  11. Reaction spreading on graphs

    NASA Astrophysics Data System (ADS)

    Burioni, Raffaella; Chibbaro, Sergio; Vergni, Davide; Vulpiani, Angelo

    2012-11-01

    We study reaction-diffusion processes on graphs through an extension of the standard reaction-diffusion equation starting from first principles. We focus on reaction spreading, i.e., on the time evolution of the reaction product M(t). At variance with pure diffusive processes, characterized by the spectral dimension ds, the important quantity for reaction spreading is found to be the connectivity dimension dl. Numerical data, in agreement with analytical estimates based on the features of n independent random walkers on the graph, show that M(t)˜tdl. In the case of Erdös-Renyi random graphs, the reaction product is characterized by an exponential growth M(t)˜eαt with α proportional to ln, where is the average degree of the graph.

  12. Nuclear reaction studies

    SciTech Connect

    Alexander, J.M.; Lacey, R.A.

    1994-11-01

    Research focused on the statistical and dynamical properties of ``hot`` nuclei formed in symmetric heavy-ion reactions. Theses included ``flow`` measurements and the mechanism for multifragment disassembly. Model calculations are being performed for the reactions C+C, Ne+Al, Ar+Sc, Kr+Nb, and Xe+La. It is planned to study {sup 40}Ar reactions from 27 to 115 MeV/nucleon. 2 figs., 41 refs.

  13. Immune reaction to propanidid.

    PubMed

    Christmas, D

    1984-05-01

    An adverse reaction to the intravenous anaesthetic agent propanidid is described in which the main features were hypotension, facial erythema, and abdominal pain. Changes in serum complement levels and differential white cell counts indicate that this was an immune reaction mediated by the classical complement pathway. The immune reaction apparently involved antibodies other than those of the IgE (reagin) class, and circumstantial evidence suggests that it was specific to propanidid rather than to the entire formulation or to Cremophor EL.

  14. Sleeve reaction chamber system

    DOEpatents

    Northrup, M. Allen; Beeman, Barton V.; Benett, William J.; Hadley, Dean R.; Landre, Phoebe; Lehew, Stacy L.; Krulevitch, Peter A.

    2009-08-25

    A chemical reaction chamber system that combines devices such as doped polysilicon for heating, bulk silicon for convective cooling, and thermoelectric (TE) coolers to augment the heating and cooling rates of the reaction chamber or chambers. In addition the system includes non-silicon-based reaction chambers such as any high thermal conductivity material used in combination with a thermoelectric cooling mechanism (i.e., Peltier device). The heat contained in the thermally conductive part of the system can be used/reused to heat the device, thereby conserving energy and expediting the heating/cooling rates. The system combines a micromachined silicon reaction chamber, for example, with an additional module/device for augmented heating/cooling using the Peltier effect. This additional module is particularly useful in extreme environments (very hot or extremely cold) where augmented heating/cooling would be useful to speed up the thermal cycling rates. The chemical reaction chamber system has various applications for synthesis or processing of organic, inorganic, or biochemical reactions, including the polymerase chain reaction (PCR) and/or other DNA reactions, such as the ligase chain reaction.

  15. Sub- and near-barrier fusion reactions experimental results

    NASA Astrophysics Data System (ADS)

    Montagnoli, G.

    2016-05-01

    Early data of sub-barrier fusion teached us that cross sections may strongly depend on the structure of colliding nuclei and on couplings to transfer channels. The influence of transfer is clearly indicated in the excitation functions of different nickel isotopes and various Ca+Zr systems. Fusion barrier distributions often yield the fingerprint of the relevant inelastic and transfer couplings. At lower energies, far below the barrier the slope of the excitation function keeps increasing in many cases, so that the cross sections are strongly over-predicted by standard coupled-channels (CC) calculations; this was named a hindrance effect. Furthermore, light heavy-ion systems show cross section oscillations above the Coulomb barrier. Recent experiments have been performed on the fusion of 28,30Si+28,30Si systems where all phenomena cited above show up. In particular regular oscillations that have been revealed above the barrier for 28Si+28Si and have been interpreted as the consequence of the strong channel couplings and/or the oblate deformation of 28Si.

  16. Experimental Design and Optimization: Application to a Grignard Reaction

    ERIC Educational Resources Information Center

    Bouzidi, Naoual; Gozzi, Christel

    2008-01-01

    This project is conducted by students during the second semester of their second year in our educational institution. This project constitutes an initiation into research and allows a broadening of knowledge, a development in autonomy, organization, team work, and initiative. It helps prepare the student-engineer for an internship in industry. The…

  17. Experimental macroevolution†

    PubMed Central

    Bell, Graham

    2016-01-01

    The convergence of several disparate research programmes raises the possibility that the long-term evolutionary processes of innovation and radiation may become amenable to laboratory experimentation. Ancestors might be resurrected directly from naturally stored propagules or tissues, or indirectly from the expression of ancestral genes in contemporary genomes. New kinds of organisms might be evolved through artificial selection of major developmental genes. Adaptive radiation can be studied by mimicking major ecological transitions in the laboratory. All of these possibilities are subject to severe quantitative and qualitative limitations. In some cases, however, laboratory experiments may be capable of illuminating the processes responsible for the evolution of new kinds of organisms. PMID:26763705

  18. Experimental macroevolution.

    PubMed

    Bell, Graham

    2016-01-13

    The convergence of several disparate research programmes raises the possibility that the long-term evolutionary processes of innovation and radiation may become amenable to laboratory experimentation. Ancestors might be resurrected directly from naturally stored propagules or tissues, or indirectly from the expression of ancestral genes in contemporary genomes. New kinds of organisms might be evolved through artificial selection of major developmental genes. Adaptive radiation can be studied by mimicking major ecological transitions in the laboratory. All of these possibilities are subject to severe quantitative and qualitative limitations. In some cases, however, laboratory experiments may be capable of illuminating the processes responsible for the evolution of new kinds of organisms. PMID:26763705

  19. Reaction profiles in porous electrodes. Final report

    SciTech Connect

    Katan, T.; Carlen, P.J.

    1985-05-01

    An experimental program was conducted to ascertain causes of alkaline zinc electrode shape change and to determine the development of reaction profiles within the pores of porous zinc electrodes. Various analog electrochemical cells were operated to isolate and evaluate the individual processes occurring during charge and discharge. It was found that both edge effects and osmosis can be responsible for the shape change phenomenon.

  20. Nuclear reactions for nucleosynthesis beyond Fe

    SciTech Connect

    Rauscher, Thomas

    2015-10-15

    Many more nuclear transitions have to be known in the determination of stellar reactivities for trans-iron nucleosynthesis than for reactions of light nuclei. This requires different theoretical and experimental approaches. Some of the issues specific for trans-iron nucleosynthesis are discussed.