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Sample records for copolymerization reactions experimental

  1. Copolymerization on Selective Substrates: Experimental Test and Computer Simulations.

    Science.gov (United States)

    Kozhunova, Elena Yu; Gavrilov, Alexey A; Zaremski, Mikhail Yu; Chertovich, Alexander V

    2017-03-28

    We explore the influence of a selective substrate on the composition and sequence statistics during the free radical copolymerization. In particular, we study the radical copolymerization of styrene and acrylic acid in bulk and in silica pores of different sizes. We show that the substrate affects both polymer composition and sequence statistics. We use dissipative particle dynamics simulations to study the polymerization process in detail, trying to pinpoint the parameters responsible for the observed differences in the polymer chain composition and sequences. The magnitude of the observed effect depends on the fraction of adsorbed monomer units, which cannot be described in the framework of the copolymerization theories based on the terminal unit model.

  2. Time programmed feed of semi-batch reactors with non-linear radical copolymerizations: an experimental study of the system styrene+divinylbenzene using SEC/MALLS

    OpenAIRE

    Gonçalves, Miguel; Dias, Rolando; Costa, Mário Rui

    2007-01-01

    The radical crosslinking copolymerization of mono and divinyl monomers was experimentally studied with a 2.5 dm3 semi-batch reactor using styrene + divinylbenzene as a model system. The analysis of products was carried out by SEC with a MALLS detector. The influence of the feed policy of divinylbenzene on the time evolution of the copolymer molecular weights and z-average mean square radius of gyration was assessed. A detailed kinetic model, in the absence of intramolecular reactions but taki...

  3. Knockout reactions: experimental aspects

    Energy Technology Data Exchange (ETDEWEB)

    Cortina Gil, D. [Santiago de Compostela Univ. (Spain)

    2007-07-01

    The availability of radioactive beams has given rise to intense activity in the field of direct reactions. The removal of one(two)-nucleon (referred to as nucleon knockout in this text) from a fast exotic projectile has been extensively investigated. This lecture provides a general overview of the experimental results achieved using this technique. The sensitivity of the method to different experimental aspects is illustrated with a few examples. Special attention is given to the application of nucleon-knockout reactions as a general purpose spectroscopic tool. (author)

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

    Science.gov (United States)

    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. Starch Modification by Graft Copolymerization of Acrylonitrile

    Institute of Scientific and Technical Information of China (English)

    刘瑞贤; 李莉; 茹宗玲; 张黎明; 高建平; 田汝川

    2003-01-01

    The graft copolymerization of acrylonitrile (AN) onto starch under the initiation of potassium permanganate was investigated. The effect of various reaction conditions on the graft copolymerization was studied. The relationships between the grafting rate and the initiator concentration of potassium permanganate, monomer acrylonitrile and backbone starch, as well as reaction temperature were established. The oxidation reaction of starch with manganic ions and valence changes of manganic ions during the graft copolymerization were discussed. The results show that manganic ion Mn7+ underwent a series of valence changes during the graft copolymerization: Mn(Ⅶ) → Mn(Ⅳ) → Mn(Ⅲ) → Mn(Ⅱ). The grafting rate of the graft copolymerization of acrylonitrile onto starch is also given.

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

    Science.gov (United States)

    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.

  7. On the Use of Quantum Chemistry for the Determination of Propagation, Copolymerization, and Secondary Reaction Kinetics in Free Radical Polymerization

    Directory of Open Access Journals (Sweden)

    Evangelos Mavroudakis

    2015-09-01

    Full Text Available Throughout the last 25 years, computational chemistry based on quantum mechanics has been applied to the investigation of reaction kinetics in free radical polymerization (FRP with growing interest. Nowadays, quantum chemistry (QC can be considered a powerful and cost-effective tool for the kinetic characterization of many individual reactions in FRP, especially those that cannot yet be fully analyzed through experiments. The recent focus on copolymers and systems where secondary reactions play a major role has emphasized this feature due to the increased complexity of these kinetic schemes. QC calculations are well-suited to support and guide the experimental investigation of FRP kinetics as well as to deepen the understanding of polymerization mechanisms. This paper is intended to provide an overview of the most relevant QC results obtained so far from the investigation of FRP. A comparison between computational results and experimental data is given, whenever possible, to emphasize the performances of the two approaches in the prediction of kinetic data. This work provides a comprehensive database of reaction rate parameters of FRP to assist in the development of advanced models of polymerization and experimental studies on the topic.

  8. The Growth of Latex Particles during the VAc/BA Copolymerization

    Institute of Scientific and Technical Information of China (English)

    QIN Shaoxiong; LIN Jindong; WANG Juan; ZHANG Xinya; CHEN Huanqin

    2006-01-01

    The semi-continuous seeded emulsion copolymerization of vinyl acetate and butyl acrylate was carried out with hydroxyethyl cellulose as a colloid stabilizer. The morphology of the latex particle and the relationship between the reaction time and the average particle diameter and/or the conversion ratio during the polymerization were investigated. The experimental results show that the morphology of the latex particle possesses the stable steric construction. In the seeded polymerization, the average particle diameter of latex decreased while the conversion ratio increased. At the second term of the emulsion copolymerization (the growth stage of particle size), the latex particle average diameter increased with copolymerization continuously, but the instantaneous conversation ratio was not large, so it was very necessary to properly prolong the time during the holding temperature stage.

  9. Mathematical Simulation of High-Conversion Binary Copolymerization

    Institute of Scientific and Technical Information of China (English)

    JiangWei; QinJiguang

    2005-01-01

    A new model for mathematical simulation of high-conversion binary copolymerization was established by combination of the concept of the three stage polymerization model (TSPM) proposed by Qin et al. for bulk free radical homopolymerization with the North equation to describe high-conversion copolymerization reaction exhibiting a strong gel effect, and the mathematical expressions of this new model were derived. Like TSPM, the new model also assmnes that the whole course of binary copolymerization can be divided into three different stages: low conversion, gel effect and glass effect stages. In addition, the reaction rate constants and the initiator efficiency at each copolymerization stage do not vary with conversion. Based on the expressions derived, a plot method for determining the overall rate constants and critical conversions was proposed. The literature data on conversion history for styrene (St)-methyl methacrylate (MMA) and ethylene glycol dimethacrylate (EGDMA)-MMA copolymerizations were treated to examine the model, which shows that the model is satisfactory.

  10. Experimental Demonstrations in Teaching Chemical Reactions.

    Science.gov (United States)

    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…

  11. Effect of the 1-hexene, the Al-Zr ratio and the temperature in ethylene copolymerization reactions with catalyst systems grafted on silica; Efeito do teor de hexeno-1, da relacao Al-Zr e da temperatura em reacoes de copolimerizacao de eteno, com sistemas cataliticos hibridos suportados em silica

    Energy Technology Data Exchange (ETDEWEB)

    Loureiro, Silvia R.R.; Silveira, Fernando; Galland, Griselda B.; Santos, Joao H.Z. dos [Rio Grande do Sul Univ., Porto Alegre, RS (Brazil). Inst. de Quimica]. E-mail:griselda@iq.ufrgs.br

    2003-07-01

    A series of copolymerization reactions with ethylene-1-hexene was performed with different amount of co-monomer, different aluminium-zirconium ratio and in two different temperature (40 deg C and 60 deg C). The reactions were accomplished by combining (nBuCp){sub 2} ZrCl{sub 2} and Cp{sub 2}ZrCl{sub 2} grafted on silica in different ratio (1:1, 3:1 and 1:3) and immobilization order. The catalyst activity in copolymerization reactions was shown to be dependent on the amount of the co-monomer, the Al-Zr ratio and the temperature. (author)

  12. Recent Experimental Progress on Surrogate Reactions

    Science.gov (United States)

    Beausang, Cornelius

    2014-09-01

    Reactions on unstable nuclei are important in a wide variety of nuclear physics scenarios. Cross sections for neutron (or light charged particle) induced reactions on target nuclei spanning the chart of the nuclei are important for nuclear astrophysics (r-process, s-process rp- and p-processes etc.), for nuclear energy generation and for national security applications. Many such reactions occur on short-lived unstable nuclei. Even with the present generation of radioactive beam facilities, many such reactions are difficult, if not impossible, to measure directly. For these reactions, often the surrogate reaction technique provides the only option to provide some experimental guidance for the calculations. The experimental and theoretical techniques required are described in some detail in the recent review article by Escher et al.. Originally introduced in the 1970's the last decade has seen a resurgence of interest in the surrogate technique. Various ratio techniques, external, internal and hybrid, have been developed to minimize the effect of target contamination. In the actinide region, a large number of surrogate (n,f) cross sections have been measured. In general, these show agreement to within 5--10%, with directly measured (n,f) data where these data exist (benchmarking), for equivalent neutron energies ranging from ~100 keV up to tens of MeV. For (n, γ) reactions, measurements have been attempted for select nuclei in various mass regions (A ~ 90, 150 and 235) and for these the agreement with directly measured data is less good. The various experimental techniques employed will be described as well as the current state of the experimental data. Some future directions will be described. Reactions on unstable nuclei are important in a wide variety of nuclear physics scenarios. Cross sections for neutron (or light charged particle) induced reactions on target nuclei spanning the chart of the nuclei are important for nuclear astrophysics (r-process, s

  13. Preparation of polystyrene/silica nanocomposites by radical copolymerization of styrene with silica macromonomer

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    A two-stage process has been developed to generate the silica-based macromonomer through surface-modification of silica with polymerizable vinyl groups. The silica surfaces were treated with excess 2,4-toluene diisocynate (TDI), after which the residual isocyanate groups were converted into polymerizable vinyl groups by reaction with hydroxypropylacrylate (HPA). Thus, polystyrene/silica nanocomposites were prepared by conventional radical copolymerization of styrene with silica macromonomer. The main effecting factors, such as ratios of styrene to the macromonomer, together with polymerization time on the copolymerization were studied in detail. FTIR, DSC and TGA were utilized to characterize the nanocomposites. Experimental results revealed that the silica nanoparticles act as cross-linking points in the polystytene/silica nanocomposites, and the glass transition temperatures of the nanocomposites are higher than that of the corresponding pure polystyrene. The glass transition temperatures of nanocomposites increased with the increasing of silica contents, which were further ascertained by DSC.

  14. NEW CATALYTIC SYSTEMS FOR THE FIXATION OF CO2 Ⅲ. INFLUENCE OF ADDITIVES AND REACTION MEDIUM ON THE COPOLYMERIZATION OF CARBON DIOXIDE-EPICHLOROHYDRIN IN THE PRESENCE OF Nd(P204)3-Al(i-Bu)3

    Institute of Scientific and Technical Information of China (English)

    CHEN Xianhai; ZHANG Yifeng; SHEN Zhiquan

    1994-01-01

    Copolymerization of carbon dioxide with epichlorohydrin was successfully carried out by using Nd (P204)3-A1 (i-Bu)3 as catalyst (P204) = (RO)2POO -, R=CH3 (CH2)3CH(C2H5)CH2-). Addition of carbonyl compounds into the catalyst decreased the carbon dioxide content of the copolymer to some extent. Compared to nonpolar solvents, ethereal and moderate polar solvents were favourable to obtaining higher carbon dioxide content copolymer. The coincidence of these results with the assumed copolymerization scheme clearly indicated that the copolymerization proceeds via coordinate anionic mechanism.

  15. DMC催化CO_2和环氧丙烷的调节共聚反应及其影响因素%Regulated Copolymerization of Carbon Dioxide and Propylene Oxide with DMC Catalyst and Effects of Reaction Conditions

    Institute of Scientific and Technical Information of China (English)

    周统昌; 邹志强; 刘言平; 罗建新; 张敏; 陈立班

    2011-01-01

    A group of multi-functional aliphatic polycarbonate polyols(APC),molecular weight between 3000 and 6000,was synthesized by regulated copolymerization of carbon dioxide and propylene oxide(PO) on double metal cyanide complex(Co-Zn DMC)catalyst with polyether alcohol,pentaerythritol(PER) or triethylene glycol as regulators.The molecular weight of the copolymer complied with the design requirements.All the regulators could successfully produce copolymers with two or four functionality.In the mean time the highest carbonate content of the copolymer is up to 60% and the highest catalystic efficiency could get to 663g of polymer /g of catalyst,with cyclic carbonate is only 4%.In this paper we also examined the effect of the temperature,pressure and the dosage of regulator on reaction.The results reveal that 60 ℃ is in favor of the copolymerization.The regulator and catalyst should be controlled in certain proportion to get high carbonate content.%以聚醚多元醇、二缩三乙二醇或季戊四醇作为分子量调节剂,用Zn-Co双金属氰化物(DMC)高效催化CO2和环氧丙烷(PO)调节共聚合成了数均分子量为3000~8000的多官能度脂肪族聚碳酸酯多元醇,共聚物的分子量基本符合设计要求。几种分子量调节剂均能成功合成两官能度或四官能度的共聚产物,产物中碳酸酯键含量最高可达60%,催化效率最高达663 g/g催化剂,副产物最低可控制到4%。文中还考察了温度、压力、调节剂及催化剂用量对共聚反应的影响,发现60℃的低温更有利于CO2和环氧丙烷的共聚反应,而且要获得碳酸酯键含量较高的产物,需控制调节剂和催化剂的比例。

  16. INFLAMMATORY REACTIONS IN EXPERIMENTAL MYOCARDIAL DAMAGE

    Directory of Open Access Journals (Sweden)

    L. D. Khidirova

    2015-12-01

    Full Text Available Aim. To study the role of hormonal and metabolic changes specific to myocardial infarction in the development of inflammatory reactions in the experimental non-coronarogenic myocardial damage. Material and methods. Wistar male rats weighing 180–220 g (n=80 were used in the study. Metabolic myocardial infarction in intact rats and rats with alloxan diabetes was induced by epinephrine injected subcutaneously as single dose or daily (7 days. Myocardial infarction was verified by ECG analysis, and by histological control. Nitroblue tetrazolium test (NBT-test both spontaneous and zymosan induced NBT-test was used to determine the oxygen-dependent functional activity of neutrophils and their biocidal reserve. Determination of cationic proteins in neutrophils of peripheral blood was performed using lysosomal-cationic test. Results. Increase in oxygen-dependent neutrophil biocidal activity was found as well as reduction in biocidal reserves. Indicators of zymosan induced NBT-test raised according to aggravation of hormonal changes much slower: alloxan increased them by 10% only , epinephrine single dose — by 35%, long-term epinephrine administration simultaneously with alloxan — by 54%. At the same time oxygen-independent neutrophil activity determined by intra-neutrophil cationic proteins level was significantly reduced. Blood levels of pro-inflammatory cytokines raised according to progression of the changes in myocardium: tumor necrosis factor-α (from 5.5±0.03 to 12.6±1.23 pg/ml and interleukin-1β (from 6.0±0.18 to 11.1±0.78 pg/ml. Conclusion. Experimental model of hormonal changes specific to myocardial infarction detected a relationship between inflammatory reactions accompanying myocardial damage and increased catecholamine production.

  17. Tuning the critical solution temperature of polymers by copolymerization

    Energy Technology Data Exchange (ETDEWEB)

    Schulz, Bernhard; Chudoba, Richard; Dzubiella, Joachim, E-mail: joachim.dzubiella@helmholtz-berlin.de [Institut für Weiche Materie und Funktionale Materialien, Helmholtz-Zentrum Berlin, 14109 Berlin (Germany); Institut für Physik, Humboldt-Universität zu Berlin, 12489 Berlin (Germany); Heyda, Jan [Department of Physical Chemistry, University of Chemistry and Technology, Prague, 166 28 Praha 6 (Czech Republic)

    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.

  18. Enhancing both the mechanical and chemical properties of paper sheet by graft co-polymerization with acrylonitrile/methyl methacrylate

    OpenAIRE

    H.M. Abd El Salam; Sayyh, S.M.; Kamal, E.H.M.

    2014-01-01

    The chemical graft copolymerization reaction of acrylonitrile (AN) and methyl methacrylate (MMA) binary mixture onto paper sheet was performed. The effect of initiator concentration, monomer concentration and temperature on the reaction rate was studied. The reaction rate equation of the graft copolymerization reaction is found to be RP = K2 [Initiator]0.795[Monomer]2.007. The apparent activation energy (Ea) of the copolymerization reaction is found to be 75.01 kJ/mol. The infrared characteri...

  19. Algorithm and application of Monte Carlo simulation for multi-dispersive copolymerization system

    Institute of Scientific and Technical Information of China (English)

    凌君; 沈之荃; 陈万里

    2002-01-01

    A Monte Carlo algorithm has been established for multi-dispersive copolymerization system, based on the experimental data of copolymer molecular weight and dispersion via GPC measurement. The program simulates the insertion of every monomer unit and records the structure and microscopical sequence of every chain in various lengths. It has been applied successfully for the ring-opening copolymerization of 2,2-dimethyltrimethylene carbonate (DTC) with (-caprolactone (ε-CL). The simulation coincides with the experimental results and provides microscopical data of triad fractions, lengths of homopolymer segments, etc., which are difficult to obtain by experiments. The algorithm presents also a uniform frame for copolymerization studies under other complicated mechanisms.

  20. Unique syndio-selectivity in CO/styrene copolymerization reaction catalyzed by palladium complexes with 2-(2'-oxazolinyl)-1,10-phenanthrolines.

    Science.gov (United States)

    Meduri, Angelo; Cozzula, Daniela; D'Amora, Angela; Zangrando, Ennio; Gladiali, Serafino; Milani, Barbara

    2012-07-07

    The reaction of the neutral Pd complex [Pd(CH(3))Cl(cod)] with the potentially terdentate 2-oxazolinyl phenanthroline ligands 1-3 affords the corresponding cationic dinuclear Pd-complexes 1a-3a, which can be isolated in the solid state in good yields. By treatment with AgPF(6) the complexes 1a-3a were converted into the corresponding hexafluorophosphate derivatives 1b-3b, where both the ligand units feature a terdentate coordination around the two Pd-centres with the phenanthroline fragment of each unit displaying a chelate coordination to one Pd-centre, while the corresponding oxazolinyl pendant acts as a bridging ligand towards the second Pd-centre. The persistence of this dimeric structure of 1b-3b in CD(2)Cl(2) solution was confirmed by (15)N-NMR experiments at natural abundance, which clearly show the binding to the metal of all of the nitrogen donors, as well as the overall C(2) symmetry of the compound. In consequence of the different strengths of the relevant ion-pair, the dimeric structure of the complex undergoes partial fragmentation in the case of the chloride derivatives 1a-3a, as evidenced from the (15)N-NMR spectra. Complexes 1b-3b are active catalysts in styrene alternate carbonylation, where, under very mild conditions (30 °C and 1 atm of CO), they provide oligomers with 3-5 repetitive units as the exclusive or prevailing product. When traces of the CO/styrene polyketones are also formed, their (13)C-NMR characterization shows that they are stereochemically homogeneous with a unique syndio-tacticity. This result implies that Pd-complexes able to induce a complete enantioface discrimination in the insertion step of the alkene during the catalytic cycle of the styrene alternate carbonylation have been produced for the first time.

  1. P-chiral phosphine-sulfonate/palladium-catalyzed asymmetric copolymerization of vinyl acetate with carbon monoxide.

    Science.gov (United States)

    Nakamura, Akifumi; Kageyama, Takeharu; Goto, Hiroki; Carrow, Brad P; Ito, Shingo; Nozaki, Kyoko

    2012-08-01

    Utilization of palladium catalysts bearing a P-chiral phosphine-sulfonate ligand enabled asymmetric copolymerization of vinyl acetate with carbon monoxide. The obtained γ-polyketones have head-to-tail and isotactic polymer structures. The origin of the regio- and stereoregularities was elucidated by stoichiometric reactions of acylpalladium complexes with vinyl acetate. The present report for the first time demonstrates successful asymmetric coordination-insertion (co)polymerization of vinyl acetate.

  2. Blood compatibility of polyurethane surface grafted copolymerization with sulfobetaine monomer.

    Science.gov (United States)

    Jiang, Yuan; Rongbing, Bian; Ling, Tong; Jian, Shen; Sicong, Lin

    2004-07-01

    Surface modification is an effective way to improve the hemocompatibility and remain bulk properties of biomaterials. Recently, polymer tailed with zwitterions was found having good blood compatibility. In this study, the grafting copolymerization of sulfobetaine onto polyurethane surface was obtained through two steps. In the first step, polyurethane film coupled with vinyl groups was obtained through the reaction between the carboxyl group of acrylic acid (AA) and the NH-urethane group of polyurethane by dicyclohexylcarbodiimide (DCC). In the second step, sulfobetaine was grafted copolymerization on the surface using AIBN as an initiator. The reaction process was monitored with ATR-IR spectra and X-ray photoelectron spectroscopy (XPS) spectra. The wettability of films was investigated by water contact angle measurement. The blood compatibility of the grafted films was evaluated by platelet adhesion in platelet rich plasma (PRP) and protein absorption in bovine fibrinogen (BFG). Low platelet adhesion was observed on the grafted films incubated in PRP for 1 and 3 h, respectively. The protein absorption was reduced on the grafted films after incubated in bovine fibrinogen for 2 h. All of these results revealed that the improved blood compatibility was obtained by grafting copolymerization with zwitterionic monomer of sulfobetaine onto polyurethane film. In addition, introducing vinyl groups onto surface through DCC and AA is a novel method to functionalize polyurethane for further modification.

  3. Study on Alternating Copolymerization of Polyester-amides

    Institute of Scientific and Technical Information of China (English)

    WEI Wen-liang; LI Jian-mei; ZHU Fang-liang

    2002-01-01

    The preparing methods, choice of catalysts and reaction kinetics of one of the monomers, diesteramide(DEA), of polyester-amides were investigated in details. The chemical structure of DEA was analyzed. And the Polyester-amides (PEA) were obtained by melt copolymerization with DEA. It is shown that DEA can be synthesized by DMT and hexamethylene diamine with the catalyst EX - 1 or EX - 2. The relationship between reaction rate of synthesizing monomer and concentration of hexamethylene diamine is first order kinetic relation.

  4. Status of experimental data for neutron induced reactions

    Energy Technology Data Exchange (ETDEWEB)

    Baba, Mamoru [Tohoku Univ., Sendai (Japan)

    1998-11-01

    A short review is presented on the status of experimental data for neutron induced reactions above 20 MeV based on the EXFOR data base and journals. Experimental data which were obtained in a systematic manner and/or by plural authors are surveyed and tabulated for the nuclear data evaluation and the benchmark test of the evaluated data. (author). 61 refs.

  5. Kinetic Treatment for Copolymerization of Styrene or Methyl Methacrylate with N-phenylmaleimide

    Institute of Scientific and Technical Information of China (English)

    单国荣; 翁志学; 黄志明; 潘祖仁

    2000-01-01

    Shirota's kinetic model and our kinetic model were used to treat the kinetic data of styrene (St) and N-phenylmaleimide (PMI) copolymerization in which chaxge-transfer complex (CTC) was formed. The results obtained by Shirota's kinetic model were disagreed with the experiments and the experimental phenomena could not be explained. The kinetic data of all feed fractions can be treated with our kinetic model, and the experimental phenomena can be explained from the propagation constants and reactivity ratios. Our kinetic model is also suitable for the kinetic data of methyl methacrylate (MMA) and PMI copolymerization in which CTC can not be formed.

  6. Algorithm and application of Monte Carlo simulation for multi-dispersive copolymerization system

    Institute of Scientific and Technical Information of China (English)

    凌君; 沈之荃; 陈万里

    2002-01-01

    A Monte Carlo algorithm has been established for multi-dispersive copolymerization system, based on the experimental data of copolymer molecular weight and dispersion via GPC measurement. The program simulates the insertion of every monomer unit and records the structure and microscopical sequence of every chain in various lengths. It has been applied successfully for the ring-opening copolymerization of 2,2-dimethyltrimethylene carbonate (DTC) with δ-caprolactone (δ-CL). The simulation coincides with the experimental results and provides microscopical data of triad fractions, lengths of homopolymer segments, etc., which are difficult to obtain by experiments. The algorithm presents also a uniform frame for copolymerization studies under other complicated mechanisms.

  7. Graft Copolymerization of Acrylic Acid onto Fungal Cell Wall Structural Polysaccharide

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Acrylic acid was graft-copolymerized onto Rhi. oryzae's cell wall structural polysacchaxide directly and efficiently in aqueous solution with ceric ammonium nitrate as initiator. The maximal grafting percentage of 135.5% was obtained under the condition of [Ce4+]=5mmol.L-1, [AA]=1mol.L-1, T=60°C and t=3h. Graft copolymerization was suggested to proceed through free radical reaction mechanism. Grafting occurred primarily on chitosan. Acrylic acid was also attempted to be grafted onto Asp. niger cell wall structural polysaccharide, and only 44.2% of grafting percentage was resulted.

  8. SYNTHESIS OF POLY(ETHYLENE TEREPHTHALATE)-POLYCAPROLACTONE BLOCK COPOLYMER BY DIRECT COPOLYMERIZATION

    Institute of Scientific and Technical Information of China (English)

    Shen-guo Wang; Kai Tang

    1999-01-01

    Poly(ethylene terephthalate)-polycaprolactone block copolymer (PCL-b-PET) is a polyester with improved biodegradability. In the present paper, a new direct copolymerization method of ε-caprolactone (ε-CL) and bishydroxyethylene terephthalate (BHET) in the presence of Ti(OBu)4 was proposed for the synthesis of PCL-b-PET. The PCL-b-PET copolymer was characterized by IR, GPC and 1H-NMR techniques, and the effects of synthesis conditions, such as temperature, reaction time and concentration of catalyst on the copolymerization were discussed.

  9. GRAFT COPOLYMERIZATION OF ACRYLAMIDE ONTO POLY(N-PARA-TOLYLACRYLAMIDE) FILMS INITIATED BY CERIC ION

    Institute of Scientific and Technical Information of China (English)

    QIU Kunyuan; SONG Ye

    1988-01-01

    Functional monomers having phenylcarbarnoyl and p-tolylcarbamoyl were synthesized. Binary initiation system consisted of Ce4+ andthese functional monomers could initiate acrylamide polymerization.It was found that acrylamide could graft copolymerize onto macromolecules having these functional monomers units. The formation of graft copolymer has been verified by its percentage of water absorption,contact angle with water, XPS and SEM photographs. The reaction mechanism was proposed and the main reactive site of graft copolymerization initiated by Ce4+ would take place predominantly at the functional pendant group.

  10. “Living”/controlled radical copolymerization of N-phenylmaleimide and styrene using Fréchet-type dendritic initiators

    Institute of Scientific and Technical Information of China (English)

    ZHAO; Youliang(赵优良); JIANG; Jing(姜静); LIU; Hongwei(刘宏伟); CHEN; Chuanfu(陈传福); XI; Fu(习复)

    2002-01-01

    Polyarylether dendrons as macroinitiators for the "living"/controlled free radical copolymerization of N-phenylmaleimide (PhMI) and styrene (St) have been demonstrated. The copolymerization was carried out in bulk or anisole with CuBr/bipy catalyst at 100-130℃. It is found that the resulting copolymers possess predetermined molecular weights and narrower polydispersities (1.18 < Mw / Mn < 1.32). The effects of reaction temperature and monomer feed on the copolymerization kinetics were investigated in detail. By using the Fineman-Ross method, the apparent monomer reactivity ratios for the atom transfer radical copolymerization of PhMI and St were determined to be rPhMI = 0.0207, and rSt = 0.0484, respectively.

  11. Current experimental situation in heavy-ion reactions

    Energy Technology Data Exchange (ETDEWEB)

    Scott, D.K.

    1978-06-01

    A detailed survey of the present experimental situation in heavy-ion physics is presented. The discussion begins by considering the simple excitation of discrete states in elastic scattering, transfer, and compound-nucleus reactions; it then turns to more drastic perturbations of the nucleus high in the continuum through fusion, fission, and deeply inelastic scattering, and concludes with the (possibly) limiting asymptotic phenomena of relativistic heavy-ion collisions. 138 figures, 5 tables, 451 references. (RWR)

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

    Science.gov (United States)

    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.

  13. Understanding organometallic reaction mechanisms and catalysis experimental and computational tools computational and experimental tools

    CERN Document Server

    Ananikov, Valentin P

    2014-01-01

    Exploring and highlighting the new horizons in the studies of reaction mechanisms that open joint application of experimental studies and theoretical calculations is the goal of this book. The latest insights and developments in the mechanistic studies of organometallic reactions and catalytic processes are presented and reviewed. The book adopts a unique approach, exemplifying how to use experiments, spectroscopy measurements, and computational methods to reveal reaction pathways and molecular structures of catalysts, rather than concentrating solely on one discipline. The result is a deeper

  14. [Ergopsychometry. New methods in experimental psychodiagnosis of pathologic stress reactions].

    Science.gov (United States)

    Beiglböck, W; Feselmayer, S; Bischof, B

    1989-01-01

    Ergopsychometry--testing under physiological and/or psychological stress--has proved to be increasingly successful in recent years. In particular in sports psychology, in which only physiological stress had been considered, have experimental results been successfully implemented into practice. The fact that some subjects appear unchanged or even yield better results under stress than under stress-free conditions applies not only to physiological stress, but also holds true for psychological stress. These results have consequences for the experimental psychodiagnoses of pathological stress reactions, e.g., with alcoholics or psychosomatic patients. Proceeding from the above hypothesis we investigated 20 gamma-alcoholics (so-called relieve drinkers) and 20 psychosomatic inpatients under stress-free as well as under stress conditions, according to the ergopsychometric approach. The control group consisted of 23 subjects matched with respect to age, sex, and profession. We used a test battery to assess concentration, memory, and choice-reaction as well as the subjective state of activation, stress-coping-mechanisms, and self-concepts. Essentially, the validity of ergopsychometric designs was confirmed by our results. In accordance with our expectations, 27.5% of the experimental group showed increasing efficiency scores, compared to 56.5% in the control group. Possible explanations for the findings can be derived from the assessment of subjective activity, but not from of the personality questionnaires.

  15. STUDIES ON THE OXIDATION AND GRAFT COPOLYMERIZATION OF POLY(ETHER-URETHANE)

    Institute of Scientific and Technical Information of China (English)

    SUN Yanhui; QIU Kunyuan; FENG Xinde

    1983-01-01

    A new method of graft copolymerization of acrylamide (AAM) on poly(ether-urethane) (PEU)which was prepared from poly(tetramethylene ether) glycol (PTMG), 4,4'-diphenylmethane diisocyanate (MDI) and ethylene diamine or butanediol extender was investigated. Hydroperoxide group was first introduced onto the surface of PEU through photo-oxidation in the presence of hydrogen peroxide, then it was reacted with ferrous ion or N,N-dimethyl toluidine (DMT) to initiate AAM graft copolymerization on PEU surface. The graft reaction could be carried out effectively at low temperature. The formation of graft copolymer has been verified by its water absorption % and the scanning electron microscopy photographs. Some model compounds of PEU soft segment and hard segment were synthesized in order to clarify the site of graft reaction. The results of oxidation and graft copolymerization of model compounds showed that this graft copolymerization possesses higher selectivity, and it takes place predominately at the polyether segments, because the ether linkage in soft segment is very sensitive to oxidation and can form hydroperoxide easily. Thus,the grafting site appears to be at a-carbon of the ether linkage.

  16. An experimental and theoretical study of reaction steps relevant to the methanol-to-hydrocarbons reaction

    Energy Technology Data Exchange (ETDEWEB)

    Svelle, Stian

    2004-07-01

    The primary objective of the present work is to obtain new insight into the reaction mechanism of the zeolite catalyzed methanol-to-hydrocarbons (MTH) reaction. It was decided to use both experimental and computational techniques to reach this goal. An investigation of the n-butene + methanol system was therefore initiated. Over time, it became apparent that it was possible to determine the rate for the methylation of n-butene by methanol. The ethene and propene systems were therefore reexamined in order to collect kinetic information also for those cases. With the development of user-friendly quantum chemistry programs such as the Gaussian suite of programs, the possibility of applying quantum chemical methods to many types of problems has become readily available even for non-experts. When performing mechanistic studies, there is quite often a considerable synergy effect when combining experimental and computational approaches. The methylation reactions mentioned above turned out to be an issue well suited for quantum chemical investigations. The incentive for examining the halomethane reactivity was the clear analogy to the MTH reaction system. Alkene dimerization was also a reaction readily examined with quantum chemistry. As discussed in the introduction of this thesis, polymethylbenzenes, or their cationic counterparts, are suspected to be key intermediates in the MTH reaction. It was therefore decided to investigate the intrinsic reactivity of these species in the gas-phase by employing sophisticated mass spectrometric (MS) techniques in collaboration with the MS group at the Department of Chemistry, University of Oslo The data thus obtained will also be compared with results from an ongoing computational study on gas phase polymethylbenzenium reactivity. 6 papers presenting various studies are included. The titles are: 1) A Theoretical Investigation of the Methylation of Alkenes with Methanol over Acidic Zeolites. 2) A Theoretical Investigation of the

  17. Radiation initiated copolymerization of allyl alcohol with acrylonitrile

    Energy Technology Data Exchange (ETDEWEB)

    Solpan, Dilek; Guven, Olgun [Hacettepe Univ., Ankara (Turkey). Dept. of Chemistry

    1996-07-01

    Copolymerization of allyl alcohol (AA) with acrylonitrile (AN) initiated by {gamma}-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-Tudos (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. (Author).

  18. Radiation initiated copolymerization of allyl alcohol with acrylonitrile

    Science.gov (United States)

    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.

  19. Mechanism of alternating copolymerization of methyl methacrylate with styrene in the presence of diethylaluminum chloride

    Energy Technology Data Exchange (ETDEWEB)

    Zubov, V.P.; Lachinov, M.B.; Ignatova, E.V.; Georgiev, G.S.; Golubev, V.B.; Kabanov, V.A.

    1982-03-01

    A kinetic study of the propagation mechanism of the alternating copolymerization of styrene (St) with methyl methacrylate (MMA) in the presence of a complexing agent (diethylaluminum chloride, DEAC) in bulk and in tetrachloroethylene solutions at a molar ratio DEAC/MMA = 0.5 has been carried out. It has been shown that the copolymerization is a chain radical process characterized by a short active-center lifetime, bimolecular termination, and high rate of chain transfer to the complexed MMA. A kinetic scheme has been proposed for the propagation mechanism of alternating copolymerization in the presence of a complexing agent not requiring independent measurements of the equilibrium constant of complexation. It has been found that spontaneous and uv-initiated copolymerizations in the system have different mechanisms of initiation and a common mechanism of propagation. The propagation proceeds by addition of single monomers as well as donor-acceptor complexes of the comonomers to the propagation radicals, with the first mechanism being predominant. Inclusion of the monomers in the complex leads to an increase of the St reactivity and to a decrease of the MMA reactivity in propagation to the corresponding macroradicals in comparison with the reactivity of the free monomers. A number of kinetic and statistical parameters of the propagation reaction have been calculated.

  20. Invertase immobilization onto radiation-induced graft copolymerized polyethylene pellets

    Science.gov (United States)

    de Queiroz, Alvaro Antonio Alencar; Vitolo, Michele; de Oliveira, Rômulo Cesar; Higa, Olga Zazuco

    1996-06-01

    The graft copolymer poly(ethylene-g-acrylic acid) (LDPE-g-AA) was prepared by radiation-induced graft copolymerization of acrylic acid onto low density polyethylene (LDPE) pellets, and characterized by infrared photoacoustic spectroscopy and scanning electron microscopy (SEM). The presence of the grafted poly(acrylic acid) (PAA) was established. Invertase was immobilized onto the graft polymer and the thermodynamic parameters of the soluble and immobilized enzyme were determined. The Michaelis constant, Km, and the maximum reaction velocity, Vmax, were determined for the free and the immobilized invertase. The Michaelis constant, Km was larger for the immobilized invertase than for the free enzyme, whereas Vmax was smaller for the immobilized invertase. The thermal stability of the immobilized invertase was higher than that of the free enzyme.

  1. STUDIES ON THE OXIDATION AND GRAFT COPOLYMERIZATION OF POLYETHERS

    Institute of Scientific and Technical Information of China (English)

    SUN Yanhui; QIU Kunyuan; FENG Xinde VOONG Sing-tuh

    1984-01-01

    Polyethers could form hydroperoxide under air-oxidation or photo-oxidation in the presence of H2O2. The scission of ether linkage induced by moderate oxidation was prevented by controlling the reaction time and hydroperoxide concentration. The oxidation rate was affected by the end groups of polyethers. The decreasing order of oxidation rate for various poly(tetramethylene ether) glycol derivatives having different end groups are as follows: poly(tetramethylene ether) glycol (PTMG)> poly(tetramethylene ether)acetate (PTMGAC) > poly(tetramethylene ether) phenyl carbamate (PTMGPC). The urethane end groups in PTMGPC increase the resistance toward oxidation. Polyether hydroperoxide reacts with ferrous ion or N,N-dimethyl toluidine (DMT) to form polymericoxy radical which then initiates the graft copolymerization of vinyl monomers at low temperature,and was devoid of homopolymerization. The copolymer after separation and purification was proved to be a graft one by IR analysis and elemental analysis.

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

    Science.gov (United States)

    Gaspard, P.; Andrieux, D.

    2014-07-01

    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.

  3. Optimizing the bulk copolymerization of D,L-lactide and glycolide by response surface methodology

    Directory of Open Access Journals (Sweden)

    J. F. Rodriguez

    2013-11-01

    Full Text Available Poly(D,L-lactide-co-glycolide, PLGA, is a biodegradable polyester with high interest in medical industry, especially when zinc (II 2-ethylhexanoate (ZnOct2 is used as catalyst substitute in polymerization processes as a substitute of the toxic tin (II 2-ethylhexanoate (SnOct2 together an initiator such as methanol to improve the reaction rate. This article shows the optimization of the bulk copolymerization method by using a factorial design approach on three experimental parameters: temperature (T, molar ratio monomers/catalyst (MC ratio and molar ratio initiator/catalyst (IC ratio. Their influence on mass conversion (X and number-average molecular weight (Mn was also discussed. Also it provides a useful tool to select in a fast way the proper experimental conditions for the obtaining of this polymer as a previous stage in the synthesis and impregnation of biodegradable scaffolds. This analysis revealed that the most relevant variable in the process is the temperature, being desirable to use the high value (160ºC in order to obtain high values of conversion and molecular weight.

  4. Copolymerization of Carbon–carbon Double-bond Monomer (Styrene with Cyclic Monomer (Tetrahydrofuran

    Directory of Open Access Journals (Sweden)

    Sari Fouad

    2012-12-01

    Full Text Available We reported in this work that the cationic copolymerization in one step takes place between carbon–carbon double-bond monomer styrene with cyclic monomer tetrahydrofuran. The comonomers studied belong to different families: vinylic and cyclic ether. The reaction is initiated with maghnite-H+ an acid exchanged montmorillonite as acid solid ecocatalyst. Maghnite-H+ is already used as catalyst for polymerization of many vinylic and heterocyclic monomers. The oxonium ion of tetrahydrofuran and carbonium ion of styrene propagated the reaction of copolymerization. The acetic anhydride is essential for the maintenance of the ring opening of tetrahydrofuran and the entry in copolymerization. The temperature was kept constant at 40°C in oil bath heating for 6 hours. A typical reaction product was analyzed by 1H-NMR, 13C-NMR and IR and the formation of the copolymer was confirmed. The reaction was proved by matched with analysis. The maghnite-H+ allowed us to obtain extremely pure copolymer in good yield by following a simples operational conditions. Copyright © 2012 by BCREC UNDIP. All rights reservedReceived: 29th October 2012; Revised: 29th November 2012; Accepted: 29th November 2012[How to Cite: S. Fouad, M.I. Ferrahi, M. Belbachir. (2012. Copolymerization of Carbon–carbon Double-bond Monomer (Styrene with Cyclic Monomer (Tetrahydrofuran. Bulletin of Chemical Reaction Engineering & Catalysis, 7(2: 165-171. (doi:10.9767/bcrec.7.2.4074.165-171][How to Link / DOI: http://dx.doi.org/10.9767/bcrec.7.2.4074.165-171 ] | View in 

  5. In-situ copolymerization of aniline with alkyl amine by APS:Kinetics and application

    Institute of Scientific and Technical Information of China (English)

    M.Rashid; Shams Qamar Usmani; Suhail Sabir

    2008-01-01

    The kinetic study of in-situ copolymerization of aniline with o-and p-methylaniline by ammonium persulfate (APS) has been carried out.UV-vis spectroscopic method was used to investigate the course of copolymerization.Structural characterization was studied by FT-IR spectral analysis.The electronic spectra of the copolymers poly(aniline-co-p-toluidine) and poly(aniline-co-o-tolnidine) show blue shift.The shift has been observed in the bands corresponding to π→π* transition as well as in the exciton transition.The increase in absorbance recorded during the reaction for different concentration of aniline,o-and p-toluidine at various intervals of time of polymerization reaction indicates a growth in the polymer formation.The resulting first-order rateconstant was used to calculate the rate of copolymer formation using the rate equation-d[A]/dt=kcn.

  6. Graftig Copolymerization of Hydrophilic Monomers Onto Alginate for Modification it,s Structure

    Directory of Open Access Journals (Sweden)

    Mohammad Sadeghi

    2014-03-01

    Full Text Available In this research, we synthesize of a graft copolymer based on alginate via simultaneously graft copolymerization acrylamide (AAm and 2-acrylamido-2-methylpropanesulfonic acid (AMPS onto alginate backbones. The polymerization reaction was carried out in an aqueous medium and in the presence of ammonium persulfate (APS as an initiator. Infrared spectroscopy and TGA thermal analysis were carried out to confirm the chemical structure of the copolymer. A proposed mechanism for hydrogel formation was suggested.

  7. ELECTROCHEMICAL COPOLYMERIZATION OF ANILINE AND AZURE B

    Institute of Scientific and Technical Information of China (English)

    Dan Shan; Shao-lin Mu; Bing-wei Mao; Yong-fang Li

    2001-01-01

    The electrochemical copolymerization of aniline and N,N,N'-trimethylthionin (azure B) in aqueous solutions has been carried out using the potential sweep method. The optimum conditions for the coelectrodeposition are that the pH value and the temperature of the electrolytic solution are controlled at 5.57 and 30℃, respectively, and the scan potential range is set between -0.25 and 1.10 V (versus SCE). The copolymerization rate of aniline and azure B is about 3 times larger than that of aniline in the absence of azure B. The copolymerization of aniline and azure B was verified from the results of visible spectra during electrolysis, FTIR spectra and the atomic force microscopy (AFM) images of the polymers. The in situ visible spectrum for the electrolysis of the solution containing aniline and azure B is different from that of the respective aniline and azure B. The FTIR spectrum of the copolymer is not a superposition of that of polyaniline and poly(azure B). The AFM image of the copolymer is different from those of polyaniline and poly(azure B) and is not a mixture of individual polymers. The conductivity of the copolymer synthesized at pH 5.57 is four orders of magnitude higher than that of polyaniline synthesized under the same conditions, but in the absence of azure B. The electrochemical properties of the copolymer are mainly attributed to polyaniline, but the copolymer has a better electrochemical reversibility and a much faster charge transfer than those of polyaniline.``

  8. PROPERTIES AND SYNTHESIS OF NEW SUPPORTS FOR IMMOBILIZATION OF ENZYMES BY COPOLYMERIZATION OF VINYLENE CARBONATE AND METHACRYLIC ACID

    Institute of Scientific and Technical Information of China (English)

    Lun-han Ding; Yue Li; Yan Jiang; Zhe Cao; Jia-xian Huang

    2000-01-01

    Methacrylic acid first was neutralized with an aqueous solution of NaOH to pH = 6.0~7.0, vinylene carbonate (VCA) was added to the solution, then monomers were copolymerized in paraffin oil by means of reverse-phase suspension polymerization and hydrophilic copolymeric supports were prepared. The properties of the supports were determined using trypsin and results show that the amount of enzymes coupled to the supports and the specific activity of immobilized trypsin are related to the content of VCA structure units, reaction time and concentration of enzyme solution, etc.

  9. RAFT copolymerization of itaconic anhydride and 2-methoxyethyl acrylate: a multifunctional scaffold for preparation of “clickable” gold nanoparticles

    DEFF Research Database (Denmark)

    Javakhishvili, Irakli; Kasama, Takeshi; Jankova, Katja Atanasova

    2013-01-01

    RAFT copolymerization of 2-methoxyethyl acrylate and itaconic anhydride – a monomer derived from renewable resources – is carried out in a controlled fashion. The copolymer allows preparation of gold nanoparticles with abundant surficial carboxyl and alkyne functional groups that are dendronized ...... via Cu(i)-mediated “click” reaction....

  10. Experimental study of $\\eta$ meson photoproduction reaction at MAMI

    CERN Document Server

    Kashevarov, V L

    2015-01-01

    New data for the differential cross sections, polarization observables $T$, $F$, and $E$ in the reaction of $\\eta$ photoproduction on proton from the threshold up to a center-of-mass energy of W=1.9 GeV are presented. The data were obtained with the Crystal-Ball/TAPS detector setup at the Glasgow tagged photon facility of the Mainz Microtron MAMI. The polarization measurements were made using a frozen-spin butanol target and circularly polarized photon beam. The results are compared to existing experimental data and different PWA predictions. The data solve a long-standing problem related the angular dependence of older $T$ data close to threshold. The unexpected relative phase motion between $s$- and $d$-wave amplitudes required by the old data is not confirmed. At higher energies, all model predictions fail to reproduce the new polarization data indicating a significant impact on our understanding of the underlying dynamics of $\\eta$ meson photoproduction. Furthermore, we present a fit of the new data and e...

  11. Experimental study of η meson photoproduction reaction at MAMI

    Directory of Open Access Journals (Sweden)

    Kashevarov V. L.

    2015-01-01

    Full Text Available New data for the differential cross sections, polarization observables T, F, and E in the reaction of η photoproduction on proton from the threshold up to a center-of-mass energy of W=1.9 GeV are presented. The data were obtained with the Crystal-Ball/TAPS detector setup at the Glasgow tagged photon facility of the Mainz Microtron MAMI. The polarization measurements were made using a frozen-spin butanol target and circularly polarized photon beam. The results are compared to existing experimental data and different PWA predictions. The data solve a long-standing problem related the angular dependence of older T data close to threshold. The unexpected relative phase motion between s- and d-wave amplitudes required by the old data is not confirmed. At higher energies, all model predictions fail to reproduce the new polarization data indicating a significant impact on our understanding of the underlying dynamics of η meson photoproduction. Furthermore, we present a fit of the new data and existing data from GRAAL for ∑ asymmetry based on an expansion in terms of associated Legendre polynomials. A Legendre decomposition shows the sensitivity to small partialwave contributions. The sensitivity of the Legendre coefficients to the nucleon resonance parameters is shown using the ηMAID isobar model.

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

    Energy Technology Data Exchange (ETDEWEB)

    Maeda, Kiminori [Department of Chemistry, University of Oxford, Centre for Advanced Electron Spin Resonance, Inorganic Chemistry Laboratory, Oxford (United Kingdom); Liddell, Paul; Gust, Devens [Department of Chemistry and Biochemistry, Arizona State University, Tempe, Arizona, 85287-1604 (United States); Hore, P. J. [Department of Chemistry, University of Oxford, Physical and Theoretical Chemistry Laboratory, Oxford (United Kingdom)

    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.

  13. Copolymerization of ε-caprolactone with Epichlorohydrin by a Green Catalyst, Maghnite

    Directory of Open Access Journals (Sweden)

    Abdelghani Bouchama

    2012-06-01

    Full Text Available Most of the cationic initiators used in the synthesis of copolymers are expensive. They may be poisoned by products of the reaction or impurities present in the monomer feed, and contain heavy metals, such as chromium, mercury, antimony, etc., that presents environmental disposal problems for the user. Maghnite is a montmorillonite sheet silicate clay that is exchanged with protons to produce Maghnite-H+ (Mag-H+. This non-toxic and cheaper cationic catalyst was used for the copolymerization of ε-caprolactone (CL with epichlorohydrin (ECH. The effects of the amounts of Mag-H+ and the temperature on the synthesis of poly (ε-caprolactone-co-epichlorohydrin were studied. Increasing Maghnite-H+ proportion and temperature produced the increase in copolymerization yield. The copolymer obtained was characterized by 1H-NMR and IR spectroscopy. Copyright © 2012 BCREC UNDIP. All rights reserved.Received: 24th September 2011, Revised: 12nd December 2011; Accepted: 9th January 2012[How to Cite: A. Bouchama, M.I. Ferrahi, and M. Belbachir. (2012. Copolymerization of ε-caprolactone with Epichlorohydrin by a Green Catalyst, Maghnite. Bulletin of Chemical Reaction Engineering & Catalysis, 7 (1: 43-48.  doi:10.9767/bcrec.7.1.1211.43-48][How to Link / DOI: http://dx.doi.org/10.9767/bcrec.7.1.1211.43-48 ] | View in 

  14. Inflammatory reaction in experimental hepatic amebiasis. An ultrastructural study.

    Science.gov (United States)

    Tsutsumi, V.; Martinez-Palomo, A.

    1988-01-01

    One of the hallmarks of tissue necrosis produced by the human protozoan parasite Entamoeba histolytica, the causative agent of human amebiasis, appeared to be the lack of inflammatory reaction to the invading trophozoites. Recent evidence suggests, however, that inflammatory cells do appear during early stages of amebic destructive lesions and that they contribute to the establishment of foci of tissue necrosis in intestinal and liver lesions. The present analysis of the fine-structural changes that take place during early stages of amebic liver abscesses induced in hamsters after the intraportal inoculation of axenic amebas has shown that large numbers of polymorphonuclear leukocytes (PMNs) are recruited around invading amebas. These leukocytes lyse as a consequence of contact-mediated damage induced by the trophozoites. Amebas were also capable of ingesting apparently intact PMNs. Macrophages and eosinophils were also recruited at the foci of inflammation. At all times examined, trophozoites of Entamoeba histolytica survived in spite of being in close contact with PMNs or degranulating eosinophils. The ultrastructural observations have also shown the lack of direct contact between amebas and liver parenchymal cells during the initial stages of the focal liver necrosis induced by the parasite, therefore supporting the view that hepatic damage may be effected indirectly through lysis of inflammatory cells. The results also provide a basis for the understanding of the induction of experimental protective immunity against invasive amebiasis, a process which seems to be mostly dependent on cellular mechanisms. Images Figure 1 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Figure 10 Figure 11 Figure 12 PMID:3337207

  15. Kinetics and thermodynamics of living copolymerization processes.

    Science.gov (United States)

    Gaspard, Pierre

    2016-11-13

    Theoretical advances are reported on the kinetics and thermodynamics of free and template-directed living copolymerizations. Until recently, the kinetic theory of these processes had only been established in the fully irreversible regime, in which the attachment rates are only considered. However, the entropy production is infinite in this regime and the approach to thermodynamic equilibrium cannot be investigated. For this purpose, the detachment rates should also be included. Inspite of this complication, the kinetics can be exactly solved in the regimes of steady growth and depolymerization. In this way, analytical expressions are obtained for the mean growth velocity, the statistical properties of the copolymer sequences, as well as the thermodynamic entropy production. The results apply to DNA replication, transcription and translation, allowing us to understand important aspects of molecular evolution.This article is part of the themed issue 'Multiscale modelling at the physics-chemistry-biology interface'. © 2016 The Author(s).

  16. Kinetics and thermodynamics of living copolymerization processes

    Science.gov (United States)

    Gaspard, Pierre

    2016-11-01

    Theoretical advances are reported on the kinetics and thermodynamics of free and template-directed living copolymerizations. Until recently, the kinetic theory of these processes had only been established in the fully irreversible regime, in which the attachment rates are only considered. However, the entropy production is infinite in this regime and the approach to thermodynamic equilibrium cannot be investigated. For this purpose, the detachment rates should also be included. Inspite of this complication, the kinetics can be exactly solved in the regimes of steady growth and depolymerization. In this way, analytical expressions are obtained for the mean growth velocity, the statistical properties of the copolymer sequences, as well as the thermodynamic entropy production. The results apply to DNA replication, transcription and translation, allowing us to understand important aspects of molecular evolution. This article is part of the themed issue 'Multiscale modelling at the physics-chemistry-biology interface'.

  17. EPR investigation on radiation-induced graft copolymerization of styrene onto polyethylene: Energy transfer effects

    Science.gov (United States)

    Salih, M. A.; Buttafava, A.; Ravasio, U.; Mariani, M.; Faucitano, A.

    2007-08-01

    In this paper, energy transfer phenomena concerning the in-source graft copolymerization of styrene onto LDPE were investigated through the EPR analysis of the radical intermediates. The model solution experiments have shown a substantial deviation of the experimental G (radicals) values with respect to the additivity law, which reflect the negative effect of the styrene monomer concentration on the initiation rate of the graft copolymerization. The EPR measurements performed on polyethylene- co-styrene graft copolymers of various composition following low-temperature vacuum gamma irradiation have confirmed the decrease of the total radical yields with increasing the styrene concentration. The effect was partly attributed to the heterogeneity of the graft copolymer matrix and to the lack of molecular mobility in the solid state at low temperature, which prevents the attainment of the favourable geometrical configurations in intermolecular energy and charge transfer events.

  18. Recent direct reaction experimental studies with radioactive tin beams

    CERN Document Server

    Jones, K L; 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; Matos, 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 131Sn from across the N=82 shell closure. The second example utilizes a one-neutron knockout reaction on fragmentation beams of neutron-deficient 106,108Sn...

  19. Cobaltoporphyrin-Catalyzed CO 2 /Epoxide Copolymerization: Selectivity Control by Molecular Design

    KAUST Repository

    Anderson, Carly E.

    2012-09-11

    A series of cobalt(III) chloride porphyrin complexes of the general formula 5,10,15,20-tetra(p-alkoxy)phenylporphyrin cobalt chloride (4b-e) and the related 5,10,15,20-tetra(p-nitro)phenylporphyrin cobalt chloride (4f) are presented and their reactivity toward propylene oxide (PO)/CO 2 coupling/copolymerization is explored. While the nitro-substituted complex (4f), in conjunction with an onium salt, shows moderate activity toward cyclization, the 4b-e/onium systems show superior copolymerization activity in comparison to tetraphenylporphyrin Co(III) chloride (4a) with high selectivity and conversion to poly(propylene carbonate) (PPC). A comprehensive copolymerization behavior study of the alkoxy-substituted porphyrin complexes 4b-e in terms of reaction temperature and CO 2 pressure is presented. Complexes bearing longer alkoxy-substituents demonstrate the highest polymerization activity and molecular weights, however all substituted catalyst systems display a reduced tolerance to increased temperature with respect to PPC formation. Studies of the resulting polymer microstructures show excellent head-to-tail epoxide incorporation and near perfectly alternating poly(carbonate) character at lower polymerization temperatures. © 2012 American Chemical Society.

  20. Tailored synthesis of amine N-halamine copolymerized polystyrene with capability of killing bacteria.

    Science.gov (United States)

    Cai, Qian; Bao, Sarina; Zhao, Yue; Zhao, Tianyi; Xiao, Linghan; Gao, Ge; Chokto, Harnoode; Dong, Alideertu

    2015-04-15

    Novel amine N-halamine copolymerized polystyrene (ANHCPS) nanostructures were controllably fabricated as potent antibiotics by using the surfactant-free emulsion copolymerization for killing pathogenic bacteria. The morphology and size of the ANHCPS were well tailored by tuning reaction conditions such as monomer molar ratio, temperature, and copolymerization time. Effect of chlorination aging time on the oxidative chlorine content in the ANHCPS was established, and the oxidative chlorine content was determined by the modified iodometric/thiosulfate technique. Antibacterial behavior of the ANHCPS on bacterial strain was evaluated using Staphylococcus aureus and Escherichia coli as model pathogenic bacteria via the plate counting technique, inhibition zone study, and time-kill assay. Antimicrobial results illustrated that the ANHCPS possessed superior antibacterial capability of killing pathogenic bacteria. The destruction induced by the ANHCPS on bacterial surface structure was proven by using SEM technique. The effect of the oxidative chlorine content and morphology/size on the antimicrobial capability was constructed as well. This study provides us a novel approach for controllably synthesizing amine N-halamine polymers, and making them the potent candidates for killing bacteria or even the control of microorganism contamination.

  1. A method of analysing experimental data of nuclear reaction cross sections

    Institute of Scientific and Technical Information of China (English)

    FengJun; ShenWen-Qing

    1997-01-01

    A method of analysing experimental data of nuclear reaction cross sections σr induced by radioactive beam is described.It can be used in analysis of experimental unclear reaction cross section data obtained by Na-isopope radioactive beams on different targets.Neutron halo has not been found in these nuclei.

  2. Singlet oxygen reactions with flavonoids. A theoretical-experimental study.

    Directory of Open Access Journals (Sweden)

    Javier Morales

    Full Text Available Detection of singlet oxygen emission, λ(max = 1270 nm, following laser excitation and steady-state methods were employed to measure the total reaction rate constant, k(T, and the reactive reaction rate constant, k(r, for the reaction between singlet oxygen and several flavonoids. Values of k(T determined in deuterated water, ranging from 2.4×10(7 M(-1 s(-1 to 13.4×10(7 M(-1 s(-1, for rutin and morin, respectively, and the values measured for k(r, ranging from 2.8×10(5 M(-1 s(-1 to 65.7×10(5 M(-1 s(-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.

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

    Science.gov (United States)

    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

  4. SEED SEMICONTINUOUS EMULSION MULTI-COPOLYMERIZATION OF (METH)ACRYLATES WITH HIGH-SOLID CONTENT:EFFECT OF THE OPERATION CONDITIONS

    Institute of Scientific and Technical Information of China (English)

    WANG Wenjun; YU Zaizhang; LI Bogeng; PAN Zuren

    1995-01-01

    The seeded semicontinuous emulsion multi-copolymerization of butyl acrylate (BA),2-ethylhexyl acrylate (2EHA), methyl methacrylate (MMA), 2-hydroxyl propyl acrylate(HOPA) and acrylic acid (AA) was used to prepare the acrylic latexes with high-solidcontent. The effects of monomer emulsion feed rates (Ra) and (R/E)E values, the ratio ofemulsifier amount between the initial charge (R) and the addition monomer emulsion (E) ,on the polymerization reaction features, the viscosities, surface tensions,particle sizes andparticle sizes distributions of latexes,Tg and the insoluble fractions of films, the 180° peelstrength, tack and holding power of pressure-sensitive adhesive (PSA) tapes, preparedfrom the latexes, were studied. Experimental study shows that the grafting and cross-linking fraction in the PSA tapes must be controlled within a suitable range to keep thebalance of the 180° peel strength, tack and holding power.

  5. Copolymerization Kinetics of Ethylene Oxide and Propylene Oxide

    Institute of Scientific and Technical Information of China (English)

    尹红; 陈志荣

    2002-01-01

    The copolymerization kinetics of ethylene oxide and propylene oxide in an atomizing-circulation reactorunder semi-continuous operation is studied which is of great importance for molecular designation. The kineticparameters are obtained by numerical optimization of the kinetic model.

  6. KINETICS OF VINYL CHLORIDE (CO)POLYMERIZATION AT HIGH CONVERSION

    Institute of Scientific and Technical Information of China (English)

    Zu-ren Pan; Zhi-xue Weng; Zhi-ming Huang

    1999-01-01

    This paper provides a summarized review on the kinetics of vinyl chloride homopolymerization in the absence and presence of chain transfer agents, of VC/DAP(diallyl phthalate) copolymerization with chain extension and/or slightly crosslinking functions, and of vinylidene chloride/VC random copolymerization.Models of rate, degree of polymerization or molecular weight, copolymer composition, gel fraction and crosslinking density were proposed and interpreted mechanistically.

  7. Micellar Copolymerization:the State of the Arts

    Institute of Scientific and Technical Information of China (English)

    FENG Yu-jun

    2004-01-01

    Over the past two decades, hydrophobically modified water-soluble polymers (HMWSPs),particularly hydrophobically associating polyacrylamides (HAPAMs), have attracted increased interest owing to their practical and fundamental importance[1]. This system usually consists of a hydrophilic backbone with a small proportion (generally less than 2 mol %) of hydrophobic pendent groups. When dissolved in aqueous solutions, the apolar moieties tend to exclude water and are held together by intra- and intermolecular hydrophobic associations. This leads to a transitional network structure that induces a substantial increase in solution viscosity. Such viscosity-building ability is further elevated upon adding salt or increasing temperature due to the enhanced polarity.Additionally, the dynamic associating junctions can be ruptured upon high shear stress, but re-formed when the force ceases. All these unique properties enable HAPAMs attractiveness to various industrial uses in which the control of fluid theology is required.However, it is a great challenge to synthesize HAPAMs since acrylamide and hydrophobic comonomers are mutually incompatible. After attempts using heterogeneous, inverse emulsion,microemulsion, and precipitation copolymerization processes, the commonly accepted method is micellar free radical copolymerization in which an appropriate surfactant is used to solubilize the hydrophobic comonomer[2].In this paper, the sate of the arts for micellar copolymerization is comprehensively reviewed:1. the mechanism of micellar copolymerization;2. parameters affecting micellar copolymerization, including:(1) nature and level of hydrophobic comonomer;(2) nature and content of surfactant used;(3) initiator and temperature.3. structural characteristics of HAPAMs prepared via micellar copolymerization;4. properties of HAPAMs prepared via micellar copolymerization:(1) dilute solution properties;(2) semi-dilute solution properties.5. applications of micellar copolymerization

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

    Energy Technology Data Exchange (ETDEWEB)

    Jones, K. L., E-mail: kgrzywac@utk.edu; Ayres, A.; Bey, A.; Burcher, S.; Cartegni, L.; Cerizza, G. [Department of Physics and Astronomy, University of Tennessee, Knoxville, TN 37996 (United States); Ahn, S. [Department of Physics and Astronomy, University of Tennessee, Knoxville, TN 37996 (United States); National Superconducting Cyclotron Laboratory and Department of Physics and Astronomy, Michigan State University, East Lansing, MI 48824 (United States); 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. [Physics Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Bardayan, D. W. [Physics Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Department of Physics, University of Notre Dame, Notre Dame, IN 46556 (United States); Baugher, T. [National Superconducting Cyclotron Laboratory and Department of Physics and Astronomy, Michigan State University, East Lansing, MI 48824 (United States); Department of Physics and Astronomy, Rutgers University, New Brunswick, NJ 08903 (United States); 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.

  9. Toxoplasma polymerase chain reaction on experimental blood samples.

    Science.gov (United States)

    Joss, A W; Chatterton, J M; Evans, R; Ho-Yen, D O

    1993-01-01

    A two-stage polymerase chain reaction (PCR) assay employing oligonucleotide primers from the B1 gene of Toxoplasma gondii was developed and assessed for sensitivity and specificity. It was able to detect T. gondii DNA from as little as one parasite/sample in mock-infected rat or mouse leucocyte preparations. Parasitaemia was also identified in animals at five stages between 16 and 66 h after infection with the virulent RH strain, and at 12 stages between 2 and 38 days after infection with the cyst-forming Beverley strain. In the latter case, PCR was more sensitive than animal culture. No cross-reactions were observed in samples containing various opportunist pathogens which may also be found in the blood of immunocompromised patients.

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

    Energy Technology Data Exchange (ETDEWEB)

    Jones, K. L. [University of Tennessee, Knoxville (UTK); Ahn, S.H. [University of Tennessee, Knoxville (UTK); Allmond, James M [ORNL; Ayres, A. [University of Tennessee, Knoxville (UTK); Bardayan, Daniel W [ORNL; Baugher, T. [Michigan State University, East Lansing; Bazin, D. [Michigan State University, National Superconducting Cyclotron Laboratory (NSCL); Beene, James R [ORNL; Berryman, J. S. [Michigan State University, East Lansing; Bey, A. [University of Tennessee, Knoxville (UTK); Bingham, C. R. [University of Tennessee, Knoxville (UTK); Cartegni, L. [University of Tennessee, Knoxville (UTK); Chae, K. Y. [University of Tennessee, Knoxville (UTK)/Sungkyunkwan University, Korea; Cizewski, J. A. [Rutgers University; Gade, A. [Michigan State University, National Superconducting Cyclotron Laboratory (NSCL); Galindo-Uribarri, Alfredo {nmn} [ORNL; Garcia-Ruiz, R.F. [Instituut voor Kernen Stralingsfysica, KU Leuven, B-3001, Leuven, Belgium; Grzywacz, Robert Kazimierz [ORNL; Howard, Meredith E [ORNL; Kozub, R. L. [Tennessee Technological University (TTU); Liang, J Felix [ORNL; Manning, Brett M [ORNL; Matos, M. [Louisiana State University; McDaniel, S. [Michigan State University, East Lansing; Miller, D. [University of Tennessee, Knoxville (UTK); Nesaraja, Caroline D [ORNL; O' Malley, Patrick [Rutgers University; Padgett, S [University of Tennessee, Knoxville (UTK); Padilla-Rodal, Elizabeth [Universidad Nacional Autonoma de Mexico (UNAM); Pain, Steven D [ORNL; Pittman, S. T. [University of Tennessee (UTK) and Oak Ridge National Laboratory (ORNL); Radford, David C [ORNL; Ratkiewicz, Andrew J [ORNL; Schmitt, Kyle [ORNL; Smith, Michael Scott [ORNL; Stracener, Daniel W [ORNL; Stroberg, S. [Michigan State University, East Lansing; Tostevin, Jeffrey A [ORNL; Varner Jr, Robert L [ORNL; Weisshaar, D. [Michigan State University, East Lansing; Wimmer, K. [Michigan State University, National Superconducting Cyclotron Laboratory (NSCL)/Central Michigan University; Winkler, R. [Michigan State University, East Lansing

    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.

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

    Science.gov (United States)

    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.

  12. Effects of stereochemistry and copolymerization on the LCST of PNIPAm

    Science.gov (United States)

    de Oliveira, Tiago E.; Mukherji, Debashish; Kremer, Kurt; Netz, Paulo A.

    2017-01-01

    Poly(N-isopropylacrylamide) (PNIPAm) is a smart polymer that presents a lower critical transition temperature (LCST) of 305 K. Interestingly, this transition point falls within the range of the human body temperature, making PNIPAm a highly suitable candidate for bio-medical applications. However, it is sometimes desirable to have a rather flexible tuning of the LCST of these polymers to further increase their range of applications. In this work, we use all-atom molecular dynamics simulations to study the LCST of PNIPAm-based (co-)polymers. We study different molecular architectures where the polymer sequences are tuned either by modifying its stereochemistry or by the co-polymerization of PNIPAm with acrylamide (Am) units. Our analysis connects global polymer conformations with the microscopic intermolecular interactions. These findings suggest that the collapse of a PNIPAm chain upon heating is dependent on the hydration structure around the monomers, which is strongly dependent on the tacticity and the presence of more hydrophilic acrylamide monomers. Our results are found to be in good agreement with the existing experimental data.

  13. MODIFICATION OF SILK FIBER via EMULSION GRAFT COPOLYMERIZATION WITH FLUOROACRYLATE

    Institute of Scientific and Technical Information of China (English)

    Zhan-xiong Li; Fei-fei Jin; Ben-wen Cao; Xiao-fei Wang

    2008-01-01

    2,2,3,3,4,4,5,5-Octafluoropentyl acrylate was grafted onto silk fiber in a two-step heterogeneous system through the vinyl bonds of acryloyloxyethyl isocyanate modified on the silk. The grafted copolymer was analyzed by FTIR and WAXD, and the results revealed that the fluoroacrylate was successfully grafted onto silk fiber and the crystalline structure of silk fibroin with β-sheet structure was not changed after graft copolymerization. The FT-IR corrected method was used to simulate the grafting yield onto silk compared with the weight increasing method. The results obtained from these two methods were roughly consistent. The influence of the initiator concentration, monomer concentration, react time and temperature on the graft yield was also investigated. The experimental data of thermogravimetry (TG) and differential thermal analysis (DTA) showed that the thermal stability of the modified silk fibers was improved due to the introduction of fluoroacrylate. In comparison with the untreated silk fibers, the water repellence of the modified silk fibers was also improved.

  14. Experimental and Theoretical Investigation of Shock-Induced Reactions in Energetic Materials.

    Energy Technology Data Exchange (ETDEWEB)

    Kay, Jeffrey J; Park, Samuel; Kohl, Ian Thomas; Knepper, Robert

    2017-09-01

    In this work, shock-induced reactions in high explosives and their chemical mechanisms were investigated using state-of-the-art experimental and theoretical techniques. Experimentally, ultrafast shock interrogation (USI, an ultrafast interferometry technique) and ultrafast absorption spectroscopy were used to interrogate shock compression and initiation of reaction on the picosecond timescale. The experiments yielded important new data that appear to indicate reaction of high explosives on the timescale of tens of picoseconds in response to shock compression, potentially setting new upper limits on the timescale of reaction. Theoretically, chemical mechanisms of shock-induced reactions were investigated using density functional theory. The calculations generated important insights regarding the ability of several hypothesized mechanisms to account for shock-induced reactions in explosive materials. The results of this work constitute significant advances in our understanding of the fundamental chemical reaction mechanisms that control explosive sensitivity and initiation of detonation. * Principal Investigator. jjkay@sandia.gov

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

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

    KAUST Repository

    Pei, Cuiying

    2014-01-01

    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 CO 2 adsorption properties both at low and high pressures. This journal is © the Partner Organisations 2014.

  19. EFFECT OF SOLVENT ON THE COPOLYMERIZATION OF 2,2,6,6-TETRAMETHYL 4-PIPERIDINYL METHACRYLATE WITH STYRENE

    Institute of Scientific and Technical Information of China (English)

    ZHAO Ruinian; LIANG Wenzhong

    1988-01-01

    The radical copolymerizations of 2,2,6,6-tetramethyl 4-piperidinyl methacrylate (TMPM) with styrene in various solvents have been studied. The monomer reactivity ratios r1 and r2 were determined. It is observed that in all of these reaction systems, there are appreciable solvent effects on both r1 and r2, which can be correlated to the difference in chemical shifts of olefinic protons of TMPM. And the variance of the copolymer microstructure in various media was discussed.

  20. Status of experimental data of proton-induced reactions for intermediate-energy nuclear data evaluation

    Energy Technology Data Exchange (ETDEWEB)

    Watanabe, Yukinobu; Kawano, Toshihiko [Kyushu Univ., Fukuoka (Japan); Yamano, Naoki; Fukahori, Tokio

    1998-11-01

    The present status of experimental data of proton-induced reactions is reviewed, with particular attention to total reaction cross section, elastic and inelastic scattering cross section, double-differential particle production cross section, isotope production cross section, and activation cross section. (author)

  1. Tissue reactions to abutment shift: an experimental study in dogs.

    Science.gov (United States)

    Abrahamsson, Ingemar; Berglundh, Tord; Sekino, Satoshi; Lindhe, Jan

    2003-01-01

    Standard protocols for the clinical use of dental implants often include the placement of healing abutments prior to standard or custom-made abutments. The tissue response to a single shift from a healing abutment to a permanent abutment has not been studied. The aim of the present experiment was to study tissue reactions that may occur following the removal of a healing abutment and the placement of a permanent abutment. In six beagle dogs, all mandibular premolars were extracted. Three months later three fixtures of the Astra Tech Implants Dental System (Astra Tech AB, Mölndal, Sweden) were installed in each edentulous premolar region. An additional 3 months later, the first abutment connection was performed. In two sites on each side of the mandible, healing abutments were placed; in the remaining site, a Uni-abutment (Astra Tech AB) was used. The two healing abutments were removed 2 weeks later, and one Uni-abutment and one prepable abutment were placed. A plaque-control period was initiated, and 6 months later block biopsies were obtained. The biopsies were prepared for histometric and morphometric examination. Radiographs were obtained at fixture placement, 2 weeks after the first abutment connection, and 6 months later. The length of the barrier epithelium, the height of the connective tissue attachment, and the level of the marginal bone did not differ between the three abutment groups. The major part of the radiographic bone loss during the experiment took place prior to or immediately after abutment connection; only small bone level alterations occurred during the subsequent 6-month period. The shift from a healing abutment to a permanent abutment resulted in the establishment of a transmucosal attachment, the dimension and quality of which did not differ from those of the mucosal barrier formed to a permanent abutment placed during a second-stage surgery.

  2. Study of n-Butyl Acrylate Self-Initiation Reaction Experimentally and via Macroscopic Mechanistic Modeling

    Directory of Open Access Journals (Sweden)

    Ahmad Arabi Shamsabadi

    2016-04-01

    Full Text Available This paper presents an experimental study of the self-initiation reaction of n-butyl acrylate (n-BA in free-radical polymerization. For the first time, the frequency factor and activation energy of the monomer self-initiation reaction are estimated from measurements of n-BA conversion in free-radical homo-polymerization initiated only by the monomer. The estimation was carried out using a macroscopic mechanistic mathematical model of the reactor. In addition to already-known reactions that contribute to the polymerization, the model considers a n-BA self-initiation reaction mechanism that is based on our previous electronic-level first-principles theoretical study of the self-initiation reaction. Reaction rate equations are derived using the method of moments. The reaction-rate parameter estimates obtained from conversion measurements agree well with estimates obtained via our purely-theoretical quantum chemical calculations.

  3. STUDIES ON THE RING-OPENING POLYMERIZATION OF TETRAHYDROFURAN Ⅳ. COPOLYMERIZATION OF TETRAHYDROFURAN AND PROPYLENE OXIDE INITIATED BY FUMING SULFURIC ACID AND PERCHLORIC ACID CATALYST SYSTEM

    Institute of Scientific and Technical Information of China (English)

    ZHANG Hongzhi; GAO Guozhen; WANG Yin; FENG Xinde(S. T. Voong)

    1983-01-01

    The yield of copolymerization of tetrahydrofuran and propylene oxide (THF: PO = 100: 5-15, by wt) using a binary catalyst of fuming sulfuric acid (21% or 28%) and perchloric acid is around 50-60%, and the loss of THF in the reaction is below 10-15%. The average molecular weight of the product can be controlled in the range of 1000-2000 by varying the binary catalyst system.The present method, which is different from the usual copolymerization initiated by BF3-diol or SbCl5-diol system, shows the pecularities i.e. the yield of copolymerization with the low PO feed is not decreased, the hydroxyl functionality is equal to 2, and the end-groups are predominantly primary hydroxyls (around 65-70%).

  4. Derivation of capture and reaction cross sections from experimental quasi-elastic and elastic backscattering probabilities

    CERN Document Server

    Sargsyan, V V; Antonenko, N V; Gomes, P R S

    2013-01-01

    The direct measurement of the reaction or capture (fusion) cross section is a difficult task since it would require the measurement of individual cross sections of many reaction channels, and most of them could be reached only by specific experiments. This would require different experimental set-ups not always available at the same laboratory and, consequently, such direct measurements would demand a large amount of beam time and would take probably some years to be reached. Because of that, the measurements of elastic scattering angular distributions that cover full angular ranges and optical model analysis have been used for the determination of reaction cross sections. This traditional method consists in deriving the parameters of the complex optical potentials which fit the experimental elastic scattering angular distributions and then of deriving the reaction cross sections predicted by these potentials. Even so, both the experimental part and the analysis of this latter method are not so simple. In the...

  5. Study on Copolymerization of Rare Earth-Carboxylic Acid Complex

    Institute of Scientific and Technical Information of China (English)

    Qiu Guanmin(邱关明); Zhang Ming(张明); Yan Chang hao(严长浩); Zhou Lanxiang(周兰香); Dai Shaojun(戴少俊); Okamo to Hiroshi

    2003-01-01

    Complex of rare earth with carboxylic acid was prepared by precipita tion and direct method. It was copolymerized with such monomers as acrylic acid and other ones to synthesize ionomer of rare earth and organic polymer with different rare earth contents. Its glass-transition temperature and heat stability were analyzed by TG and DTA. Infra-red detector was used to show its structure. The effect of rare earth complex prepared by different methods on copolymerization and properties of copolymers was also discussed.

  6. Copolymerization of Styrene with Dodecyl Methacrylate and Octadecyl Methacrylate

    OpenAIRE

    Vidović, Elvira; SARIĆ, Karla; JANOVIĆ, Zvonimir

    2002-01-01

    Styrene (Sty) was copolymerized with dodecyl methacrylate (DDMA) and with octadecyl methacrylate (ODMA) in toluene solution using 2,2'-azobis(isobutyronitrile) (AIBN) as a free radical initiator over a wide composition and conversion range. The copolymer composi-tion was determined from NMR spectra. The copolymerization reactivity ratios were found to be r1 = 0.52 (Sty) and r2 = 0.42 (DDMA) for the Sty-DDMA system, and r1 = 0.58 (Sty) and r2 = 0.45 (ODMA) for the Sty-ODMA system, showing a te...

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

    Science.gov (United States)

    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

  8. Organostibine mediated controlled/living random copolymerization of styrene and methyl methacrylate

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    The first example of organostibine mediated controlled/living random copolymerization of styrene(St) and methyl methacrylate(MMA) was achieved by heating a solution of St/MMA/organostibine mediator at 100 °C or St/MMA/organostibine mediator/AIBN with various monomer feed ratios at 60 °C.The addition of AIBN significantly decreased the reaction temperature and enhanced the rate of copolymerization.The structure of poly(St-co-MMA) was verified by 1H NMR.The reactivity ratios at 60 °C were determined by the extended Kelen-Tüds method to be YSt = 0.40 and YMMA = 0.44.The ln([M]0/[M]) increased linearly with increasing reaction time.The number-average molecular weights of poly(St-co-MMA) increased linearly with conversion.Poly(St-co-MMA) with expected number-average molecular weight and low polydispersity index was formed.The living characteristic was further confirmed by chain-extension of poly(St-co-MMA) to form poly(St-co-MMA)-b-PMMA.

  9. ON COPOLYMERIZATION KINETICS OF N-VINYL PYRROLIDONE METHYL METHACRYLATE AT HIGH CONVERSION

    Institute of Scientific and Technical Information of China (English)

    WEN Jianyie; Sun Yishi

    1988-01-01

    In this work, Fourier transform infrared spectroscopy was used to study the copolymerization kinetics of N-vinyl pyrrolidone-methyl methacrylate (VPMMA) at high conversion. Through computer simulation,copolymerization rate equation based on the free volume theory, diffusion theory and modified MH model was established. The activation energy of copolymerization was also estimated.

  10. SELECTIVE SEPARATION OF WATER—ETHANOL MIXTURE THROUGH COPOLYMERIC MEMBRANES.Ⅱ.ACRYLONITRILE AND MALEIC ANHYDRIDE COPOLYMERIC MEMBRANES

    Institute of Scientific and Technical Information of China (English)

    ZHangFuyao; ZhangYifeng; 等

    1993-01-01

    Acrylonitrile(AN) and maleic anhydride(MA) copolymer has been synthesized by radical polymerization using ammonium persulfate and sodium bisulfite as initiator.The pervaporation properties of the copolymeric membranes prepared have been investigated for the first time. The dependences of pervaporation characteristics on coplymer composition,feed concentration and operating temperature have been studied.In order to improve the separation properties of the copolymeric membranes,the membranes were hydrolyzed with 10 wt% soldium hydroxide or potassium hydroxide aqueous solution.The hydrolyzed membranes containing more than 0.069MA mol fraction showed higher tensile strength and separation properties than the original membranes.

  11. SYNTHESIS OF FUNCTIONAL POLYETHYLENE via COPOLYMERIZATION OF ETHYLENE AND SUBSTITUTED ALLENE USING BIS(β-ENAMINOKETONATO)TITANIUM CATALYSTS

    Institute of Scientific and Technical Information of China (English)

    Miao Hong; Bai-xiang Li; Yue-sheng Li

    2011-01-01

    Novel copolymerization of ethylene with substituted allenes (CH2=C=CH-R,1:R =n-butyl,2:R =n-octyl)using bis(β-enaminoketonato)titanium catalysts [PhN=C(R2)CHC(R1)O]2TiCl2 (1a:R1 =CF3,R2 =CH3; 1b:R1 =Ph,R2 =CF3) has been investigated.In the presence of modified methylaluminoxane,these catalysts can copolymerize ethylene with substituted allenes,affording copolymers with unimodal molecular weight distributions and homogeneous compositions.By varying the reaction conditions,the comonomer incorporation can be tuned in the range of 0-3.6 mol%.1H-NMR spectra reveal that the copolymerization proceeds through 1,2-insertion fashion of allene comonomer exclusively,and the regioselective nature maintains under various reaction conditions.The retained intra-chain double bond can be converted into the epoxy group under mild conditions.

  12. EFFECT OF 2—HYDROXYETHYL METHACRYLATE ON SEMIBATCH EMULSIFIER—FREE EMULSION COPOLYMERIZATION OF METHYL METHACRYLATE AND BUTYL ACRYLATE

    Institute of Scientific and Technical Information of China (English)

    GUOTianying; SONGMoudao; 等

    1999-01-01

    The semibatch emulsifier-free emulsion copolymerization of methyl methacrylate (MMA) and butyl acrylate(BA) in the presence of 2-hydroxyethyl methacrylate(HEMA) initiated by K2S2O8(PSP) was studied.The latex particles can maintain an appreciable stability during the emulsifier-free emulsion copolymerization of MMA and BA in the presence of HEMA.The average particle diameter increase with an increase of total solids content,HEMA content,PSP content,ionic strength of the system and monomer feed rate,and decrease with the monomer feed ration from 3/1 (MMA/BA:molar ration).to 1/3.The stability of this reaction system is improved by adding HEMA as nonionic comonomer,High solids content (50%) latex with monodisperse particle can be obtained using this process.

  13. The reaction between iodine and organic coatings under severe PWR accident conditions. An experimental parameter study

    Energy Technology Data Exchange (ETDEWEB)

    Hellmann, S.; Funke, F.; Greger, G.U.; Bleier, A.; Morell, W. [Siemens AG, Power Generation Group, Erlangen (Germany)

    1996-12-01

    An extensive experimental parameter study was performed on the deposition and on the resuspension kinetics in the reaction system iodine/organically coated surfaces. Both reactions in the gas phase and in the liquid phase were investigated and kinetic rate constants suitable for modelling were derived. Previous experimental studies on the reaction of iodine with organic coated surfaces were mostly limited to temperatures below 100{sup o}C. Thus, this parameter study aims at filling a gap and providing kinetic data on heterogeneous reactions with organic surfaces in the accident-relevant temperature range of 100-160{sup o}C. Two types of laboratory experiments carried out at Siemens/KWU using coatings representative for German power plants (epoxy-tape paint), namely gas phase tests and liquid phase tests. (author) 6 figs., 6 tabs., 5 refs.

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

    Energy Technology Data Exchange (ETDEWEB)

    Semkova, V. [IAEA Nuclear Data Section, Vienna (Austria); Pritychenko, B. [Brookhaven National Lab. (BNL), Upton, NY (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Semkova, V. [IAEA Nuclear Data Section, Vienna (Austria); Pritychenko, B. [Brookhaven National Lab. (BNL), Upton, NY (United States)

    2014-12-01

    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.

  16. EXFOR – a global experimental nuclear reaction data repository: Status and new developments

    Directory of Open Access Journals (Sweden)

    Semkova Valentina

    2017-01-01

    Full Text Available Members of the International Network of Nuclear Reaction Data Centres (NRDC have collaborated since the 1960s on the worldwide collection, compilation and dissemination of experimental nuclear reaction data. New publications are systematically complied, and all agreed data assembled and incorporated within the EXFOR database. Recent upgrades to achieve greater completeness of the contents are described, along with reviews and adjustments of the compilation rules for specific types of data.

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

    DEFF Research Database (Denmark)

    Mijatovic, Nenad; Jensen, Bogi Bech

    2014-01-01

    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....

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

    Science.gov (United States)

    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.

  19. EFFECT OF PRESSURE INDUCED GRAFT COPOLYMERIZATION ON THE PHYSICO-CHEMICAL PROPERTIES OF BIO-FIBERS

    Directory of Open Access Journals (Sweden)

    Amar Singh Singha

    2010-04-01

    Full Text Available The present study deals with the surface modification of Agave americana L. fiber through graft copolymerization of methyl methacrylate under pressure in the presence of ceric ammonium nitrate as redox initiator. The various reaction parameters such as reaction time, pressure, concentration of nitric acid, initiator, and monomer, etc. were optimized to have the maximum graft yield of 13.6%. The grafted fibers were then subjected to the evaluation of different physico-chemical properties such as swelling behavior, solubility, moisture absorption under different humidity levels, resistance to acids and bases, etc. It was observed that swelling behavior, solubility behavior, and moisture absorbance decreased with increase in grafting, whereas resistance to acids and bases increased with grafting. The fibers grafted under the optimized conditions were then characterized by Fourier transform infra-red spectroscopy, scanning electron microscopy, thermogravimetric analysis, and x-ray diffraction techniques.

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

    Science.gov (United States)

    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.

  1. Observing Proton Transfer Reactions Inside the MALDI Plume: Experimental and Theoretical Insight into MALDI Gas-Phase Reactions

    Science.gov (United States)

    Mirabelli, Mario F.; Zenobi, Renato

    2017-08-01

    We evaluated the contribution of gas-phase in-plume proton transfer reactions to the formation of protonated and deprotonated molecules in the MALDI process. A split sample holder was used to separately deposit two different samples, which avoids any mixing during sample preparation. The two samples were brought very close to each other and desorbed/ionized by the same laser pulse. By using a combination of deuterated and non-deuterated matrices, it was possible to observe exclusively in-plume proton transfer processes. The hydrogen/deuterium exchange (HDX) kinetics were evaluated by varying the delayed extraction (DE) time, allowing the desorbed ions and neutrals to interact inside the plume for a variable period of time before being extracted and detected. Quantum mechanical calculations showed that the HDX energy barriers are relatively low for such reactions, corroborating the importance of gas-phase proton transfer in the MALDI plume. The experimental results, supported by theoretical simulations, confirm that the plume is a very reactive environment, where HDX reactions could be observed from 0 ns up to 400 ns after the laser pulse. These results could be used to evaluate the relevance of previously proposed (and partially conflicting) ionization models for MALDI.

  2. Nuclear reactions in astrophysics: Recent experimental and theoretical studies, and further quests

    Energy Technology Data Exchange (ETDEWEB)

    Arnould, M. (Inst. d' Astronomie et d' Astrophysique, Univ. Libre, Brussels (Belgium))

    1992-03-09

    A brief review is presented of recent theoretical and experimental efforts that have led to an improvement in our knowledge of nuclear reaction rates of interest in astrophysics. Emphasis is also put on the still existing (sometimes very large) uncertainties that affect some important rates. This is especially the case when short-lived nuclei are involved in the entrance channel. (orig.).

  3. Investigation of the quasifission process by theoretical analysis of experimental data of fissionlike reaction products

    CERN Document Server

    Giardina, G; Mandaglio, G; Curciarello, F; De Leo, V; Fazio, G; Manganaro, M; Romaniuk, M; Saccá, C; 10.1088/1742-6596/282/1/012006

    2011-01-01

    The fusion excitation function is the important quantity in planning experiments for the synthesis of superheavy elements. Its values seem to be determined by the experimental study of the hindrance to complete fusion by the observation of mass, angular and energy distributions of the fissionlike fragments. There is ambiguity in establishment of the reaction mechanism leading to the observed binary fissionlike fragments. The fissionlike fragments can be produced in the quasifission, fast fission, and fusion-fission processes which have overlapping in the mass (angular, kinetic energy) distributions of fragments. The branching ratio between quasifission and complete fusion strongly depends on the characteristics of the entrance channel. In this paper we consider a wide set of reactions (with different mass asymmetry and mass symmetry parameters) with the aim to explain the role played by many quantities on the reaction mechanisms. We also present the results of study of the $^{48}$Ca+$^{249}$Bk reaction used t...

  4. Polar-Nonpolar Radical Copolymerization under Li+ Catalysis

    Science.gov (United States)

    2008-09-21

    description of our copolymerization results. The polyisobutylene (b- PIB ) that is produced by homopolymerization of IB in an inert solvent such as 1,2...the linear polyisobutylene (l- PIB ) produced under the usual cationic initiation. The difference is clear in spectral (NMR) and physical (DSC, TGA...HPLC) properties. A detailed 2D-NMR examination of b- PIB obtained from ordinary IB and several isotopically labeled versions of IB revealed that its

  5. Dynamic optimization of a mma with vac copolymerization

    OpenAIRE

    Lima, Nádson Murilo Nascimento; Liñan, Lamia Zuñiga; Maciel Filho,Rubens; Manenti, Flavio; Manca, Davide; Embiruçu, Marcelo

    2009-01-01

    p. 1377-1382. Increasing worldwide market competitiveness and reduced profit margins are pressing chemical and process industries to move towards a predictive control approach, based on first-principles mathematical models, as well as plant dynamic optimization. In this perspective, the paper focuses on the development of a nonlinear model predictive control (NMPC) to manage the copolymerization process of methyl methacrylate (MMA) with vinyl acetate (VAc), consisting of a j...

  6. Comparison of Polymer Networks Synthesized by Conventional Free Radical and RAFT Copolymerization Processes in Supercritical Carbon Dioxide

    Directory of Open Access Journals (Sweden)

    Patricia Pérez-Salinas

    2017-05-01

    Full Text Available There is a debate in the literature on whether or not polymer networks synthesized by reversible deactivation radical polymerization (RDRP processes, such as reversible addition-fragmentation radical transfer (RAFT copolymerization of vinyl/divinyl monomers, are less heterogeneous than those synthesized by conventional free radical copolymerization (FRP. In this contribution, the syntheses by FRP and RAFT of hydrogels based on 2-hydroxyethylene methacrylate (HEMA and ethylene glycol dimethacrylate (EGDMA in supercritical carbon dioxide (scCO2, using Krytox 157 FSL as the dispersing agent, and the properties of the materials produced, are compared. The materials were characterized by differential scanning calorimetry (DSC, swelling index (SI, infrared spectroscopy (FTIR and scanning electron microscopy (SEM. Studies on ciprofloxacin loading and release rate from hydrogels were also carried out. The combined results show that the hydrogels synthesized by FRP and RAFT are significantly different, with apparently less heterogeneity present in the materials synthesized by RAFT copolymerization. A ratio of experimental (Mcexp to theoretical (Mctheo molecular weight between crosslinks was established as a quantitative tool to assess the degree of heterogeneity of a polymer network.

  7. Experimental study to explore the $\\rm ^8Be$ induced nuclear reaction via the Trojan Horse Method

    CERN Document Server

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

    2014-01-01

    To explore a possible indirect method for $\\rm ^8Be$ induced astrophysical reactions, the $\\rm ^9Be=({}^8Be+\\it n)$ cluster structure was studied via the Trojan Horse Method. It is the first time to study a super short life nucleus $\\rm ^8Be$ via the Trojan Horse Method, and it is the first time to make a valid test for $l=1$ Trojan-horse nucleus. The $\\rm ^9Be$ nucleus is assumed to have a ($\\rm {}^8Be+\\it n$) cluster structure and used as the Trojan-horse nucleus. The $\\rm ^8Be$ nucleus acts as a participant, while the neutron is a spectator to the virtual $\\rm ^8Be +{\\it d}\\rightarrow \\alpha + {}^6Li$ reaction via a suitable 3-body reaction $\\rm ^9Be +{\\it d}\\rightarrow \\alpha + {}^6Li +\\it n$. The experimental neutron momentum distribution inside $\\rm ^9Be$ was reconstructed. The agreement between experimental and theoretical momentum distribution indicates that there should be a ($\\rm {}^8Be+\\it n$) cluster structure inside $\\rm ^9Be$. Therefor the experimental study of $\\rm ^8Be$ induced reactions, for ...

  8. Eclogite-melt/peridotite reaction: Experimental constrains on the destruction mechanism of the North China Craton

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    To study the mechanism of melt-peridotite reaction pertinent to the destruction of the North China Craton (NCC) lithosphere, a series of experiments were performed at a pressure of 2.0 GPa and temperatures from 1250 to 1400°C using Bixiling eclogite and Damaping peridotite as starting materials. The experimental results show that the reaction between eclogite melt and peridotite causes dissolution of olivine and orthopyroxene and precipitation of clinopyroxene in the melt. The experimental run products, characterized by a lherzolite/pyroxenite/garnet-pyroxenite sequence, are consistent with the mantle xenoliths in the Neogene Hannuoba basalt of the NCC found by Liu et al. (2005). It suggests that the mafic lower continental crust was probably recycled into the mantle during the Mesozoic Era. In the experiments conducted at 1300 and 1350°C, the resulting melts have a high Mg# andesite signature, indicating that the melt-peridotite reaction may have played a major role in the generation of high Mg# andesite. Our experimental results support the hypothesis that melts derived from foundered eclogite in the asthenosphere will consume the lithospheric peridotites. Therefore, melt-peridotite reaction is an important mechanism for the destruction/thinning of the lithosphere.

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

    Energy Technology Data Exchange (ETDEWEB)

    Ruff, Kiersten M. [Computational and Systems Biology Program and Center for Biological Systems Engineering, Washington University in St. Louis, St. Louis, Missouri 63130-4899 (United States); Harmon, Tyler S. [Department of Physics and Center for Biological Systems Engineering, Washington University in St. Louis, St. Louis, Missouri 63130-4899 (United States); Pappu, Rohit V., E-mail: pappu@wustl.edu [Department of Biomedical Engineering and Center for Biological Systems Engineering, Washington University in St. Louis, CB 1097, St. Louis, Missouri 63130-4899 (United States)

    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.

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

    Science.gov (United States)

    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. Copyright © 2015 The Authors. Published by Elsevier Ireland Ltd.. All rights reserved.

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

    Science.gov (United States)

    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.

  12. Modeling of a fluidized bed reactor for the ethylene-propylene copolymerization

    Directory of Open Access Journals (Sweden)

    Juan Guillermo Cadavid Estrada

    2010-04-01

    Full Text Available A mathematical model for the ethylene - propylene copolymerization with a Ziegler - Natta catalyst in a gas phase fludized bed reactor is presented. The model includes a two active site kinetic model with spontaneous transfer reactions and site deactivation. Also, it is studied and simulated the growth of a polymeric particle which is exposed to an outside atmosphere (monomers concentrations and temperature that represent the emulsion phase conditions of the reactor. Particle growth model is the basis for the study of the sizes distribution into the reactor. Two phase model of Kunii-Levenspiel is the basis for the modelling and simulation of the fluid bed reactor, the models developed consider two extreme cases for the gas mixed grade in emulsion phase (perfectly mixed and plug flow. The solution of the models includes mass (for the two monomers and energy balances, coupled with the particle growth and residence time distribution models.

  13. Surrogate Models for Online Monitoring and Process Troubleshooting of NBR Emulsion Copolymerization

    Directory of Open Access Journals (Sweden)

    Chandra Mouli R. Madhuranthakam

    2016-03-01

    Full Text Available Chemical processes with complex reaction mechanisms generally lead to dynamic models which, while beneficial for predicting and capturing the detailed process behavior, are not readily amenable for direct use in online applications related to process operation, optimisation, control, and troubleshooting. Surrogate models can help overcome this problem. In this research article, the first part focuses on obtaining surrogate models for emulsion copolymerization of nitrile butadiene rubber (NBR, which is usually produced in a train of continuous stirred tank reactors. The predictions and/or profiles for several performance characteristics such as conversion, number of polymer particles, copolymer composition, and weight-average molecular weight, obtained using surrogate models are compared with those obtained using the detailed mechanistic model. In the second part of this article, optimal flow profiles based on dynamic optimisation using the surrogate models are obtained for the production of NBR emulsions with the objective of minimising the off-specification product generated during grade transitions.

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

    Science.gov (United States)

    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.

  15. Radiation-induced graft copolymerization of binary monomer mixture containing acrylonitrile onto polyethylene films

    Science.gov (United States)

    Choi, Seong-Ho; Nho, Young Chang

    2000-04-01

    Graft copolymerization of acrylonitrile (AN)/acrylic acid (AA), acrylonitrile (AN)/methacrylic acid (MA), and acrylonitrile (AN)/glycidyl methacrylate (GMA) onto pre-irradiated polyethylene (PE) films were studied. The effect of reaction conditions such as solvents, additives, and monomer composition on the grafting yields was investigated. The extent of grafting was found to increase with increasing sulfuric acid concentration when sulfuric acid as an additive was added to the grafting solution. In AN/AA mixture, the proportion of acrylonitrile in the copolymer increased with an increasing AN component in feed monomers. On the other hand, in AN/MA mixture, acrylonitrile component in copolymer was very slight in spite of the increase AN component in feed monomers. In the AN/GMA mixture, the proportion of acrylonitrile in the copolymer increased with increasing acrylonitrile component in AN/GMA feed monomer.

  16. Experimental methods for quantifying the activity of platinum electrocatalysts for the oxygen reduction reaction.

    Science.gov (United States)

    Garsany, Yannick; Baturina, Olga A; Swider-Lyons, Karen E; Kocha, Shyam S

    2010-08-01

    A tutorial is provided for methods to accurately and reproducibly determine the activity of Pt-based electrocatalysts for the oxygen reduction reaction in proton exchange membrane fuel cells and other applications. The impact of various experimental parameters on electrocatalyst activity is demonstrated, and explicit experimental procedures and measurement protocols are given for comparison of electrocatalyst activity to fuel cell standards. (To listen to a podcast about this article, please go to the Analytical Chemistry multimedia page at pubs.acs.org/page/ancham/audio/index.html.).

  17. On adduct formation and reactivity in the OCS + OH reaction: A combined theoretical and experimental study

    Science.gov (United States)

    Schmidt, Johan A.; Kyte, Mildrid; Østerstrøm, Freja F.; Joelsson, Lars M. T.; Knap, Hasse C.; Jørgensen, Solvejg; Nielsen, Ole John; Murakami, Tatsuhiro; Johnson, Matthew S.

    2017-05-01

    The OCS + OH reaction occurs either via adduct formation or direct S-abstraction. We investigate OH-oxidation of OCS using quantum chemical methods and find that the OC(OH)S adduct reacts rapidly with O2 forming SOOH + CO2. SOOH rapidly dissociates under atmospheric conditions regenerating OH. We interpret earlier experimental results based on monitoring OH-loss, and find that OH-regeneration in presence of O2 may explain the insensitivity of the reaction rate to pressure and O2. We calculate a rate constant of 3.52 ×10-16 cm3 s-1 at 10 Torr increasing to 7.20 ×10-16 cm3 s-1 at 700 Torr. In addition we present a new experimental determination of the OCS + OH rate constant of (5.3 ± 3.6) ×10-15 cm3 s-1 at 296 K and 700 Torr using relative-rate technique.

  18. Concerning the Deactivation of Cobalt(III)-Based Porphyrin and Salen Catalysts in Epoxide/CO 2 Copolymerization

    KAUST Repository

    Xia, Wei

    2015-02-05

    © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. Functioning as active catalysts for propylene oxide (PO) and carbon dioxide copolymerization, cobalt(III)-based salen and porphyrin complexes have drawn great attention owing to their readily modifiable nature and promising catalytic behavior, such as high selectivity for the copolymer formation and good regioselectivity with respect to the polymer microstructure. Both cobalt(III)-salen and porphyrin catalysts have been found to undergo reduction reactions to their corresponding catalytically inactive cobalt(II) species in the presence of propylene oxide, as evidenced by UV/Vis and NMR spectroscopies and X-ray crystallography (for cobalt(II)-salen). Further investigations on a TPPCoCl (TPP=tetraphenylporphyrin) and NaOMe system reveal that such a catalyst reduction is attributed to the presence of alkoxide anions. Kinetic studies of the redox reaction of TPPCoCl with NaOMe suggests a pseudo-first order in cobalt(III)-porphyrin. The addition of a co-catalyst, namely bis(triphenylphosphine)iminium chloride (PPNCl), into the reaction system of cobalt(III)-salen/porphyrin and PO shows no direct stabilizing effect. However, the results of PO/CO2 copolymerization by cobalt(III)-salen/porphyrin with PPNCl suggest a suppressed catalyst reduction. This phenomenon is explained by a rapid transformation of the alkoxide into the carbonate chain end in the course of the polymer formation, greatly shortening the lifetime of the autoreducible PO-ring-opening intermediates, cobalt(III)-salen/porphyrin alkoxides. CO2 saves: The deactivation of cobalt(III)-porphyrin and salen catalysts in propylene oxide/carbon dioxide copolymerization is systematically investigated, revealing a proposed mechanism for the catalyst reduction (see scheme).

  19. Experimental investigation of the gamma-ray quasi-continuum emitted after alpha induced fusion reactions.

    NARCIS (Netherlands)

    Ockels, Wubbo Johannes

    1978-01-01

    Various experimental investigations on the γ-ray cascades of the deexcitation after the 160Gd(α,xn)^(164-x)Dy reactions at bombarding energies of Eα=40-110 MeV are presented. Of special interest are the so-called quasi-continuum γ-rays, the first γ-rays emitted before the lower-lying states of the

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

    Science.gov (United States)

    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. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Synthesis, Characterization and Swelling Characteristics of Graft Copolymerized Isotactic Polypropylene Film

    Directory of Open Access Journals (Sweden)

    Teena Sehgal

    2010-01-01

    Full Text Available Grafted membranes were prepared through chemical graft copolymerization of methyl methacrylate (MMA onto isotactic polypropylene film (IPP. The IPP films were grafted with MMA molecules resulting in IPP-g-MMA grafts using benzoyl peroxide as an initiator in an inert nitrogen atmosphere. Using this method, the degree of grafting and morphology could be controlled through the variation of reaction parameters such as initiator concentration, monomer concentration, reaction time, and the reaction temperature. Optimum conditions pertaining to maximum percentage of grafting (%G were evaluated as a function of these parameters. Maximum percentage of grafting (50% was obtained at [BPO]=0.03 M, [MMA]=10% V/V, and [Reaction Temperature] = 70∘C in a [Reaction time] of 120 minutes. IPP-g-MMA films were investigated for their swelling behavior. Water-swelling analysis of IPP-g-MMA was carried out as a function of different percentage of grafting, temperatures, and time. Maximum swelling percentage of IPP-g-MMA (92% was observed in 8 hours at 60∘C. The evidence of grafting was carried out by Fourier transform spectroscopy (FTIR, atomic force microscopy (AFM, and scanning electron microscopy (SEM before and after grafting, respectively. The swelling pattern was characterized by two distinct stages, an initial diffusion-controlled fast swelling, followed by a subsequent slower process controlled by the relaxation of polymer fragments. Swelling chrematistics of IPP-g-MMA make it a potentially useful material.

  2. An experimental and theoretical investigation of the C(1D) + D2 reaction

    CERN Document Server

    Hickson, Kevin M

    2016-01-01

    In a previous joint experimental and theoretical study of the barrierless chemical reaction C(1D) + H2 at low temperatures (300-50 K) [K. M. Hickson, J.-C. Loison, H. Guo, Y. V. Suleimanov, J. Phys. Chem. Lett., 2015, 6, 4194.], excellent agreement was found between experimental thermal rate constants and theoretical estimates based on ring polymer molecular dynamics (RPMD) over the two lowest singlet potential energy surfaces (PESs). Here, we extend this work to one of its deuterated counterparts, C(1D) + D2, over the same temperature range. Experimental and RPMD results are in very good agreement when contributions from both PESs to this chemical reaction are included in the RPMD simulations. The deviation between experiment and the RPMD calculations does not exceed 25 % and both results exhibit a slight negative temperature dependence. The first excited 1A" PES plays a more important role than the ground 1A' PES as the temperature is decreased, similar to our previous studies of the C(1D) + H2 reaction but...

  3. Experimental Study on Reaction Characteristics of PTFE/Ti/W Energetic Materials under Explosive Loading

    Directory of Open Access Journals (Sweden)

    Yan Li

    2016-11-01

    Full Text Available Metal/fluoropolymer composites represent a new category of energetic structural materials that release energy through exothermic chemical reactions initiated under shock loading conditions. This paper describes an experiment designed to study the reaction characteristics of energetic materials with low porosity under explosive loading. Three PTFE (polytetrafluoroethylene/Ti/W mixtures with different W contents are processed through pressing and sintering. An inert PTFE/W mixture without reactive Ti particles is also prepared to serve as a reference. Shock-induced chemical reactions are recorded by high-speed video through a narrow observation window. Related shock parameters are calculated based on experimental data, and differences in energy release are discussed. The results show that the reaction propagation of PTFE/Ti/W energetic materials with low porosity under explosive loading is not self-sustained. As propagation distance increases, the energy release gradually decreases. In addition, reaction failure distance in PTFE/Ti/W composites is inversely proportional to the W content. Porosity increased the failure distance due to higher shock temperature.

  4. Experimental and numerical investigation of coupled microvibration dynamics for satellite reaction wheels

    Science.gov (United States)

    Addari, D.; Aglietti, G. S.; Remedia, M.

    2017-01-01

    Microvibrations of a satellite reaction wheel assembly are commonly analysed in either hard-mounted or coupled boundary conditions, though coupled wheel-to-structure disturbance models are more representative of the real environment in which the wheel operates. This article investigates the coupled microvibration dynamics of a cantilever configured reaction wheel assembly mounted on either a stiff or flexible platform. Here a method is presented to cope with modern project necessities: (i) need of a model which gives accurate estimates covering a wide frequency range; (ii) reduce the personnel and time costs derived from the test campaign, (iii) reduce the computational effort without affecting the quality of the results. The method involves measurements of the disturbances induced by the reaction wheel assembly in a hard-mounted configuration and of the frequency and speed dependent dynamic mass of the reaction wheel. In addition, it corrects the approximation due to missing speed dependent dynamic mass in conventional reaction wheel assembly microvibration analysis. The former was evaluated experimentally using a previously designed and validated platform. The latter, on the other hand, was estimated analytically using a finite element model of the wheel assembly. Finally, the validation of the coupled wheel-structure disturbance model is presented, giving indication of the level of accuracy that can be achieved with this type of analyses.

  5. Experimental Study on Reaction Characteristics of PTFE/Ti/W Energetic Materials under Explosive Loading.

    Science.gov (United States)

    Li, Yan; Jiang, Chunlan; Wang, Zaicheng; Luo, Puguang

    2016-11-18

    Metal/fluoropolymer composites represent a new category of energetic structural materials that release energy through exothermic chemical reactions initiated under shock loading conditions. This paper describes an experiment designed to study the reaction characteristics of energetic materials with low porosity under explosive loading. Three PTFE (polytetrafluoroethylene)/Ti/W mixtures with different W contents are processed through pressing and sintering. An inert PTFE/W mixture without reactive Ti particles is also prepared to serve as a reference. Shock-induced chemical reactions are recorded by high-speed video through a narrow observation window. Related shock parameters are calculated based on experimental data, and differences in energy release are discussed. The results show that the reaction propagation of PTFE/Ti/W energetic materials with low porosity under explosive loading is not self-sustained. As propagation distance increases, the energy release gradually decreases. In addition, reaction failure distance in PTFE/Ti/W composites is inversely proportional to the W content. Porosity increased the failure distance due to higher shock temperature.

  6. Enhancement of the Deuteron-Fusion Reactions in Metals and its Experimental Implications

    CERN Document Server

    Huke, A; Heide, P; Ruprecht, G; Targosz, N; Zebrowski, W \\

    2008-01-01

    Recent measurements of the reaction d(d,p)t in metallic environments at very low energies performed by different experimental groups point to an enhanced electron screening effect. However, the resulting screening energies differ strongly for divers host metals and different experiments. Here, we present new experimental results and investigations of interfering processes in the irradiated targets. These measurements inside metals set special challenges and pitfalls which make them and the data analysis particularly error-prone. There are multi-parameter collateral effects which are crucial for the correct interpretation of the observed experimental yields. They mainly originate from target surface contaminations due to residual gases in the vacuum as well as from inhomogeneities and instabilities in the deuteron density distribution in the targets. In order to address these problems an improved differential analysis method beyond the standard procedures has been implemented. Profound scrutiny of the other ex...

  7. Hydrogenation reactions in interstellar CO ice analogues. A combined experimental/theoretical approach

    Science.gov (United States)

    Fuchs, G. W.; Cuppen, H. M.; Ioppolo, S.; Romanzin, C.; Bisschop, S. E.; Andersson, S.; van Dishoeck, E. F.; Linnartz, H.

    2009-10-01

    Context: Hydrogenation reactions of CO in inter- and circumstellar ices are regarded as an important starting point in the formation of more complex species. Previous laboratory measurements by two groups of the hydrogenation of CO ices provided controversial results about the formation rate of methanol. Aims: Our aim is to resolve this controversy by an independent investigation of the reaction scheme for a range of H-atom fluxes and different ice temperatures and thicknesses. To fully understand the laboratory data, the results are interpreted theoretically by means of continuous-time, random-walk Monte Carlo simulations. Methods: Reaction rates are determined by using a state-of-the-art ultra high vacuum experimental setup to bombard an interstellar CO ice analog with H atoms at room temperature. The reaction of CO + H into H2CO and subsequently CH3OH is monitored by a Fourier transform infrared spectrometer in a reflection absorption mode. In addition, after each completed measurement, a temperature programmed desorption experiment is performed to identify the produced species according to their mass spectra and to determine their abundance. Different H-atom fluxes, morphologies, and ice thicknesses are tested. The experimental results are interpreted using Monte Carlo simulations. This technique takes into account the layered structure of CO ice. Results: The formation of both formaldehyde and methanol via CO hydrogenation is confirmed at low temperature (T = 12{-}20 K). We confirm that the discrepancy between the two Japanese studies is caused mainly by a difference in the applied hydrogen atom flux, as proposed by Hidaka and coworkers. The production rate of formaldehyde is found to decrease and the penetration column to increase with temperature. Temperature-dependent reaction barriers and diffusion rates are inferred using a Monte Carlo physical chemical model. The model is extended to interstellar conditions to compare with observational H2CO/CH3OH data.

  8. System Identification for Experimental Study for Polymerization Catalyst Reaction in Fluidized Bed

    Directory of Open Access Journals (Sweden)

    Ahmmed Saadi Ibrehem

    2011-11-01

    Full Text Available In this work, system identification method is used to capture the reactor characteristics of production rate of polyethylene (PE based on published experimental data. The identification method is used to measure the percentage effect on the production rate of PE by measuring the effect of input factors of temperature of reaction, hydrogen concentration, and [Al]/[Ti] molar catalyst ratio. Temperature of reaction has big effects equal 52.4 % on the output of the system and 47.6 % on interaction of the system's parameters compare to other two factors. Also, hydrogen concentration has big effect equal 45.66 % on the output of the system and 14.7 % on interaction of the system's parameters. [Al]/[Ti] molar catalyst ratio has big effect on interaction of the system equal 28.6 and 1.94 % on the output of the system but less than the reaction temperature and hydrogen concentration. All these results depend on experiment results and these results are very important in industrial plants. ©2011 BCREC UNDIP. All rights reserved(Received: 13rd May 2011; Revised: 27th July 2011; Accepted: 22th September 2011[How to Cite: Ahmmed S. Ibrehem. (2011. System Identification for Experimental Study for Polymerization Catalyst Reaction in Fluidized Bed. Bulletin of Chemical Reaction Engineering & Catalysis, 6 (2: 137-146. doi:10.9767/bcrec.6.2.874.137-146][How to Link / DOI: http://dx,doi.org/10.9767/bcrec.6.2.874.137-146 || or local:  http://ejournal.undip.ac.id/index.php/bcrec/article/view/874 ] | View in 

  9. Kinetic investigations of graft copolymerization of sodium styrene sulfonate onto electron beam irradiated poly(vinylidene fluoride) films

    Energy Technology Data Exchange (ETDEWEB)

    Mahmoud Nasef, Mohamed, E-mail: mahmoudeithar@fkkksa.utm.m [Institute of Hydrogen Economy, International City Campus, Universiti Teknologi Malaysia, Jalan Semarak, 54100 Kuala Lumpur (Malaysia); Chemical Engineering Department, Faculty of Chemical and Natural Resources Engineering, Universiti Teknologi Malaysia, 81310 UTM Skudai, Johor (Malaysia); Saidi, Hamdani [Institute of Hydrogen Economy, International City Campus, Universiti Teknologi Malaysia, Jalan Semarak, 54100 Kuala Lumpur (Malaysia); Chemical Engineering Department, Faculty of Chemical and Natural Resources Engineering, Universiti Teknologi Malaysia, 81310 UTM Skudai, Johor (Malaysia); Mohd Dahlan, Khairul Zaman [Radiation Processing Technology Division, Malaysian Nuclear Agency, Bangi, 43000 Kajang, Selangor (Malaysia)

    2011-01-15

    Graft copolymerization of sodium styrene sulfonate (SSS) onto electron beam (EB) irradiated poly(vinylidene fluoride) (PVDF) films was investigated to find out a simple preparation process for sulfonic acid proton exchange membranes with respect to monomer concentration, absorbed dose, temperature, film thickness and storage time. The reaction order of the monomer concentration and absorbed dose of grafting was found to be 2.84 and 1.20, respectively. The overall activation energy for graft copolymerization reaction was calculated to be 11.36 kJ/mol. The initial rate of grafting was found to decrease with an increase in the film thickness. The trapped radicals in the irradiated PVDF films remained effective in initiating the reaction without considerable loss in grafting level up to 180 days, when stored under -60 {sup o}C. The presence and distribution of polystyrene sulfonate grafts in the obtained membranes were observed by Fourier transform infrared (FTIR) spectroscopic analysis, scanning optical microscope and scanning transmission electron microscopy (STEM) coupled with X-ray energy dispersive (EDX), respectively.

  10. Synthesis of chemically cross-linked polyvinyl alcohol-co-poly (methacrylic acid) hydrogels by copolymerization; a potential graft-polymeric carrier for oral delivery of 5-fluorouracil

    OpenAIRE

    Muhammad Usman Minhas; Mahmood Ahmad; Liaqat Ali; Muhammad Sohail

    2013-01-01

    Background of the Study The propose of the present work was to develop chemically cross-linked polyvinyl alcohol-co-poly(methacrylic acid) hydrogel (PVA-MAA hydrogel) for pH responsive delivery of 5-Fluorouracil (5-FU). Methods PVA based hydrogels were prepared by free radical copolymerization. PVA has been cross-linked chemically with monomer (methacrylic acid) in aqueous medium, cross-linking agent was ethylene glycol di-methacrylate (EGDMA) and benzoyl peroxide was added as reaction initia...

  11. An experimental and theoretical investigation of the N + C2 reaction at low temperature

    CERN Document Server

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

    2014-01-01

    Rate constants for the N + C2 reaction have been measured in a continuous supersonic flow reactor over the range 57 K to 296 K by the relative rate technique employing the N + OH - H + NO 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 14A" 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...

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

    Science.gov (United States)

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

    2012-08-06

    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.

  13. Computational and Experimental Studies of Regioselective SNAr Halide Exchange (Halex) Reactions of Pentachloropyridine.

    Science.gov (United States)

    Froese, Robert D J; Whiteker, Gregory T; Peterson, Thomas H; Arriola, Daniel J; Renga, James M; Shearer, Justin W

    2016-11-18

    The Halex reaction of pentachloropyridine with fluoride ion was studied experimentally and computationally with a modified ab initio G3MP2B3 method. The G3 procedure was altered, as the anionic transition state optimizations failed due to the lack of diffuse functions in the small 6-31G* basis set. Experimental Halex regioselectivities were consistent with kinetic control at the 4-position. The reverse Halex reaction of fluoropyridines with chloride sources was demonstrated using precipitation of LiF in DMSO as a driving force. Reverse Halex regioselectivity at the 4-position was predicted by computations and was consistent with kinetic control. Scrambling of halide ions between chlorofluoropyridines was catalyzed by n-Bu4PCl, and the products of these reactions were shown to result from a combination of kinetic and thermodynamic control. Comparison of the C-F and C-Cl homolytic bond dissociation energies suggests that an important thermodynamic factor which controls regioselectivity in this system is the weak C2-Cl bond. The differences between ΔH° values of chlorofluoropyridines can be explained by a combination of three factors: (1) the number of fluorine atoms in the molecule, (2) the number of fluorine atoms at the C2 and C6 positions, and (3) the number of pairs of fluorine atoms which are ortho to one another.

  14. The reaction between iodine and silver under severe PWR accident conditions. An experimental parameter study

    Energy Technology Data Exchange (ETDEWEB)

    Funke, F.; Greger, G.U.; Bleier, A.; Hellmann, S.; Morell, W. [Siemens AG, Power Generation Group, Erlangen (Germany)

    1996-12-01

    An extensive experimental parameter study was performed on the kinetics in the reaction system I{sub 2}/Ag and I{sup -}/Ag in a laboratory-scale apparatus.Starting with I{sub 2} or I{sup -} solutions and silver powder suspensions, the decrease of soluted I{sub 2} or I{sup -}, respectively, due to fixation on the silver particles, was monitored as function of time using the radioactive tracer I-131. The measured data were analyzed using a model of first order kinetics with respect to the iodine concentration. However, the analysis using first order kinetics had to be performed separately in an early, fast reaction phase and in a late, slow reaction phase. The reason for this unexpected behaviour was not identified. Thus, rate constant, two for each test, were deduced from 14 I{sub 2}/Ag main tests and from 36 I{sup -}/Ag tests. No dependencies of the rate constants were found on the parameters temperature, initial iodine concentration, presence of boric acid, type of silver educt, and pretreatment of the silver educt prior to the tests. However, the stirring of the reaction solution generally enhanced the kinetics highlighting the importance of mass transfer. The I{sup -}/Ag reaction proceeded only if there was no inertization of the reaction solution by sparging with nitrogen. The temperature-independent rate constant for the early, fast I{sub 2}/Ag reaction phase is 2E-5 m/s. However, a smaller rate constant of 6E-6 m/s is recommended for use in source term calculations with IMPAIR, which already contains a first order model. Analogously, the temperature-independent I{sup -}/Ag reaction rate constant is 8E-6 m/s in an early, fast reaction phase. For use in source term calculations, a smaller rate constant of 2E-6 m/s is recommended. The lower bound of the I{sup -}/Ag rate constant was 3E-8 m/s which could be used in very conservative source term calculations. (author) 20 figs., 6 tabs., 15 refs.

  15. GRAFT COPOLYMERIZATION OF ACRYLAMIDE ONTO POLYPROPYLENE FILMS BY PLASMA TECHNIQUE

    Institute of Scientific and Technical Information of China (English)

    WANG Shicai; YE Mu; LU Lizhen; CHEN Jie

    1988-01-01

    The graft copolymerization of acrylamide onto polypropylene (PP) film was carried out by using a capacitively coupled rf plasma apparatus with external plate electrodes. The relationship between the surface structure of the Ar plasma-treated PP films and the extent of grafting of acrylamide on the films was studied through observing the effects of discharge power and exposure time on the relative content of free-radical on the film surface. Meanwhile, the wettability and surface energy of the PP film were measured.

  16. Modeling of continuous free-radical butadiene-styrene copolymerization process by the Monte Carlo method

    Directory of Open Access Journals (Sweden)

    T. A. Mikhailova

    2016-01-01

    Full Text Available In the paper the algorithm of modeling of continuous low-temperature free-radical butadiene-styrene copolymerization process in emulsion based on the Monte-Carlo method is offered. This process is the cornerstone of industrial production butadiene – styrene synthetic rubber which is the most widespread large-capacity rubber of general purpose. Imitation of growth of each macromolecule of the formed copolymer and tracking of the processes happening to it is the basis of algorithm of modeling. Modeling is carried out taking into account residence-time distribution of particles in system that gives the chance to research the process proceeding in the battery of consistently connected polymerization reactors. At the same time each polymerization reactor represents the continuous stirred tank reactor. Since the process is continuous, it is considered continuous addition of portions to the reaction mixture in the first reactor of battery. The constructed model allows to research molecular-weight and viscous characteristics of the formed copolymerization product, to predict the mass content of butadiene and styrene in copolymer, to carry out calculation of molecular-weight distribution of the received product at any moment of conducting process. According to the results of computational experiments analyzed the influence of mode of the process of the regulator introduced during the maintaining on change of characteristics of the formed butadiene-styrene copolymer. As the considered process takes place with participation of monomers of two types, besides listed the model allows to research compositional heterogeneity of the received product that is to carry out calculation of composite distribution and distribution of macromolecules for the size and structure. On the basis of the proposed algorithm created the software tool that allows you to keep track of changes in the characteristics of the resulting product in the dynamics.

  17. An experimental and theoretical study of reaction mechanisms between nitriles and hydroxylamine.

    Science.gov (United States)

    Vörös, Attila; Mucsi, Zoltán; Baán, Zoltán; Timári, Géza; Hermecz, István; Mizsey, Péter; Finta, Zoltán

    2014-10-28

    The industrially relevant reaction between nitriles and hydroxylamine yielding amidoximes was studied in different molecular solvents and in ionic liquids. In industry, this procedure is carried out on the ton scale in alcohol solutions and the above transformation produces a significant amount of unexpected amide by-product, depending on the nature of the nitrile, which can cause further analytical and purification issues. Although there were earlier attempts to propose mechanisms for this transformation, the real reaction pathway is still under discussion. A new detailed reaction mechanistic explanation, based on theoretical and experimental proof, is given to augment the former mechanisms, which allowed us to find a more efficient, side-product free procedure. Interpreting the theoretical results obtained, it was shown that the application of specific imidazolium, phosphonium and quaternary ammonium based ionic liquids could decrease simultaneously the reaction time while eliminating the amide side-product, leading to the targeted product selectively. This robust and economic procedure now affords a fast, selective amide free synthesis of amidoximes.

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

    Directory of Open Access Journals (Sweden)

    Wang Xiaowei

    2008-12-01

    Full Text Available Abstract 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.

  19. Experimental study of the cross-sections of alpha-particle induced reactions on $^{209}$Bi

    CERN Document Server

    Hermanne, A; Shubin, Yu N; Szucs, Z; Takács, S; Tarkanyi, F; 10.1016/j.apradiso.2005.01.015

    2005-01-01

    alpha -particle-induced nuclear reactions for generation of /sup 211 /At used in therapeutic nuclear medicine and possible contaminants were investigated with the stacked foil activation technique on natural bismuth targets up to E/sub alpha /=39 MeV. Excitation functions are reported for the reactions /sup 209/Bi( alpha ,2n)/sup 211/At, /sup 209/Bi( alpha ,3n)/sup 210/At and /sup 209/Bi( alpha , x)/sup 210/Po. Results obtained from direct alpha -emission measurements and gamma -spectra from decay products are compared and correspond well with earlier literature values. Thick target yields have been deduced from the experimental cross-sections and optimised production pathways for minimal contamination are presented. A comparison with the results of the theoretical model code ALICE-IPPE is discussed.

  20. GRAFT COPOLYMERIZATION OF ACRYLAMIDE ONTO THE UV-RAY IRRADIATED FILM OF POLYESTER-POLYETHER

    Institute of Scientific and Technical Information of China (English)

    CHEN Chuanfu; LI Xuefen; LI Zhifen

    1988-01-01

    In this paper the Ce(Ⅳ) salt initiated graft copolymerization of acrylamide onto the film of polyester-polyether block copolymer irradiated by UV-ray was reported. The UV-irradiation of the film and its graft process have been investigated by UV spectrum, ESR and ESCA and the influence of other factors on the graft copolymerization has been discussed.

  1. Lipase-catalyzed synthesis of aliphatic polyesters via copolymerization of lactone, dialkyl diester, and diol.

    Science.gov (United States)

    Jiang, Zhaozhong

    2008-11-01

    Candida antarctica lipase (CALB) has been successfully used as catalyst for copolymerization of dialkyl diester with diol and lactone to form aliphatic polyesters. The polymerization reactions were performed using a two stage process: first stage oligomerization under low vacuum followed by second stage polymerization under high vacuum. Use of the two-stage process is required to obtain products with high molecular weights at high yields for the following reasons: (i) the first stage reaction ensures that the monomer loss via evaporation is minimized to maintain 1:1 diester to diol stoichiometric ratio, and the monomers are converted to nonvolatile oligomers; (ii) use of high vacuum during the second stage accelerates equilibrium transesterification reactions to transform the oligomers to high molecular weight polymers. Thus, terpolymers of omega-pentadecalactone (PDL), diethyl succinate (DES), and 1,4-butanediol (BD) with a M w of whole product (nonfractionated) up to 77000 and M w/ M n between 1.7 and 4.0 were synthesized in high yields (e.g., 95% isolated yield). A desirable reaction temperature for the copolymerizations was found to be around 95 degrees C. At 1:1:1 PDL/DES/BD monomer molar ratio, the resultant terpolymers contained equal moles of PDL, succinate, and butylene repeat units in the polymer chains. (1)H and (13)C NMR analyses were used to determine the polyester microstructures. The synthesized PDL-DES-BD terpolymers possessed near random structures with all possible combinations of PDL, succinate, and butylene units via ester linkages in the polymer backbone. Furthermore, thermal stability and crystallinity of a pure PDL-DES-BD terpolymer with 1:1:1 PDL to succinate to butylene unit ratio and M w of 85400 were studied by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The copolyester was found to be a semicrystalline material with a T g of -34 degrees C and a T m of 64 degrees C, which degrades in a single weight loss

  2. Graft copolymerization of acrylic acid onto polyamide fibers

    Science.gov (United States)

    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. Reaction time effects in lab- versus Web-based research: Experimental evidence.

    Science.gov (United States)

    Hilbig, Benjamin E

    2016-12-01

    Although Web-based research is now commonplace, it continues to spur skepticism from reviewers and editors, especially whenever reaction times are of primary interest. Such persistent preconceptions are based on arguments referring to increased variation, the limits of certain software and technologies, and a noteworthy lack of comparisons (between Web and lab) in fully randomized experiments. To provide a critical test, participants were randomly assigned to complete a lexical decision task either (a) in the lab using standard experimental software (E-Prime), (b) in the lab using a browser-based version (written in HTML and JavaScript), or (c) via the Web using the same browser-based version. The classical word frequency effect was typical in size and corresponded to a very large effect in all three conditions. There was no indication that the Web- or browser-based data collection was in any way inferior. In fact, if anything, a larger effect was obtained in the browser-based conditions than in the condition relying on standard experimental software. No differences between Web and lab (within the browser-based conditions) could be observed, thus disconfirming any substantial influence of increased technical or situational variation. In summary, the present experiment contradicts the still common preconception that reaction time effects of only a few hundred milliseconds cannot be detected in Web experiments.

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

    Science.gov (United States)

    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.

  5. Experimental studies of neutron emission spectra in Li(d,xn) reactions for IFMIF

    Energy Technology Data Exchange (ETDEWEB)

    Hagiwara, Masayuki, E-mail: hagi@post.kek.jp [Cyclotron and Radioisotope Center, Tohoku University, Aoba 6-3, Aramaki, Aoba-ku, Sendai, Miyagi 980-8578 (Japan); Radiation Science Center, High Energy Accelerator Research Organization (KEK), Oho 1-1, Tsukuba, Ibaraki 305-0801 (Japan); Itoga, Toshiro, E-mail: itoga@spring8.or.jp [Cyclotron and Radioisotope Center, Tohoku University, Aoba 6-3, Aramaki, Aoba-ku, Sendai, Miyagi 980-8578 (Japan); Oishi, Takuji, E-mail: oishi.takuji@canon.co.jp [Cyclotron and Radioisotope Center, Tohoku University, Aoba 6-3, Aramaki, Aoba-ku, Sendai, Miyagi 980-8578 (Japan); Baba, Mamoru [Cyclotron and Radioisotope Center, Tohoku University, Aoba 6-3, Aramaki, Aoba-ku, Sendai, Miyagi 980-8578 (Japan)

    2011-10-01

    To improve the accuracy of the neutron emission data in the {sup nat}Li(d,xn) reaction, which will be used as the neutron source in the International Fusion Materials Irradiation Facility (IFMIF), we measured the double-differential neutron emission cross-sections (DDXs) of the d-Li reaction at 25 MeV at the cyclotron facility of Tohoku University. The DDXs were measured at ten laboratory angles between 0{sup o} and 110{sup o} by the time-of-flight method, using a beam-swinger system and a well-collimated neutron flight channel. We used a two-gain method to obtain over most of the energy range of secondary neutrons and reveal the shape of the overall emission spectra including the breakup peak of incident deuterons near half the incidence energy, and several peaks in the high-energy tail due to stripping reactions. The experimental results compared favorably with those obtained using the extended Serber model.

  6. Experimental and phenomenological comparison between Piezonuclear reactions and Condensed Matter Nuclear Science phenomenology

    CERN Document Server

    Cardone, F; Petrucci, A

    2011-01-01

    The purpose of this paper is to place side by side the experimental results of Piezonu- clear reactions, which have been recently unveiled, and those collected during the last twenty years of experiments on low energy nuclear reactions (LENR). We will briefy re- port the results of our campaign of piezonuclear reactions experiments where ultrasounds and cavitation were applied to solutions of stable elements. These outcomes will be shown to be compatible with the results and evidences obtained from low energy nuclear reac- tion experiments. Some theoretical concepts and ideas, on which our experiments are grounded, will be sketched and it will be shown that, in order to trigger our measured effects, it exists an energy threshold, that has to be overcome, and a maximum inter- val of time for this energy to be released to the nuclear system. Eventually, a research hypothesis will be put forward about the chance to raise the level of analogy from the mere comparison of results up to the phenomenological level. H...

  7. Experimental constraints on mineral-melt reactions in the Middle Zone of the Skaergaard intrusion

    Science.gov (United States)

    Veksler, I. V.; Nielsen, T. F.

    2009-12-01

    The Eocene Skaergaard intrusion (East Greenland) is the classical example of the Fe enrichment trend in tholeitic magma. Despite numerous attempts to reproduce the trend experimentally, its direction in the Middle Zone (MZ) of the intrusion remains contentious. It remains unclear whether the strong Fe enrichment of the magma continued after the start of ilmenite and magnetite crystallization. Thy et al. (2009) recently showed that the modal ratio of Fe-Ti oxide minerals to Fe-Mg silicates in average Skaergaard rocks was lower than the experimentally determined cotectic proportions. In our view, the difference probably resulted from mineral-melt post-cumulus reactions. Cumulus assemblage in the MZ comprised plagioclase, high- and low-Ca pyroxenes, ilmenite and magnetite. Olivine is locally present as an inter-cumulus phase. All the minerals and the liquid were involved in continuous and discontinuous reaction series. Traces of the reactions are ubiquitous throughout the intrusion, and especially prominent around autolithic blocks (Irvine et al., 1998; McBirney, 2009). We examined experimental constraints on the reactions from 67 experimental equilibria compiled from 25 publications, in which dry silicate melts coexisted with plagioclase, olivine, and two pyroxenes. The experiments had been carried out at 1 atm, temperatures between 1040 and 1180 °C, and variable fO2. We found that the 4-mineral assemblage did not constrain a narrow range of liquid compositions. For example, SiO2 in the liquids varies broadly from 42 to 66 wt.%. Cotectic proportions of the crystal phases vary accordingly. FeO and alkalis impose strong and opposite effects on the cotectic proportions and equilibrium melt compositions. Thus, alkali-poor liquids evolve to FeO concentrations of up to 30 wt. %. We propose that the mineral-melt reactions compounded by migration of FeO and alkalis in the liquid may explain poorly understood phenomena such as the reverse evolution of plagioclase towards

  8. Surface modification of copolymerized films from three-armed biodegradable macromers - An analytical platform for modified tissue engineering scaffolds.

    Science.gov (United States)

    Müller, Benno M; Loth, Rudi; Hoffmeister, Peter-Georg; Zühl, Friederike; Kalbitzer, Liv; Hacker, Michael C; Schulz-Siegmund, Michaela

    2017-03-15

    The concept of macromers allows for a broad adjustment of biomaterial properties by macromer chemistry or copolymerization. Copolymerization strategies can also be used to introduce reactive sites for subsequent surface modification. Control over surface features enables adjustment of cellular reactions with regard to site and object of implantation. We designed macromer-derived polymer films which function as non-implantable analytical substrates for the investigation of surface properties of equally composed scaffolds for bone tissue engineering. To this end, a toolbox of nine different biodegradable, three-armed macromers was thermally cross-copolymerized with poly(ethylene glycol)-methacrylate (PEG-MA) to films. Subsequent activation of PEG-hydroxyl groups with succinic anhydride and N-hydroxysuccinimid allowed for covalent surface modification. We quantified the capacity to immobilize analytes of low (amino-functionalized fluorescent dye, Fcad, and RGD-peptides) and high (alkaline phosphatase, ALP) molecular weight. Fcad grafting level was controlled by macromer chemistry, content and molecular weight of PEG-MA, but also the solvent used for film synthesis. Fcad molar amount per surface area was twentyfive times higher on high-swelling compared to low-swelling films, but differences became smaller when large ALP (appr. 2:1) were employed. Similarly, small differences were observed on RGD peptide functionalized films that were investigated by cell adhesion studies. Presentation of PEG-derivatives on surfaces was visualized by atomic force microscopy (AFM) which unraveled composition-dependent domain formation influencing fluorescent dye immobilization. Surface wetting characteristics were investigated via static water contact angle. We conclude that macromer ethoxylation and lactic acid content determined film swelling, PEG domain formation and eventually efficiency of surface decoration.

  9. Graft copolymerization onto cellulose-based filter paper and its further development as silver nanoparticles loaded antibacterial food-packaging material.

    Science.gov (United States)

    Tankhiwale, Rasika; Bajpai, S K

    2009-03-01

    The present work describes ceric ammonium nitrate (CAN) initiated graft copolymerization of acrylamide onto cellulose-based filter paper followed by entrapment of silver nanoparticles. The copolymerization was carried out in aqueous solution, containing 2M acrylamide monomer and 16mM N,N'-methylene bisacrylamide (MB) crosslinker. The optimum initiation time and grafting reaction temperature were found to be 15min and 30 degrees C, respectively. The silver nanoparticles were loaded into grafted filter paper by equilibration in silver nitrate solution followed by citrate reduction. The formation of silver nanoparticles has been confirmed by TEM and SAED analysis. The novel nano silver loaded filter paper has been investigated for its antimicrobial properties against E.coli. This newly developed material shows strong antibacterial property and thus offers its candidature for possible use as antibacterial food-packaging material.

  10. Investigation on the Cellulose Graft Copolymerization With Caprolactam%纤维素与己内酰胺接枝共聚改性研究

    Institute of Scientific and Technical Information of China (English)

    李政; 王鑫

    2014-01-01

    Cellulose is an important natural biodegradable polymer. The deficiency of cellulose can be improved by graft copolymerization with caprolactam. In this paper, dissolution property of cellulose in organic phase of DMAC/LiCl was discussed as well as the graft copolymerization reaction of cellulose and caprolactam, and grafted copolymer was characterized.%纤维素是一种重要的天然生物可降解聚合物,将纤维素与己内酰胺接枝共聚可以改性天然纤维素的不足。以纤维素为原料,讨论其在DMAC/LiCl体系有机相中溶解性质及与己内酰胺的接枝共聚反应,并对接枝物进行了表征测试。

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

    Science.gov (United States)

    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 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.

  12. Experimental and theoretical studies of the reaction between cationic vanadium oxide clusters and acetylene

    Institute of Scientific and Technical Information of China (English)

    YIN Shi; MA YanPing; DU Lin; HE ShengGui; GE MaoFa

    2008-01-01

    The time of flight mass spectrometer coupled with a laser ablation/supersonic expansion cluster source and a fast flow reactor was adopted to study the reactivity of cationic vanadium oxide clusters (VmO+n) toward acetylene (C2H2) molecules under gas phase (P, ~ 1.14 kPa), under near room temperature (T, ~ 350 K) conditions. Association products, VmOnC2H+2 (m,n = 2,4; 2,6; 3,7-8; 4,9-11; 5,12-13;6,13-16, and 7,17), are observed. The oxidation of C2H2 by (V2O5)+n, (n = 1-3) is experimentally identified.The reactivity of (V2O5)+n decreases as n increases. Density functional theory (DFT) calculations were carried out to interpret the reaction mechanisms. The DFT results indicate that a terminal oxygen atom from V2O+5 can transfer overall barrierlessly to C2H2 at room temperature, which is in agreement with the experimental observation. Other experimental results such as the observation of V2O6C2H+2 and nonobservation of V2O7,8C2H+2 in the experiments are also well interpreted based on the DFT calculations.The reactivity of vanadium oxide clusters toward acetylene and other hydrocarbons may be considered in identifying molecular level mechanisms for related heterogeneous catalysis.

  13. Formation of hyperbranched polymers in atom transfer radical copolymerization of MMA and DVB

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Hyperbranched poly(methyl methacrylate)s (HPMMAs) have been successfully prepared by atom transfer radical copolymerization of MMA and divinylbenzene (DVB).Kinetic study shows complete consumption of the initiator in 0.5 h,and relatively low polymerization rate when DVB content in the feed was high.By analyzing MALDI-TOF spectra of the resulting copolymers,the linear A n B (n=0,1,2,3) oligomers were formed in 0.5 h of polymerization,and then the oligomers reacted each other to form dimers,further reactions produced HPMMA.The SEC and NMR spectroscopies were used to trace the polymerization,and the results demonstrate that small amount of the branching reactions occur in the initial polymerization,and the branched polymers are significantly generated past a certain conversion depending upon the feed ratios.Raising the content of DVB in the monomer mixture can increase the pendent vinyl groups of the linear oligo-inimers,leading to gelation at low MMA conversion.

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

    Science.gov (United States)

    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.

  15. Kinetic theory and thermodynamics of template-directed copolymerization

    Science.gov (United States)

    Gaspard, Pierre

    2017-02-01

    Template-directed copolymerization is the fundamental process for the replication, transcription, and translation of genetic information. The copy of the template sequence is grown by the attachment of monomers with a molecular machine. The long-time kinetics of such processes is exactly solvable in terms of iterated function systems. This method determines the effects of sequence heterogeneity and replication errors on the growth of the copy and the statistical properties of its sequence. In particular, a transition can occur between linear and sublinear growth in time of the copy. In the linear regime, the local growth velocity along the template may have a fractal distribution. Furthermore, the growth can be driven around equilibrium by the entropic effect of replication errors in an adverse free-energy landscape.

  16. Fluorescence confocal laser scanning microscopy for in vivo imaging of epidermal reactions to two experimental irritants

    DEFF Research Database (Denmark)

    Suihko, C.; Serup, J.

    2008-01-01

    dermatitis reactions caused by established model irritants, e.g. sodium lauryl sulphate (SLS) and pelargonic acid (PA). Methods: Twelve healthy individuals volunteered. The flexor aspect of the right and the left forearm was exposed to SLS in water and PA in isopropanol and occluded under Finn Chambers...... of keratinocytes with visible nuclei in the outer layers of the epidermis, e.g. a parakeratotic shift supposed to be due to increased cell proliferation elicited by SLS. The isopropanol vehicle and PA did not interfere with the CLSM imaging technique or the experimental procedures. SLS, being a detergent, however...... more complicated than reflectance CLSM and may not be applicable to any irritant. SLS applied epicutaneously interacted with the skin surface and coupling to the microscope and was thus found to be more difficult to study technically than PA. PA dissolved in isopropanol is for technical reasons...

  17. Experimental investigation of the reaction-build-up for plastic bonded explosive JOB-9003

    Directory of Open Access Journals (Sweden)

    Xu Zhang

    2017-05-01

    Full Text Available In order to measure the shock initiation behavior of JOB-9003 explosives, Al-based embedded multiple electromagnetic particle velocity gauge technique has been developed. In addition, a gauge element called the shock tracker has been used to monitor the progress of the shock front as a function of time, thus providing a position–time trajectory of the wave front as it moves through the explosive sample. The data is used to determine the position and time for shock to detonation transition. All the experimental results show that the rising-up time of Al-based electromagnetic particle velocity gauge is very short (<20 ns; the reaction-build-up velocity profiles and the position–time for shock to detonation transition of HMX-based plastic bonded explosive (PBX JOB-9003 with 1–8 mm depth from the origin of the impact plane under different initiation pressures were obtained with high accuracy.

  18. Experimental investigation on material migration phenomena in micro-EDM of reaction-bonded silicon carbide

    Energy Technology Data Exchange (ETDEWEB)

    Liew, Pay Jun [Department of Mechanical Systems and Design, Tohoku University, Aramaki Aoba 6-6-01, Aoba-ku, Sendai, 980-8579 (Japan); Manufacturing Process Department, Faculty of Manufacturing Engineering, Universiti Teknikal Malaysia Melaka, Hang Tuah Jaya, 76100, Durian Tunggal, Melaka (Malaysia); Yan, Jiwang, E-mail: yan@mech.keio.ac.jp [Department of Mechanical Engineering, Faculty of Science and Technology, Keio University, Hiyoshi 3-14-1, Kohoku-ku, Yokohama, 223-8522 (Japan); Kuriyagawa, Tsunemoto [Department of Mechanical Systems and Design, Tohoku University, Aramaki Aoba 6-6-01, Aoba-ku, Sendai, 980-8579 (Japan)

    2013-07-01

    Material migration between tool electrode and workpiece material in micro electrical discharge machining of reaction-bonded silicon carbide was experimentally investigated. The microstructural changes of workpiece and tungsten tool electrode were examined using scanning electron microscopy, cross sectional transmission electron microscopy and energy dispersive X-ray under various voltage, capacitance and carbon nanofibre concentration in the dielectric fluid. Results show that tungsten is deposited intensively inside the discharge-induced craters on the RB-SiC surface as amorphous structure forming micro particles, and on flat surface region as a thin interdiffusion layer of poly-crystalline structure. Deposition of carbon element on tool electrode was detected, indicating possible material migration to the tool electrode from workpiece material, carbon nanofibres and dielectric oil. Material deposition rate was found to be strongly affected by workpiece surface roughness, voltage and capacitance of the electrical discharge circuit. Carbon nanofibre addition in the dielectric at a suitable concentration significantly reduced the material deposition rate.

  19. LLUSTRATION OF AMINO ACIDS REACTIONS AND PROTEINS CHARACTERIZATION FOR EXPERIMENTAL BIOCHEMISTRY CLASSES

    Directory of Open Access Journals (Sweden)

    I. Parreira

    2008-05-01

    Full Text Available New teaching methodologies have been developed to facilitate the learning of biochemistry concepts. A new  approach to Biochemistry  teaching  has become more frequent,  one that does not  require reagents but use photos, videos, softwares etc. Experimental Biochemistry classes, i.e. covering characterization of amino acids and proteins,  might be more productive with the use of complementary didactic material.  Furthermore,  if experiments cannot be implemented, classes may  be well illustrated with complementary didactic material covering from the simplest to the most  complex experiments.  In order to  aid Biochemistry classes without practical experiments, some tests and reactions were documented in our laboratory through digital photos, for  instance: (1 the biuret reaction wherein the blue reagent turns violet in the presence of proteins and changes to pink when combined with short-chain polypeptides; (2 the ninhydrin test used in amino acid analysis of proteins: most of the amino acids are hydrolyzed and react with ninhydrin; when reacting with these free amines, a deep blue or purple color appears; (3 methods for detecting proteins wherein spectrophotometry is used, that deals with the relationship between absorbance, concentration and path length, which constitute the Beer-Lambert Law. A didactic material constituted by texts, schemes and illustrated by photos has been created for each class topic. This material can be used either as a teacher script or in a presentation form to illustrate classes without experimental activities. Financial Support: Pro-Reitoria Graduação-USP, CNPq.

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

    Science.gov (United States)

    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.

  1. Experimental approaches for determining in-medium properties of hadrons from photo-nuclear reactions

    CERN Document Server

    Metag, Volker; Berghäuser, Henning; Friedrich, Stefan; Lemmer, Boris; Mosel, Ulrich

    2011-01-01

    Properties of hadrons and their modification within strongly interacting matter provide a link between experimental observables and Quantum Chromodynamics (QCD) in the non-perturbative sector. The sensitivity of various observables to in-medium modifications of mesons is discussed. The transparency ratio, comparing the meson yield per nucleon within a nucleus relative to that on a free nucleon, is related to the in-medium width of the meson. While the transparency ratio can be determined for any meson lifetime the meson line shape only contains information on in-medium properties if the meson is so short-lived that it decays in the medium after production in a nuclear reaction. Light vector mesons are thus particularly suited for these investigations. The momentum distribution of mesons produced in a photo-nuclear reaction as well as the excitation function also show some sensitivity to different in-medium modification scenarios. As an example, high statistics data taken at MAMI-C on the photoproduction of \\o...

  2. Thermodynamic Analysis and Experimental Study on Reaction of CO2 Gas with Hot Metal

    Institute of Scientific and Technical Information of China (English)

    Guo WEI; Zhi-tao LI; Zi-liang LI; Qiang-jian GAO; Feng-man SHEN

    2016-01-01

    The reaction of CO2 gas with hot metal was investigated based on the thermodynamic analysis and experi-mental results.It shows that both silicon and carbon in hot metal can be oxidized by CO2 gas in the temperature range of 1 300-1 500 ℃.When using graphite crucible,temperature has little influence on final mass percent of car-bon w[C] because of the carburization effect.Decarburization degree rises significantly with increasing gas inj ection rate and w[C] can be reduced to 3�2% at most when using MgO crucible.Lower temperature or higher gas inj ection rate is propitious to promote desilication reaction,but only 5%-10% of desilication ratio could be obtained in 20 min. The final mass percent of silicon w[Si] when using MgO crucible is lower than that when using graphite crucible.Ex-perimental results also demonstrate that CO2 injection has no effect on the concentration of manganese,sulfur and phosphorus in hot metal.In view of the weak oxidation ability and temperature drop of hot metal,CO2 gas is sugges-ted to be used as carrier gas in desilication process rather than oxidizing agent.

  3. Preparation of Thermo-Responsive Poly(ionic liquids-Based Nanogels via One-Step Cross-Linking Copolymerization

    Directory of Open Access Journals (Sweden)

    Jing Zhang

    2015-09-01

    Full Text Available In this study, thermo-responsive polymeric nanogels were facilely prepared via one-step cross-linking copolymerization of ethylene glycol dimethacrylate/divinylbenzene and ionic liquid (IL-based monomers, 1,n-dialkyl-3,3′-bis-1-vinyl imidazolium bromides ([CnVIm]Br; n = 6, 8, 12 in selective solvents. The results revealed that stable and blue opalescent biimidazolium (BIm-based nanogel solutions could be obtained without any precipitation when the copolymerizations were conducted in methanol. Most importantly, these novel nanogels were thermo-response, and could reversibly transform to precipitation in methanol with temperature changes. Turbidity analysis and dynamic light scatting (DLS measurement illustrated that PIL-based nanogel solutions presented the phase transform with upper critical solution temperature (UCST in the range of 5–25 °C. The nanogels were characterized using Fourier transform infrared (FTIR, thermogravimetric analyses (TGA, and scanning electron microscopy (SEM. In addition, BIm-based nanogels could also be used as highly active catalysts in the cycloaddition reaction of CO2 and epoxides. As a result, our attributes build a robust platform suitable for the preparation of polymeric nanomaterials, as well as CO2 conversion.

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

    Science.gov (United States)

    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…

  5. RAFT Copolymerization of Glycidyl Methacrylate and N,N-Dimethylaminoethyl Methacrylate

    Institute of Scientific and Technical Information of China (English)

    曹俊; 张丽芬; 潘向强; 程振平; 朱秀林

    2012-01-01

    In this work, copolymerization of two functional monomers, glycidyl methacrylate (GMA) and N,N-dimethylaminoethyl methacrylate (DMAEMA), was firstly carried out via reversible addition-fragmentation chain transfer (RAFT) polymerization successfully. The copolymerization kinetics was investigated under the molar ratio of n[GMA+DMAEMA]o/n[AIBN]o/n[CPDN]o=300/1/3 at 60℃. The copolymerization showed typical "living" features such as first-order polymerization kinetics, linear increase of molecular weight with monomer conversion and narrow molecular weight distribution. The reactivity ratios of GMA and DMAEMA were calculated by the extended Kelen-Tudos linearization methods. The epoxy group of the copolymer PGMA-co-PDMAEMA remained intact under the conditions of RAFT copolymerization and could easily be post-modified by ethylenedia- mine. Moreover, the modified copolymer could be used as a gene carrier.

  6. HIGH SOLIDS-CONTENT NANOSIZE POLYMER LATEXES MADE BY A MODIFIED EMULSION COPOLYMERIZATION

    Institute of Scientific and Technical Information of China (English)

    ZHANG Yuying; GUO Tianying; HAO Guangjie; SONG Maodao; Zhang Banghua

    2003-01-01

    Polymer nanoparticles were prepared in the methyl methacrylate (MMA)/buty lmethacrylate (BA) emulsion copolymerization process by a modified microemulsion copolymerization method. 2-Hydroxyethyl methacrylate(HEMA), acrylate (AA) and methyl acrylate (MAA) were used as reactive cosurfactants. With this process high polymer: surfactant weight ratios (40:1 or greater),relatively concentrated (~30wt. %) latexes and small (~60nm) particle diameters were obtained.Properties of the latexes were characterized by TEM, DSC, dynamic light scattering, and IR spectroscopy.

  7. Experimental studies of keV energy neutron-induced reactions relevant to astrophysics and nuclear physics

    Energy Technology Data Exchange (ETDEWEB)

    Shima, T.; Kii, T.; Kikuchi, T.; Okazaki, F.; Kobayashi, T.; Baba, T.; Nagai, Y. [Tokyo Inst. of Tech. (Japan). Faculty of Science; Igashira, M.

    1997-03-01

    Nuclear reactions induced by keV energy neutrons provide a plenty of informations for studies of both astrophysics and nuclear physics. In this paper we will show our experimental studies of neutron- induced reactions of light nuclei in the keV energy region by means of a pulsed keV neutron beam and high-sensitivity detectors. Also we will discuss astrophysical and nuclear-physical consequences by using the obtained results. (author)

  8. Photocrosslinkable Star Polymers via RAFT-Copolymerizations with N-Ethylacrylate-3,4-dimethylmaleimide

    Directory of Open Access Journals (Sweden)

    Philipp Vana

    2013-06-01

    Full Text Available This paper describes the Z-RAFT-star copolymerization of n-butyl acrylate (BA and N-isopropyl acrylamide (NIPAm, respectively, with N-ethylacrylate-3,4-dimethylmaleimide (1.1, a monomer carrying a UV-reactive unit that undergoes photocrosslinking. Addition of 1.1 slows down the polymerization rate both for BA and for NIPAm polymerization. Double star formation due to radical attack to the 3,4-dimethylmaleimide moiety was found in the case of BA. Dead polymer formation, presumably due to aminolysis as side-reaction, was pronounced in the NIPAm system. These two effects broadened the molar mass distributions, but did not impede the formation of functional star polymers. The composition of the copolymers as well as the reactivity ratios for the applied comonomers were determined via NMR spectroscopy (BA-co-1.1 r1.1 = 2.24 rBA = 0.95; NIPAm-co-1.1 r1.1 = 0.96 rNIPAm = 0.05. In both cases, the comonomer is consumed preferably in the beginning of the polymerization, thus forming gradient copolymer stars with the UV-reactive units being located in the outer sphere.

  9. Isolation and Characterization of 1,3-Bis(vinylbenzylthymine: Copolymerization with Vinylbenzyl Thymine Ammonium Chloride

    Directory of Open Access Journals (Sweden)

    Ngoc Chau H. Vy

    2017-01-01

    Full Text Available A novel bioinspired molecule, 1,3-bis(vinylbenzylthymine (bisVBT, was isolated as a by-product during the synthesis of 1-(4-vinylbenzylthymine (VBT and analyzed with various techniques: NMR, IR, and Single-Crystal X-ray Diffraction. In addition to embodying all the desired characteristics of VBT (i.e., having the ability to undergo a 2π+2π photodimerization reaction upon UV irradiation, a derivatization site, hydrogen bonding sites, and aromatic stacking ability the bisVBT monomer has the added benefit of having two vinyl groups for cross-polymerization. Copolymerizing the bisVBT monomer with the charged monomer vinylbenzyl triethylammonium (VBA chloride, different copolymers/terpolymers/cross-linked network were obtained, as it was shown by the absence of the vinyl resonance in the NMR spectra. Thermal Gravimetric Analysis (TGA and Differential Scanning Calorimetry (DSC showed an indication of materials with low degree of cross-linking. A Gel Permeation Chromatography (GPC method was improved to better characterize the molecular weight distributions of the cationic structures. Preliminary qualitative cross-linking studies were performed on bisVBT-VBA copolymers, and a comparison with VBT-VBA copolymers is presented.

  10. RING OPENING COPOLYMERIZATION OF SUCCINIC ANHYDRIDE-ETHYLENE OXIDE BY Al (Ⅲ) ORGANOMETALLIC CATALYSTS

    Institute of Scientific and Technical Information of China (English)

    CHEN Xianhai; ZHANG Yifeng; SHEN Zhiquan

    1997-01-01

    Ring opening copolymerization of succinic anhydride (SA) with ethylene oxide (EO)was successfully carried out by using a series of aluminum-based catalyst in 1,4-dioxane at 62±2℃. The results showed that in-situ AlR3-H2O (R=ethyl, iso-butyl) catalysts gave higher molecular weight ((-M)w ~ 104), while Al(OR)3 catalysts gave the higher alternating copolymer structure with slightly lower molecular weight. The in-situ AlR3-H2O systems have been evaluated in more detail for the reaction which showed the optimum H2O/Al molar ratio to be 0.5. The copolymers with different composition (FSA/FEO = 36/64 to 45/55 mol/mol) were synthesized by using different monomer feed ratio. The melting point (Tm), glass transition temperature (Tg) and enthalpy of fusion (ΔHf) of these copolymers are depended on the copolymer composition and in the range of 87~ 102℃,-12 ~ -18℃, and 37 ~ 66J/g, respectively. The second heating scan of DSC also indicated that the higher alternating copolymer was more easily recrystallized. The onset decomposition temperature was more than 300℃ under nitrogen and influenced by the copolymer composition.

  11. 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.

    Science.gov (United States)

    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.

  12. Statistical deduction and experimental verification on kinetic equations for the curing reactions of epoxy resins/amines

    Institute of Scientific and Technical Information of China (English)

    CHEN Ping; LU Zu-shun; YU Da-shu; HU Li-jiang

    2005-01-01

    Based on three typical mechanisms (second-order, third-order and competitive mechanisms) for the curing reactions of the epoxy resins with amines, a pair of the kinetic equations (for primary and secondary aminations) was presented to explain the uniformity and relationship among the three different kinetic mechanisms of the reactions. The presented macro-equations were deduced from the kinetic micro-equations by the statistics method. And the constitutive equations were verified by experimental data at different reaction times and temperatures (95℃, 60℃ and 39℃), taking diglycidyl ether of bisphenol A (DGEBA) /ethyleneamine (EA) as a model.

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

    Science.gov (United States)

    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.

  14. Transfer reactions in inverse kinematics, an experimental approach for fission investigations

    CERN Document Server

    Rodríguez-Tajes, C; Derkx, X; Caamaño, M; Delaune, O; Schmidt, K -H; Clément, E; Dijon, A; Heinz, A; Roger, T; Audouin, L; Benlliure, J; Casarejos, E; Cortina, D; Doré, D; Fernández-Domínguez, B; Jacquot, B; Jurado, 1 B; Navin, A; Paradela, C; Ramos, D; Romain, P; Salsac, M D; Schmitt, C

    2013-01-01

    Inelastic and multi-nucleon transfer reactions between a $^{238}$U beam, accelerated at 6.14 MeV/u, and a $^{12}$C target were used for the production of neutron-rich, fissioning systems from U to Cm. A Si telescope, devoted to the detection of the target-like nuclei, provided a characterization of the fissioning systems in atomic and mass numbers, as well as in excitation energy. Cross-sections, angular and excitation-energy distributions were measured for the inelastic and transfer channels. Possible excitations of the target-like nuclei were experimentally investigated for the first time, by means of g -ray measurements. The decays from the first excited states of $^{12}$C, $^{11}$B and $^{10}$Be were observed with probabilities of 0.12 - 0.14, while no evidence for the population of higher-lying states was found. Moreover, the fission probabilities of $^{238}$U, $^{239}$Np and $^{240,241,242}$Pu and $^{244}$Cm were determined as a function of the excitation energy.

  15. Detection of Toxoplasma gondii DNA by polymerase chain reaction in experimentally desiccated tissues

    Directory of Open Access Journals (Sweden)

    Márcia Andreia Barge Loução Terra

    2004-03-01

    Full Text Available Despite toxoplasmosis being a common infection among human and other warm-blooded animals worldwide, there are no findings about Toxoplasma gondii evolutionary forms in ancient populations. The molecular techniques used for amplification of genetic material have allowed recovery of ancient DNA (aDNA from parasites contained in mummified tissues. The application of polymerase chain reaction (PCR to paleoparasitological toxoplasmosis research becomes a promising option, since it might allow diagnosis, acquisition of paleoepidemiological data, access to toxoplasmosis information related origin, evolution, and distribution among the ancient populations.Furthermore, it makes possible the analysis of parasite aDNA aiming at phylogenetic studies. To standardize and evaluate PCR applicability to toxoplasmosis paleodiagnostic, an experimental mummification protocol was tested using desiccated tissues from mice infected with the ME49 strain cysts, the chronic infection group (CIG, or infected with tachyzoites (RH strain, the acute infection group (AIG. Tissues were subjected to DNA extraction followed by PCR amplification of T. gondii B1 gene. PCR recovered T. gondii DNA in thigh muscle, encephalon, heart, and lung samples. AIG presented PCR positivity in encephalon, lungs, hearts, and livers. Based on this results, we propose this molecular approach for toxoplasmosis research in past populations.

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

    Science.gov (United States)

    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.

  17. Theoretical and Experimental Studies on the Reaction Mechanism of Cl2+I2=2ICl

    Institute of Scientific and Technical Information of China (English)

    YANG Guo-Ying; YUAN Li-Xia; SUN De-Sheng; WANG Zun-Yao; JIANG Tao

    2006-01-01

    The gas phase reaction mechanism of Cl2 + I2 = 2ICI has been theoretically investigated by DFT method at the B3LYP/3-21G* level. Transition states of three reaction channels were consequently given. The results indicate that in the title reaction the least activation energy of bi-molecular reaction was smaller than the dissociation energies of I2 and Cl2, and thus the reaction mechanism was the course of molecule-molecule interaction at low reaction rate. If other factors such as illumination were taken into account, I2 could dissociate into I atoms and then react with Cl2,or Cl2 dissociates into Cl atoms and reacts with I2. These were photochemical reactions with high reaction speed. The theoretical results were further validated with absorbance measurement at 516 nm.

  18. Measurement of proton capture reactions in the hot cycles: an evaluation of experimental methods

    Energy Technology Data Exchange (ETDEWEB)

    Leleux, P. [Inst. de Physique Nucleaire, Univ. Catholique de Louvain, Louvain-la-Neuve (Belgium)

    1998-06-01

    In the hot cycles, most of the proton capture reactions involve radioactive nuclei in the entrance and exit channels. This paper evaluates the specific methods that were designed to measure such reactions. (orig.)

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

    Science.gov (United States)

    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

  20. Temperature-responsive copolymeric hydrogel systems synthetized by ionizing radiation

    Science.gov (United States)

    López-Barriguete, Jesús Eduardo; Bucio, Emilio

    2017-06-01

    Eight different systems of hydrogel copolymers with diverse temperature responsiveness were prepared to elaborate membranes for their biomedical application. The hydrogels were synthesized using poly(N-isopropylacrylamide) (PNIPAAm) and poly(N-vinylcaprolactam) (PNVCL), which have a low critical solution temperature (LCST) close to that of the human body temperature. The networks were synthesized using gamma radiation at a dose rate of 11.2 kGy h-1, and dose of 50 kGy. The LCST of each system was measured by differential scanning calorimetry (DSC). The effect of using hydrophilic monomers of acrylic acid (AAc), methacrylic acid (MAAc), dimethyl acrylamide (DMAAm), and hydroxyethyl methacrylate (HEMA) for the copolymerization on the critical point was evaluated. Five viable systems were obtained, with the best hydrogel being that of poly(NIPAAm-co-DMAAm), which an LCST at 39.8 °C. All the samples were characterized by FTIR-ATR, DSC, TGA, X-Ray Diffraction, and SEM. The proportion of monomers during the formation of the copolymers was decisive in the displacement of the LCST.

  1. Kinetics Model of Graft Co-Polymerization of Acrylamide onto Mechanically-Activated Starch in Inverse Emulsion%反相乳液法mSt-g-AM接枝共聚反应的动力学模型

    Institute of Scientific and Technical Information of China (English)

    谢新玲; 童张法; 黄祖强; 张友全

    2014-01-01

    The graft co-polymerization reaction mechanism of acrylamide and mechanically-activated starch in an inverse emulsion system was investigated. The effects of concentrations of initiator (with ammonium persulfate as the initiator), monomer, starch, and emulsifier on the reaction rate of graft co-polymerization (Rg) were determined. The kinetic model was studied and modified to fit the experimental results. The results show that the relationship between R g and the concentration of components in the polymerization system can be expressed for all of the four components by the following equation:Rg∞[mSt]1.24 [I]0.76 [M]1.54 [E]0.33 , which is consistent with the kinetic equation from theoretical studies:Rp∞[mSt]0.5~1 [I]0.5~1 [M]1~1.5 [E]0.6 . It can be concluded that the graft co-polymerization reaction of hydrophilic monomer onto starch in inverse emulsion follows the mechanism of free radical polymerization. Unimolecular and bimolecular termination of free radicals are both presented in the reaction process. The relation between the grafted monomer and the reacted monomer is:1/X=1+K1[M]0.5/[Mst]0.5+K2[Mst]0.5[I]0.5/[M]+K3[I]0.5/[Mst]0.5 .%采用反相乳液法进行淀粉与丙烯酰胺接枝共聚反应的机理研究,考察以过硫酸铵引发机械活化淀粉(mSt)与丙烯酰胺(AM)接枝共聚反应速率Rg与引发剂浓度[I]、乳化剂浓度[E]、单体浓度[M]和淀粉浓度[mSt]的关系,推导并验证该反应体系的动力学模型及反应机理。结果表明,本实验得出的动力学关系式为:Rg∞[mSt]1.24[I]0.76[M]1.54[E]0.33,与理论推导出的动力学关系式:Rp∞[mSt]0.5~1[I]0.5~1[M]1~1.5[E]0.6基本一致,机械活化淀粉与丙烯酰胺在反相乳液中进行接枝共聚反应符合自由基聚合机理;在聚合过程中,引发剂分解副反应、诱导分解及“笼壁效应”导致引发效率降低,单基终止和双基终止反应同时存在;推导出共聚物消耗单体量与参加反

  2. Bone reactions at implants subjected to experimental peri-implantitis and static load. A study in the dog

    DEFF Research Database (Denmark)

    Gotfredsen, K; Berglundh, T; Lindhe, J

    2002-01-01

    AIM: The aim of the present experiment was to study peri-implant tissue reactions to lateral static load at implants subjected to experimental mucositis or peri-implantitis. MATERIAL AND METHODS: 5 beagle dogs were used. The mandibular premolars were extracted. After 12 weeks, 3 implants were ins...

  3. Toluene removal by oxidation reaction in spray wet scrubber: experimental, modeling and optimization

    Directory of Open Access Journals (Sweden)

    Roumporn Nikom

    2006-11-01

    Full Text Available Toluene, an important volatile organic compound (VOC, is used in many kinds of industries, such as painting, printing, coating, and petrochemical industries. The emission of toluene causes serious air pollution, odor problem, flammability problem and affects human health. This paper proposes the removal of toluene from waste air using a spray wet scrubber combining the absorption and oxidation reaction. Aqueous sodium hypochlorite (NaOCl solution was used as the scrubbing liquid in the system. NaOCl, the strongest oxidative agent, presents an effective toluene removal. As the scrubbed toluene is reacted, recirculation of the scrubbing liquid could be operated with a constant removal efficiency throughout the operting time. The investigated variables affecting the removal efficiency were air flow rate, inlet toluene concentration, NaOCl concentration, scrubbing liquid flow rate and size of spray nozzle. Influence of the scrubbing parameters was experimentally studied to develop a mathematical model of the toluene removal efficiency. The removal model reveals that the increase of scrubbing liquid flow rate, toluene concentration, and NaOCl concentration together with the decrease of air flow rate and size of spray nozzle can increase the toluene removal efficiency. Optimization problem with an objective function and constraints was set to provide the maximum toluene removal efficiency and solved by Matlab optimization toolbox. The optimization constraints were formed from the mathematical model and process limitation. The solution of the optimization was an air flow rate of 100 m3/h, toluene concentration of 1500 ppm, NaOCl concentration of 0.02 mol/l, NaOCl solution feed rate of 0.8 m3/h, and spray nozzle size of 0.5 mm. Solution of the optimization gave the highest toluene removal efficiency of 91.7%.

  4. Computer aided design, analysis and experimental investigation of membrane assisted batch reaction-separation systems

    DEFF Research Database (Denmark)

    Mitkowski, Piotr Tomasz; Buchaly, Carsten; Kreis, Peter;

    2009-01-01

    Membrane assisted batch reaction operation offers an interesting option for equilibrium limited reaction systems in chemical and biochemical manufacturing by selective removal of one of the products and thereby increasing the product yield. The design of such hybrid systems need to take into acco...... and separation functionalities and to design/analyse the hybrid scheme. The generated hybrid scheme has been validated through experiments involving an esterification reaction....

  5. Experimental and kinetic study of (trans)esterification reactions on Lewatit K1221

    OpenAIRE

    Van de Steene, Evelien; Clercq, Jeriffa De; Thybaut, Joris

    2013-01-01

    (Trans)esterification reactions play a key role in today’s biorefineries. Conventionally, these reactions are performed using an acid and a base homogeneous catalyst, respectively for esterification and transesterification. Heterogeneous catalysis offers a competitive alternative for these reactions by not requiring dedicated catalyst separation and purification. A single, fixed bed catalytic reactor, comprising a top layer of acid catalyst for esterification of free fatty acids followed by ...

  6. Chapter 13 Theoretical and Experimental Studies of the Gas-Phase Cl-Atom Initiated Reactions of Benzene and Toluene

    Science.gov (United States)

    Ryzhkov, A.; Ariya, P. A.; Raofie, F.; Niki, H.; Harris, G. W.

    The reactions of benzene (Bz) and toluene (PhMe) with chlorine atoms in the gas phase have been studied using both theoretical and experimental techniques. Energy and geometry of reaction complexes and transition states were calculated in the Cl-atom initiated reaction of benzene and toluene using modern hybrid functional PBE0 method with the aug-pc1 basis set with an additional CCSD(T)/aug-CC-pVDZ energy single point calculation. Three stationary structures have been found for the Bz...Cl complex: hexahapto-complex, [pi]-complex and [sigma]-complex. The first one is a transition state between two opposite [pi]-complexes. PhMe...Cl has additional structures due to ipso-, ortho-, meta- and para-isomerization. The stability of all calculated complexes was determined and compared. Two reaction pathways for benzene and toluene with a Cl atom were evaluated: (a) the hydrogen abstraction of benzene and toluene by Cl atom, which is seemingly barrierless and endothermic, and (b) the hydrogen substitution reaction that in contrast has a relatively high energy of activation. Rate coefficients for these same reactions were measured using ethane, n-butane, and chloro-, dichloro- and trichloromethane, as reference compounds, with gas chromatography equipped with mass detection spectrometry and flame ionization detection (GC-MSD and GC-FID). The reaction rates were estimated as (5.57±0.15)×10-11 and for benzene and toluene, respectively. Chlorinated products of the reactions were analyzed by GS-MS. Chlorobenzene was the only identified product between a reaction of benzene and the Cl atom. The major products of the PhMe + Cl reaction were chloromethylbenzene with ortho- and para-chlorotoluenes.

  7. Lithium-Assisted Copolymerization of CO 2 /Cyclohexene Oxide: A Novel and Straightforward Route to Polycarbonates and Related Block Copolymers

    KAUST Repository

    Zhang, Dongyue

    2016-03-23

    A facile route toward alternating polycarbonates by anionic copolymerization of carbon dioxide (CO2) and cyclohexene oxide (CHO), using lithium halide or alkoxide as initiators and triisobutylaluminum (TiBA) as activator, is reported. α,ω-Heterobifunctional and α,ω-dihydroxypoly(cyclohexene carbonate)s (PCHC) as well as poly(CHC-co-CHO) copolymers with different carbonate composition could also be easily synthesized by adjusting the amount of TiBA or by adding inert lithium salts. The value of this initiating system also resides in the easy access to PSt-b-PCHC (PSt: polystyrene) and PI-b-PCHC (PI: polyisoprene) block copolymers which can be derived by mere one-pot sequential addition of styrene or dienes first and then of CO2 and CHO under the same experimental conditions. © 2016 American Chemical Society.

  8. A novel reverse flow reactor coupling endothermic and exothermic reactions: an experimental study

    NARCIS (Netherlands)

    van Sint Annaland, M.; Nijssen, R.C.

    2002-01-01

    A new reactor concept is studied for highly endothermic heterogeneously catalysed gas phase reactions at high temperatures with rapid but reversible catalyst deactivation. The reactor concept aims to achieve an indirect coupling of energy necessary for endothermic reactions and energy released by

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

    Science.gov (United States)

    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.

  10. Emprego de catalisadores à base de níquel para homo- e copolimerização de estireno The use of nickel-based catalysts for homo-and copolymerization of styrene

    Directory of Open Access Journals (Sweden)

    Luis Carlos Ferreira Jr.

    2004-12-01

    Full Text Available This review deals with the homo- and copolymerization of styrene with nickel catalysts. The catalytic activity, polymer stereoregularity, polymer molecular weight and polydispersity are dependent upon nickel ligands and reaction parameters. Catalysts supported on silica, treated with methylaluminoxane (MAO, have shown higher stereospecificity and activity compared to homogeneous ones. The influence of these parameters is discussed focusing on the elucidation of some aspects of the polymerization mechanism.

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

    CERN Document Server

    Egiyan, K S; Amaryan, M J; Ambrozewicz, P; Anefalos Pereira, S; Anghinolfi, M; Asryan, G; Audit, G; Avakian, H; Bagdasaryan, H; Baillie, N; Ball, J P; Baltzell, N A; Barrow, S; Batourine, V; Battaglieri, M; Bedlinskiy, I; Bektasoglu, M; Bellis, M; Benmouna, N; Berman, B L; Biselli, A S; Blaszczyk, L; Boiarinov, S; Bouchigny, S; Bradford, R; Branford, D; Briscoe, W J; Brooks, W K; Burkert, V D; Butuceanu, C; Bültmann, S; Calarco, J R; Careccia, S L; Carman, D S; Cazes, A; Chen, S; Cole, P L; Collins, P; Coltharp, P; Cords, D; Corvisiero, P; Crabb, D; Credé, V; Cummings, J P; Dashyan, N B; De Masi, R; De Sanctis, E; De Vita, R; Degtyarenko, P V; Denizli, H; Dennis, L; Deur, A; Dharmawardane, K V; Dickson, R; Djalali, C; Dodge, G E; Donnelly, J; Doughty, D; Dugger, M; Dytman, S; Dzyubak, O P; Egiyan, H; El Fassi, L; Elouadrhiri, L; Eugenio, P; Fatemi, R; Fedotov, G; Feldman, G; Fersch, R; Feuerbach, R J; Garçon, M; Gavalian, G; Gevorgyan, N; Gilfoyle, G P; Giovanetti, K L; Girod, F X; Goetz, J T; Gonenc, A; Gordon, C I O; Gothe, R W; Griffioen, K A; Guidal, M; Guillo, M; Guler, N; Guo, L; Gyurjyan, V; Hadjidakis, C; Hafidi, K; Hakobyan, H; Hakobyan, R S; Hanretty, C; Hardie, J; Hersman, F W; Hicks, K; Hleiqawi, I; Holtrop, M; Hyde-Wright, C E; Ilieva, Y; Ireland, D G; Ishkhanov, B S; Isupov, E L; Ito, M M; Jenkins, D; Jo, H S; Joo, K; Jüngst, H G; Kalantarians, N; Kellie, J D; Khandaker, M; Kim, W; Klein, A; Klein, F J; Klimenko, A V; Kossov, M; Krahn, Z; Kramer, L H; Kubarovski, V; Kuhn, S E; Kuleshov, S V; Kühn, J; Lachniet, J; Laget, J M; Langheinrich, J; Lawrence, D; Li, Ji; Livingston, K; Lu, H Y; MacCormick, M; Marchand, C; Markov, N; Mattione, P; McAleer, S; McKinnon, B; McNabb, J W C; Mecking, B A; Mehrabyan, S S; Melone, J J; Mestayer, M D; Meyer, C A; Mibe, T; Mikhailov, K; Minehart, R C; Mirazita, M; Miskimen, R; Mokeev, V; Moriya, K; Morrow, S A; Moteabbed, M; Munevar, E; Mutchler, G S; Müller, J; Nadel-Turonski, P; Nasseripour, R; Niccolai, S; Niculescu, G; Niculescu, I; Niczyporuk, B B; Niroula, M R; Niyazov, R A; Nozar, M; O'Rielly, G V; Osipenko, M; Ostrovidov, A I; Park, K; Pasyuk, E; Paterson, C; Pierce, J; Pivnyuk, N; Pocanic, D; Pogorelko, O I; Pozdniakov, S; Preedom, B M; Price, J W; Prok, Y; Protopopescu, D; Raue, B A; Riccardi, G; Ricco, G; Ripani, M; Ritchie, B G; Ronchetti, F; Rosner, G; Rossi, P; Sabatie, F; Salamanca, J; Salgado, C; Santoro, J P; Sapunenko, V; Schumacher, R A; Serov, V S; Sharabyan, Yu G; Shvedunov, N V; Skabelin, A V; Smith, E S; Smith, L C; Sober, D I; Sokhan, D; Stavinsky, A V; Stepanyan, S; Stepanyan, S S; Stokes, B E; Stoler, P; Strauch, S; Taiuti, M; Tedeschi, D J; Thoma, U; Tkabladze, A; Tkachenko, S I; Todor, L; Tur, C; Ungaro, M; Vineyard, M F; Vlassov, A V; Watts, D P; Weinstein, L B; Weygand, D P; Williams, M; Wolin, E; Wood, M H; Yegneswaran, A; Zana, L; Zhang, J; Zhao, B; Zhao, Z W

    2007-01-01

    The reaction $^2$H$(e,e^\\prime p)n$ has been studied with full kinematic coverage for photon virtuality $1.75experimental data with theory indicate that for very low values of neutron recoil momentum ($p_n<100$ MeV/c) the neutron is primarily a spectator and the reaction can be described by the plane-wave impulse approximation. For $100

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  13. A combined high-temperature experimental and theoretical kinetic study of the reaction of dimethyl carbonate with OH radicals.

    Science.gov (United States)

    Khaled, Fethi; Giri, Binod Raj; Szőri, Milán; Mai, Tam V-T; Huynh, Lam K; Farooq, Aamir

    2017-03-08

    The reaction kinetics of dimethyl carbonate (DMC) and OH radicals were investigated behind reflected shock waves over the temperature range of 872-1295 K and at pressures near 1.5 atm. Reaction progress was monitored by detecting OH radicals at 306.69 nm using a UV laser absorption technique. The rate coefficients for the reaction of DMC with OH radicals were extracted using a detailed kinetic model developed by Glaude et al. (Proc. Combust. Inst. 2005, 30(1), 1111-1118). The experimental rate coefficients can be expressed in Arrhenius form as: kexpt'l = 5.15 × 10(13) exp(-2710.2/T) cm(3) mol(-1) s(-1). To explore the detailed chemistry of the DMC + OH reaction system, theoretical kinetic analyses were performed using high-level ab initio and master equation/Rice-Ramsperger-Kassel-Marcus (ME/RRKM) calculations. Geometry optimization and frequency calculations were carried out at the second-order Møller-Plesset (MP2) perturbation level of theory using Dunning's augmented correlation consistent-polarized valence double-ζ basis set (aug-cc-pVDZ). The energy was extrapolated to the complete basis set using single point calculations performed at the CCSD(T)/cc-pVXZ (where X = D, T) level of theory. For comparison purposes, additional ab initio calculations were also carried out using composite methods such as CBS-QB3, CBS-APNO, G3 and G4. Our calculations revealed that the H-abstraction reaction of DMC by OH radicals proceeds via an addition elimination mechanism in an overall exothermic process, eventually forming dimethyl carbonate radicals and H2O. Theoretical rate coefficients were found to be in excellent agreement with those determined experimentally. Rate coefficients for the DMC + OH reaction were combined with literature rate coefficients of four straight chain methyl ester + OH reactions to extract site-specific rates of H-abstraction from methyl esters by OH radicals.

  14. Experimental investigations of mechanical and reaction responses for drop-weight impacted energetic particles

    Science.gov (United States)

    Bao, Xiao-Wei; Wu, Yan-Qing; Wang, Ming-Yang; Huang, Feng-Lei

    2017-02-01

    Low-velocity drop-weight impact experiments on individual and multiple Cyclotetramethylene tetranitramine (HMX) energetic particles were performed using a modified drop-weight machine equipped with high-speed photography components. Multiple particles experienced more severe burning reactions than an individual particle. Comparisons between impacted salt and HMX particle show that jetting in HMX is mainly due to the motion of fragmented particles driven by gaseous reaction products. Velocity of jetting, flame propagation, and area expansion were measured via image processing, making it possible to quantify the chemical reaction or mechanical deformation violence at different stages.

  15. Water vapor effect on the HNO3 yield in the HO2 + NO reaction: experimental and theoretical evidence.

    Science.gov (United States)

    Butkovskaya, Nadezhda; Rayez, Marie-Thérèse; Rayez, Jean-Claude; Kukui, Alexandre; Le Bras, Georges

    2009-10-22

    The influence of water vapor on the production of nitric acid in the gas-phase HO(2) + NO reaction was determined at 298 K and 200 Torr using a high-pressure turbulent flow reactor coupled with a chemical ionization mass spectrometer. The yield of HNO(3) was found to increase linearly with the increase of water concentration reaching an enhancement factor of about 8 at [H(2)O] = 4 x 10(17) molecules cm(-3) ( approximately 50% relative humidity). A rate constant value k(1bw) = 6 x 10(-13) cm(3) molecule(-1) s(-1) was derived for the reaction involving the HO(2)xH(2)O complex: HO(2)xH(2)O + NO --> HNO(3) (1bw), assuming that the water enhancement is due to this reaction. k(1bw) is approximately 40 times higher than the rate constant of the reaction HO(2) + NO --> HNO(3) (1b), at the same temperature and pressure. The experimental findings are corroborated by density functional theory (DFT) calculations performed on the H(2)O/HO(2)/NO system. The significance of this result for atmospheric chemistry and chemical amplifier instruments is briefly discussed. An appendix containing a detailed consideration of the possible contribution from the surface reactions in our previous studies of the title reaction and in the present one is included.

  16. Compound-nuclear reactions with unstable nuclei: Constraining theory through innovative experimental approaches

    Directory of Open Access Journals (Sweden)

    Escher J. E.

    2016-01-01

    Full Text Available Cross sections for compound-nuclear reactions involving unstable targets are important for many applications, but can often not be measured directly. Several indirect methods have recently been proposed to determine neutron capture cross sections for unstable isotopes. We consider three approaches that aim at constraining statistical calculations of capture cross sections with data obtained from the decay of the compound nucleus relevant to the desired reaction. Each method produces this compound nucleus in a different manner (via a light-ion reaction, a photon-induced reaction, or β-decay and requires additional ingredients to yield the sought-after cross section. We give a brief outline of the approaches and employ preliminary results from recent measurements to illustrate the methods. We discuss the main advantages and challenges of each approach.

  17. Theoretical and Experimental Study of Complex Ions from Reactions of Al+ (Cu+) with Amine Molecules

    Institute of Scientific and Technical Information of China (English)

    HU,Zheng-Fa; LUO,Li; HU,Yi-Hua

    2008-01-01

    The gas phase reactions of metal ions (Al+,Cu+) with amine molecules [CH3NH2=MA,(CH3)2NH=DMA]were investigated using a laser ablation-molecular beam method.The directly associated product complex ions,Al+-MA and Al+-DMA,and the dehydrogenation product ions,Cu+(CH2NH) and Cu+(C2H5N),as well as hydrated ion Cu+(NC2H5·H2O),have been obtained and recorded from the reactions of the metal ions and organic amine molecules,and density functional theory (B3LYP) calculations have been performed to reveal the optimized geometry,energefics,and reaction mechanism of the title reactions with basis set 6-311+G(d,p) adopted.

  18. Statistical Ring Opening Metathesis Copolymerization of Norbornene and Cyclopentene by Grubbs’ 1st-Generation Catalyst

    Directory of Open Access Journals (Sweden)

    Christiana Nikovia

    2015-08-01

    Full Text Available Statistical copolymers of norbornene (NBE with cyclopentene (CP were prepared by ring-opening metathesis polymerization, employing the 1st-generation Grubbs’ catalyst, in the presence or absence of triphenylphosphine, PPh3. The reactivity ratios were estimated using the Finemann-Ross, inverted Finemann-Ross, and Kelen-Tüdos graphical methods, along with the computer program COPOINT, which evaluates the parameters of binary copolymerizations from comonomer/copolymer composition data by integrating a given copolymerization equation in its differential form. Structural parameters of the copolymers were obtained by calculating the dyad sequence fractions and the mean sequence length, which were derived using the monomer reactivity ratios. The kinetics of thermal decomposition of the copolymers along with the respective homopolymers was studied by thermogravimetric analysis within the framework of the Ozawa-Flynn-Wall and Kissinger methodologies. Finally, the effect of triphenylphosphine on the kinetics of copolymerization, the reactivity ratios, and the kinetics of thermal decomposition were examined.

  19. Experimental study of the astrophysical gamma-process reaction 124Xe(alpha,gamma)128Ba

    CERN Document Server

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

    2016-01-01

    The synthesis of heavy, proton rich isotopes in the astrophysical gamma-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(g,a)124Xe was found to affect the abundance of the p nucleus 124Xe. 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(a,g)128Ba reaction and to compare the results with statistical model predictions. Of great importance is the fact that data below the (a,n) threshold was obtained. Studying simultaneously the 124Xe(a,n)127Ba reaction channel at higher energy allowed to further identify the source of a discrepancy between data and prediction. The 124Xe + alpha cross sections were measured with the activation method using a thin window 124Xe gas cell. The studied energy range was between E = 11 and 15 MeV close above the astrophysically relevant...

  20. Density Polyethylene (HDPE) by In-Situ Chlorinating Graft Copolymerization%制备氯引发PE接枝苯乙烯/顺丁烯二酸酐

    Institute of Scientific and Technical Information of China (English)

    赵志强; 王双双; 王娜; 闫志佩; 赵季若; 冯莺

    2011-01-01

    Attempts to enhance the grafting degree (GD) of maleric anhydride (MAH) onto high density polyethylene (HDPE) in the presence of styrene (St) by in-situ chlorinating graft copolymerization (ISCGC) were made. The product composed of MAH/St copolymer as grafted chains and polyethylene as backbone (only containing trace chlorine) was named as PE-cg-(MAH/St). The feasibility of preparing PE-cg-(MAH/St) was identified by both FTIR and 'H-NMR spectrum. The structure of the graft copolymer was characterized by FTIR,'H-NMR, DSC and GPC. The gel content (GC) close to zero showed that there was no cross-link reaction in MAH/St grafted onto PE by ISCGC. The effects of reaction temperature,mass ratio,total monomer concentration,chlorine flow rate on the GD of MAH were also investigated, and the experimental results showed that the addition of the second monomer St could significantly increased the GD of MAH. In the case of setting the reaction temperature was 80 ~ 90℃, the mass ratio of MAH and St was about 9:7, the total monomer was 16 parts per hundreds of resin,and chlorine flow 29 mmol/min.GD was up to 3.56 % .%为提高氯化原位接枝过程中聚乙烯(PE)接枝顺丁烯二酸酐(MAH)的接枝率,加入了第二单体苯乙烯(St).以FTIR,1H-NMR、GPC及凝胶含量研究PE氯化原位接枝MAH/St接枝共聚物(PE-cg-(MAH/St)的结构.实验结果表明:第二单体St的加入可以明显提高MAH的接枝率,同时没有交联结构的产生.研究了反应温度、单体配比、单体总质量分数、氯气流速等对接枝产物PE-cg-(MAH/St)接枝率的影响,并对接枝物的热性能进行了探索.当反应温度控制在80~90℃,MAH/St单体比例为9:7,单体总量16份,氯气流速29 mmol/min,MAH的接枝率可达3.56%.

  1. A convenient method for experimental determination of yields and isomeric ratios in photonuclear reactions measured by the activation technique

    Science.gov (United States)

    Kolev, D.; Dobreva, E.; Nenov, N.; Todorov, V.

    1995-02-01

    A generalized exact formula is derived for a determination of the experimental isomeric ratio in any incident particle activation. For the particular case, when the activity of the ground state results from the simultaneous decay of both states and can be conveniently measured, the appropriate modification of this formula is evaluated and applied to six photonuclear reactions induced by 43 MeV bremsstrahlung. The experimental isomeric yield ratios of (γ, 3n) 110m,gIn; (γ, p) (γ, pn), (γ, 2n2p) 117m,gIn; (γ, n) 164m,gHo and (γ, 3n) 162m,gHo are deduced.

  2. Novel rubbers from cationic copolymerization of soybean oils and dicyclopentadiene. 1. Synthesis and characterization.

    Science.gov (United States)

    Andjelkovic, Dejan D; Larock, Richard C

    2006-03-01

    Novel thermosetting copolymers, ranging from tough and ductile to very soft rubbers, have been prepared by the cationic copolymerization of regular (SOY) and 100% conjugated soybean oils (C(100)SOY) with dicyclopentadiene (DCP) catalyzed by Norway fish oil (NFO)-modified and SOY- and C(100)SOY-diluted boron trifluoride diethyl etherate (BFE). The gelation time of the reactions varies from 4 to 991 min at 110 degrees C. The yields of the bulk copolymers are essentially quantitative, while the yields of the cross-linked copolymers remaining after Soxhlet extraction with methylene chloride range from 69% to 88%, depending on the monomer stoichiometry and the catalyst used. (1)H NMR spectroscopy and Soxhlet extraction data indicate that these copolymers consist of a cross-linked soybean oil-DCP network plasticized by certain amounts of methylene chloride-soluble linear or less cross-linked soybean oil-DCP copolymers, unreacted oil, and some low molecular weight hydrolyzed oil. The molecular weights of these soluble fractions are in the range from 400 to 10,000 g/mol based on polystyrene standards. The bulk copolymers have glass transition temperatures ranging from -22.6 to 56.6 degrees C, while their tan delta peak values range from 0.7 to 1.2. Thermogravimetric analysis (TGA) indicates that these soybean oil-DCP copolymers are thermally stable below 200 degrees C, with 10% and 50% weight loss temperatures ranging from 280 to 372 degrees C and 470-554 degrees C, respectively. These properties suggest that these biobased thermosets may prove useful alternatives to current petroleum-based plastics and find widespread utility.

  3. STUDIES ON GRAFT COPOLYMERIZATION OF DL—LACTIDE ON CORN STARCH AND BIODEGRADABILITY OF THE COPOLYMERS

    Institute of Scientific and Technical Information of China (English)

    YOUYingcai; ZHUChangying; 等

    2000-01-01

    The starch/D,L-lactide graft copolymers were synthesized by reacting D,L-lactide with corn starch in N,N-dimethylacetamide(DMAM)in the presence of triethylamine(NEt3)and anhydrous lithium chloride.The effect of reaction time and the molar ratio of D,L-lactide to glucose structural unit of starch on monomer conversion(C%),graft(G%)and graft efficiency(GE%)were studied,The C%,G%and GE% could approach 37.3% 179.7%and 68.0%,respectively when the molar ratio of D,L-lactide to glucose structuralunit of starch is 10:1 and the graft copolymerization was carried out at 80-85℃ for 4hr under nitrogen atmosphere.The Fourier transforms infra-red (FTIR) spectroscopy.differential scanning calorimetry(DSC)and X_ray diffraction (XRD) spectroscopy were used in order to characterize the graft copolymers.FTIR spectra show that absorption band at 1740cm-1 confirmed the formation of ester bond,indicating the starch /D,L-lactide graft copolymers were produced,the DSC characteristic results show the melting temperature of the graft copolymer were elevated slightly as the molar ratio of D,L-lactide to glucose structural units of starch increased and the X-ray diffraction spectra show the synthesized graft copolymers were amorphous.The degradability of graft copolymer was tested with the aid of acid,alkali and microbe such as bacillus subtilis and staphylococcus aureus.The results of water rsistance show the graft copolymer produced can be used as a component of impermeable coating for cardboard.

  4. Experimental Study on Hydrocarbon Formation Due to Reactions Between Carbonates and Water or Water—Bearing Minerals in Deep Earth

    Institute of Scientific and Technical Information of China (English)

    翁克难; 汪本善; 等

    1999-01-01

    In order to investigate the mechanism of formation of abiogenetic hydrocarbons at the depth of the Earth,experimental research on reactions between carbonates and water or waterbearing minerals was carried out at the pressure of about 1GPa and the temperature range of 800-1500℃.The reactions took place in an open and nonequilibrium state.Chromatographic analyses of the gas products indicate that in the experiments there were generated CH4-dominated hydrocarbons,along with some CO2 and CO.Accordingly,we think there is no essential distinction between free-state water and hydroxy in the minerals in the process of hydrocarbon formation.This study indicates that reactions between carbonates and water or water-bearing minerals should be an important factor leading to the formation of abiogenetic hydrocarbons at the Earth's depth.

  5. Experimental and Modeling Studies of the Methane Steam Reforming Reaction at High Pressure in a Ceramic Membrane Reactor

    OpenAIRE

    Hacarlioglu, Pelin

    2007-01-01

    This dissertation describes the preparation of a novel inorganic membrane for hydrogen permeation and its application in a membrane reactor for the study of the methane steam reforming reaction. The investigations include both experimental studies of the membrane permeation mechanism and theoretical modeling of mass transfer through the membrane and simulation of the membrane reactor with 1-D and 2-D models. A hydrothermally stable and hydrogen selective membrane composed of silica and a...

  6. Mechanical properties of products of thermocatalytic and radiolytic styrene - acrylonitrile copolymerization

    Energy Technology Data Exchange (ETDEWEB)

    Gadalla, A.M.; Derini, M.A.E.

    1983-12-01

    The mechanical properties of styrene (S)-acrylonitrile (AN) mixtures, ranging from 20 to 80 wt % S, polymerized by thermocatalytic and radiolytic techniques were studied. Maximum compressive and tensile strength was obtained for the mixture containing 60 wt % styrene. The hardness increased with styrene concentration up to 40 wt % and then remained nearly constant. Radiolytic copolymerization gave stronger copolymers than thermal copolymerization since irradiation enhances crosslinking. For the same composition, as the dose increases, the strength increases to a maximum and then decreases due to competing rates of crosslinking and degradation. 5 figures.

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

    Science.gov (United States)

    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.

  8. A new approach in copolymerization: Monte Carlo method for the reactivity ratios calculation in copolymerization of furfuryl acrylate with 2-hydroxyethyl methacrylate

    Directory of Open Access Journals (Sweden)

    D. Zaldívar

    1999-01-01

    Full Text Available Copolymers of furfuryl acrylate (A with 2-hydroxyethyl methacrylate (H were prepared by free radical copolymerization in DMF solution at 50°C, using 2,2'-azobisisobutyronitrile (AIBN as initiator. The reactivity ratios of both monomers were calculated according to the general copolymerization equation using the Fineman-Röss and Kelen-Tüdos 1inearization methods, as well as the Tidwell-Mortimer non linear least-squares treatment and the Monte Carlo random method. The reactivity ratios obtained were rA = 0.93 and rH = 1.42. Similar results were obtained by both, the Monte Carlo and the non-linear least squares methods. The microstructure of copolymer chains based on the first order Markov statistics is described.

  9. Preparation of Cross-linking Copolymerization of Chitosan and AMPS in Ionic Liquid%离子液体中壳聚糖/AMPS共聚交联微球的制备

    Institute of Scientific and Technical Information of China (English)

    张聪璐; 胡筱敏; 侯晓虹; 陶颖婷

    2013-01-01

    Cross-linking copolymerization of 2-acrylamide-2-methylpro panesulfonic acid (AMPS) and chitosan in ionic liquid was studied using ceric ammonium nitrate (CAN) as an initiator, p-benzoquinone as resistance polymerization retarder, and glycine hydrochloride ionic liquid water solution as reaction medium. The obtained product was characterized by SEM, FTIR and TGA. The results showed that, the reaction rate and grafting ratio were improved greatly by [Gly]Cl as reaction medium. The obtained product was regular spherical , the particle diameter was about 2 μm. And the product had smooth surface, some resistance to acid and alkali.

  10. Electronic Effects of Aluminum Complexes in the Copolymerization of Propylene Oxide with Tricyclic Anhydrides: Access to Well-Defined, Functionalizable Aliphatic Polyesters.

    Science.gov (United States)

    Van Zee, Nathan J; Sanford, Maria J; Coates, Geoffrey W

    2016-03-02

    The synthesis of well-defined and functionalizable aliphatic polyesters remains a key challenge in the advancement of emerging drug delivery and self-assembly technologies. Herein, we investigate the factors that influence the rates of undesirable transesterification and epimerization side reactions at high conversion in the copolymerization of tricyclic anhydrides with excess propylene oxide using aluminum salen catalysts. The structure of the tricyclic anhydride, the molar ratio of the aluminum catalyst to the nucleophilic cocatalyst, and the Lewis acidity of the aluminum catalyst all influence the rates of these side reactions. Optimal catalytic activity and selectivity against these side reactions requires a careful balance of all these factors. Effective suppression of undesirable transesterification and epimerization was achieved even with sterically unhindered monomers using a fluorinated aluminum salph complex with a substoichiometric amount of a nucleophilic cocatalyst. This process can be used to synthesize well-defined block copolymers via a sequential addition strategy.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    Jiang, Zhaozhong

    2011-05-09

    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).

  13. Experimental study of the knockout reaction mechanism using O14 at 60 MeV/nucleon

    Science.gov (United States)

    Sun, Y. L.; Lee, J.; Ye, Y. L.; Obertelli, A.; Li, Z. H.; Aoi, N.; Ong, H. J.; Ayyad, Y.; Bertulani, C. A.; Chen, J.; Corsi, A.; Cappuzzello, F.; Cavallaro, M.; Furono, T.; Ge, Y. C.; Hashimoto, T.; Ideguchi, E.; Kawabata, T.; Lou, J. L.; Li, Q. T.; Lorusso, G.; Lu, F.; Liu, H. N.; Nishimura, S.; Suzuki, H.; Tanaka, J.; Tanaka, M.; Tran, D. T.; Tsang, M. B.; Wu, J.; Xu, Z. Y.; Yamamoto, T.

    2016-04-01

    Background: For the deeply bound one-nucleon removal at intermediate energies using a Be9 or C12 target, a strong reduction of cross section was observed relative to the prediction of eikonal theoretical model. The large disagreement has not been explained and the systematic trend is inconsistent with results from transfer reactions. The recently observed asymmetric parallel momentum distribution of the knockout residue indicates the significant dissipative core-target interaction in the knockout reaction with a composite target, implying new reaction mechanisms beyond the eikonal reaction descriptions. Purpose: To investigate the reaction mechanism for deeply bound nucleon removal at intermediate energies. Method: Neutron removal from O14 using a C12 target at 60 MeV/nucleon was performed. Nucleon knockout cross sections were measured. The unbound excited states of O13 were reconstructed by using the invariant mass method with the residues and the associated decay protons measured in coincidence. The measured cross sections are compared with an intra-nuclear cascade (INC) prediction. Results: The measured cross section of (O14C11,) is 60(9) mb, which is 3.5 times larger than that of (O14O13,) channel. This 2 p n -removal cross section is consistent with INC prediction, which is 66 mb with the main contribution being non-direct reaction processes. On the other hand, the upper limit of the cross section for one-neutron removal from O14 followed by proton evaporation is 4.6(20) mb, integrated up to 6 MeV above the proton separation energy of O13 . The calculated total cross section for such reaction processes by the INC model is 2.5 mb, which is within the measured upper limit. Conclusions: The data provide the first constraint on the role of core excitation and evaporation processes in deeply bound nucleon removal from asymmetric nuclei. The experiment results suggest that non-direct reaction processes, which are not considered in the eikonal model, play an

  14. A case study of the mechanism of alcohol-mediated Morita Baylis-Hillman reactions. The importance of experimental observations.

    Science.gov (United States)

    Plata, R Erik; Singleton, Daniel A

    2015-03-25

    The mechanism of the Morita Baylis-Hillman reaction has been heavily studied in the literature, and a long series of computational studies have defined complete theoretical energy profiles in these reactions. We employ here a combination of mechanistic probes, including the observation of intermediates, the independent generation and partitioning of intermediates, thermodynamic and kinetic measurements on the main reaction and side reactions, isotopic incorporation from solvent, and kinetic isotope effects, to define the mechanism and an experimental mechanistic free-energy profile for a prototypical Morita Baylis-Hillman reaction in methanol. The results are then used to critically evaluate the ability of computations to predict the mechanism. The most notable prediction of the many computational studies, that of a proton-shuttle pathway, is refuted in favor of a simple but computationally intractable acid-base mechanism. Computational predictions vary vastly, and it is not clear that any significant accurate information that was not already apparent from experiment could have been garnered from computations. With care, entropy calculations are only a minor contributor to the larger computational error, while literature entropy-correction processes lead to absurd free-energy predictions. The computations aid in interpreting observations but fail utterly as a replacement for experiment.

  15. Experimental determination of proton induced reaction cross sections on {sup nat}Ni near threshold energy

    Energy Technology Data Exchange (ETDEWEB)

    Uddin, Md. Shuza [Atomic Energy Research Establishment, Dhaka (Bangladesh). Tandem Accelerator Facilities; Forschungszentrum Juelich GmbH (Germany). Inst. fuer Neurowissenschaften und Medizin, INM-5: Nuklearchemie; Chakraborty, Animesh Kumer [Atomic Energy Research Establishment, Dhaka (Bangladesh). Tandem Accelerator Facilities; Chittagong University of Engineering and Technology (Bangladesh). Dept. of Physics; Spellerberg, Stefan; Spahn, Ingo; Qaim, Syed M. [Forschungszentrum Juelich GmbH (Germany). Inst. fuer Neurowissenschaften und Medizin, INM-5: Nuklearchemie; Shariff, Md. Asad; Das, Sopan [Atomic Energy Research Establishment, Dhaka (Bangladesh). Tandem Accelerator Facilities; Rashid, Md. Abdur [Chittagong University of Engineering and Technology (Bangladesh). Dept. of Physics

    2016-08-01

    A newly developed facility at the 3 MV Tandem Accelerator at Dhaka for measurement of proton induced reaction cross sections in the energy region below 5 MeV is outlined and tests for the beam characterization are described. The results were validated by comparison with the well-known excitation function of the {sup 64}Ni(p, n){sup 64}Cu reaction. Excitation functions of the reactions {sup nat}Ni(p, x){sup 60,61}Cu, {sup nat}Ni(p, x){sup 55,57,58m+g}Co and {sup nat}Ni(p, x){sup 57}Ni were also measured from threshold to 16 MeV using the stacked-foil technique, whereby irradiations were performed with 5 MeV protons available at the Tandem Accelerator and 16.7 MeV protons at the BC 1710 cyclotron at Juelich, Germany. The radioactivity was measured using HPGe γ-ray detectors. A few results are new, the others strengthen the database. In particular, the results of the reaction {sup nat}Ni(p, x){sup 61}Cu below 3 MeV could serve as beam monitor.

  16. Experimental evidence of the relevance of orientational correlations in photoinduced bimolecular reactions in solution.

    Science.gov (United States)

    Angulo, Gonzalo; Cuetos, Alejandro; Rosspeintner, Arnulf; Vauthey, Eric

    2013-09-12

    A major problem in the extraction of the reaction probability in bimolecular processes is the disentanglement from the influence of molecular diffusion. One of the strategies to overcome it makes use of reactive solvents in which the reactants do not need to diffuse to encounter each other. However, most of our quantitative understanding of chemical reactions in solution between free partners is based on the assumption that they can be approximated by spheres because rotation averages their mutual orientations. This condition may not be fulfilled when the reaction takes place on time scales faster than that of molecular reorientation. In this work, the fluorescence quenching of two very similar polyaromatic hydrocarbons with different electric dipole moments is measured. The concentration of a liquid electron-donating quencher is varied from very dilute solutions to pure quencher solutions. In both cases, the thermodynamics of the reactions are very similar and, according to the Marcus expression, the kinetics are expected to proceed at similar rates. However, one of them is 10 times faster in the pure quencher solution. This difference starts at relatively low quencher concentrations. An explanation based on the fluorophore-solvent dipole-dipole interaction and the consequent orientational solvent structure is provided. The orientational correlation between fluorophore and quencher is calculated by means of computer simulations. Important differences depending on the fluorophore dipole moment are found. The kinetics can be explained quantitatively with a reaction-diffusion model that incorporates the effects of the presence of the dipole moment and the rotational diffusion, only in the highest quencher concentration case, but not in dilute solutions, most likely due to fundamental limitations of the kinetic theory.

  17. Design of an experimental device dedicated to the measurement of spallation reactions; Mise au point d'un dispositif experimental pour des mesures exclusives des reactions de spallation

    Energy Technology Data Exchange (ETDEWEB)

    Lafriakh, A

    2005-12-15

    Spallation mechanisms are not yet completely understood, especially because of the difficulty of experimentally disentangling the effects of the different steps of the reaction. In order to understand these mechanisms, we have developed a new experimental device able to perform inclusive measurements. We propose a detection system based on a combination of ionization chambers and proportional counters and on a wall of plastic scintillators to measure light charged particles. In particular the detection of light charged particles is described in detail. In order to validate our device, we have compared our preliminary results obtained on the Fe{sup 56} + p system at 1 GeV/u with inclusive measurements previously obtained at the FRS spectrometer of the GSI facility. A comparison of charge differential cross section shows reasonable agreement. However, our new device allowed extension of those measurements down to Z = 1 and Z = 2. These cross sections are important for material damage studies. Taking into account our error brackets, the evolution of mean longitudinal velocities with respect to residue masses is comparable to that obtained at the FRS. These first results, although preliminary, allow us to validate our experimental device. It is now possible to exploit the strong points of our exclusive measurements, namely correlations between different measured observables. Finally, experimental problems encountered will be taken into account in the future experimental programs, in order to ensure the best measurements conditions.

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

    Science.gov (United States)

    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

  19. A combined experimental and theoretical study of reactions between the hydroxyl radical and oxygenated hydrocarbons relevant to astrochemical environments.

    Science.gov (United States)

    Shannon, R J; Caravan, R L; Blitz, M A; Heard, D E

    2014-02-28

    The kinetics of the reactions of the hydroxyl radical (OH) with acetone and dimethyl ether (DME) have been studied between 63-148 K and at a range of pressures using laser-flash photolysis coupled with laser induced fluorescence detection of OH in a pulsed Laval nozzle apparatus. For acetone, a large negative temperature dependence was observed, with the rate coefficient increasing from k1 = (1.6 ± 0.8) × 10(-12) cm(3) molecule(-1) s(-1) at 148 K to (1.0 ± 0.1) × 10(-10) cm(3) molecule(-1) s(-1) at 79 K, and also increasing with pressure. For DME, a similar behaviour was found, with the rate coefficient increasing from k2 = (3.1 ± 0.5) × 10(-12) cm(3) molecule(-1) s(-1) at 138 K to (1.7 ± 0.1) × 10(-11) cm(3) molecule(-1) s(-1) at 63 K, and also increasing with pressure. The temperature and pressure dependence of the experimental rate coefficients are rationalised for both reactions by the formation and subsequent stabilisation of a hydrogen bonded complex, with a non-zero rate coefficient extrapolated to zero pressure supportive of quantum mechanical tunnelling on the timescale of the experiments leading to products. In the case of DME, experiments performed in the presence of O2 provide additional evidence that the yield of the CH3OCH2 abstraction product, which can recycle OH in the presence of O2, is ≥50%. The experimental data are modelled using the MESMER (Master Equation Solver for Multi Energy Well Reactions) code which includes a treatment of quantum mechanical tunnelling, and uses energies and structures of transition states and complexes calculated by ab initio methods. Good agreement is seen between experiment and theory, with MESMER being able to reproduce for both reactions the temperature behaviour between ~70-800 K and the pressure dependence observed at ~80 K. At the limit of zero pressure, the model predicts a rate coefficient of ~10(-11) cm(3) molecule(-1) s(-1) for the reaction of OH with acetone at 20 K, providing evidence that the

  20. Role of the experimental filter in obtaining the Arrhenius plot in multifragmentation reactions

    CERN Document Server

    Tirel, O; Nebauer, R; Aichelin, Jörg

    1998-01-01

    Recently it has been argued that the linear relation between the transverse energy and the apparent probability to emit a fragment proves that the total system is in thermal equilibrium. It is shown, for a specific reaction Xe+Sn at 50 A.MeV, that the same behavior is obtained in the context of Quantum Molecular Dynamical without invoking the idea of equilibrium. The linear dependance is shown to be a detector effect.

  1. Experimental and theoretical study of the reactions between neutral vanadium oxide clusters and ethane, ethylene, and acetylene.

    Science.gov (United States)

    Dong, Feng; Heinbuch, Scott; Xie, Yan; Rocca, Jorge J; Bernstein, Elliot R; Wang, Zhe-Chen; Deng, Ke; He, Sheng-Gui

    2008-02-13

    Reactions of neutral vanadium oxide clusters with small hydrocarbons, namely C2H6, C2H4, and C2H2, are investigated by experiment and density functional theory (DFT) calculations. Single photon ionization through extreme ultraviolet (EUV, 46.9 nm, 26.5 eV) and vacuum ultraviolet (VUV, 118 nm, 10.5 eV) lasers is used to detect neutral cluster distributions and reaction products. The most stable vanadium oxide clusters VO2, V2O5, V3O7, V4O10, etc. tend to associate with C2H4 generating products V(m)O(n)C2H4. Oxygen-rich clusters VO3(V2O5)(n=0,1,2...), (e.g., VO3, V3O8, and V5O13) react with C2H4 molecules to cause a cleavage of the C=C bond of C2H4 to produce (V2O5)(n)VO2CH2 clusters. For the reactions of vanadium oxide clusters (V(m)O(n)) with C2H2 molecules, V(m)O(n)C2H2 are assigned as the major products of the association reactions. Additionally, a dehydration reaction for VO3 + C2H2 to produce VO2C2 is also identified. C2H6 molecules are quite stable toward reaction with neutral vanadium oxide clusters. Density functional theory calculations are employed to investigate association reactions for V2O5 + C2H(x). The observed relative reactivity of C2 hydrocarbons toward neutral vanadium oxide clusters is well interpreted by using the DFT calculated binding energies. DFT calculations of the pathways for VO3+C2H4 and VO3+C2H2 reaction systems indicate that the reactions VO3+C2H4 --> VO2CH2 + H2CO and VO3+C2H2 --> VO2C2 + H2O are thermodynamically favorable and overall barrierless at room temperature, in good agreement with the experimental observations.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  4. A combined high-temperature experimental and theoretical kinetic study of the reaction of dimethyl carbonate with OH radicals

    KAUST Repository

    Khaled, Fathi

    2017-02-08

    The reaction kinetics of dimethyl carbonate (DMC) and OH radicals were investigated behind reflected shock waves over the temperature range of 872-1295 K and at pressures near 1.5 atm. Reaction progress was monitored by detecting OH radicals at 306.69 nm using a UV laser absorption technique. The rate coefficients for the reaction of DMC with OH radicals were extracted using a detailed kinetic model developed by Glaude et al. (Proc. Combust. Inst. 2005, 30(1), 1111-1118). The experimental rate coefficients can be expressed in Arrhenius form as: kexpt\\'l = 5.15 × 10(13) exp(-2710.2/T) cm(3) mol(-1) s(-1). To explore the detailed chemistry of the DMC + OH reaction system, theoretical kinetic analyses were performed using high-level ab initio and master equation/Rice-Ramsperger-Kassel-Marcus (ME/RRKM) calculations. Geometry optimization and frequency calculations were carried out at the second-order Møller-Plesset (MP2) perturbation level of theory using Dunning\\'s augmented correlation consistent-polarized valence double-ζ basis set (aug-cc-pVDZ). The energy was extrapolated to the complete basis set using single point calculations performed at the CCSD(T)/cc-pVXZ (where X = D, T) level of theory. For comparison purposes, additional ab initio calculations were also carried out using composite methods such as CBS-QB3, CBS-APNO, G3 and G4. Our calculations revealed that the H-abstraction reaction of DMC by OH radicals proceeds via an addition elimination mechanism in an overall exothermic process, eventually forming dimethyl carbonate radicals and H2O. Theoretical rate coefficients were found to be in excellent agreement with those determined experimentally. Rate coefficients for the DMC + OH reaction were combined with literature rate coefficients of four straight chain methyl ester + OH reactions to extract site-specific rates of H-abstraction from methyl esters by OH radicals.

  5. Copolymeric polythioesters by lipase-catalyzed thioesterification and transthioesterification of alpha,omega-alkanedithiols.

    Science.gov (United States)

    Weber, N; Bergander, K; Fehling, E; Klein, E; Vosmann, K; Mukherjee, K D

    2006-04-01

    Linear copolymeric polythioesters [PTE; poly(alpha,omega-alkanedioic acid-co-alpha,omega-alkanedithiols)] were formed in good yield (approximately 69%) by thioesterification of 1,12-dodecanedioic acid with 1,6-hexanedithiol and 1,8-octanedithiol, respectively, catalyzed by immobilized lipase from Rhizomucor miehei (Lipozyme RM IM) in vacuo without a solvent. Similarly, transthioesterification (thiolysis) of diethyl 1,12-dodecanedioate with 1,6-hexanedithiol led to the formation of approximately 66% PTE. Poly (1,12-dodecanedioic acid-co-1,6-hexanedithiol) and poly (1,12-dodecanedioic acid-co-1,8-octanedithiol) were extracted from the reaction mixture using methyl-t-butylether, precipitated at -20 degrees C and the precipitates extracted with boiling i-hexane to yield two fractions of PTE. The i-hexane-insoluble fraction of poly (1,12-dodecanedioic acid-co-1,6-hexanedithiol) shows an average molecular mass (Mw) of 1,212 Da, corresponding to a molecular weight range of up to 13,200 Da and a degree of polymerization of up to 38 monomer units. The i-hexane-insoluble fraction of poly (1,12-dodecanedioic acid-co-1,8-octanedithiol) shows a Mw of 2,360 Da, corresponding to a molecular weight range of up to 19,500 Da and a maximum degree of polymerization of up to 52 monomer units. The low-molecular weight (<800 Da) reaction products of thioesterification of 1,12-dodecanedioic acid with 1,6-hexanedithiol, elucidated by gas chromatography-mass spectroscopy, show the following intermediates: (1) 9,20-dioxo-1,8-dithiacycloeicosane; (2) 17,28-dioxo-1,8,9,16-tetrathiacyclooctacosane; (3) 1,12-dodecanedioic acid methyl(O)ester 6'-S-mercaptohexyl thio(S)ester; and (4) oligomeric linear thioester, formed by thioesterification of two molecules of 1,12-dodecanedioic acid with one molecule of 1,6-hexanedithiol.

  6. Reaction of protonated tyrosine with electronically excited singlet molecular oxygen (a1Delta(g)): an experimental and trajectory study.

    Science.gov (United States)

    Fang, Yigang; Liu, Jianbo

    2009-10-22

    Reaction of protonated tyrosine with the lowest electronically excited singlet state of molecular oxygen, (1)O(2) (a(1)Delta(g)), is reported over the center-of-mass collision energy (E(col)) range from 0.1 to 3.0 eV, using an electrospray-ionization, guided-ion-beam scattering instrument, in conjunction with ab initio electronic structure calculations and direct dynamics trajectory simulations. Only one product channel is observed, corresponding to generation of hydrogen peroxide via transfer of two hydrogen atoms from protonated tyrosine. Despite being exoergic, the reaction is in competition with physical quenching of (1)O(2) and is very inefficient. At low E(col), the reaction may be mediated by intermediate complexes and shows strong inhibition by collision energy. At high E(col), the reaction efficiency drops to approximately 1% and starts to have contribution from a direct mechanism. Quasi-classical trajectory simulations were performed to probe the mechanism at high collision energies. Analysis of trajectories shows that, at E(col) of 3.0 eV, a small fraction of hydrogen peroxide (25%) is produced via a direct, concerted mechanism where two hydrogen atoms are transferred simultaneously, but most hydrogen peroxide (75%) is formed by dissociation of hydroperoxide intermediates. According to ab initio calculations and trajectory simulations, collisions also lead to formation of various endoperoxides, and dissociation of endoperoxides may play a role in physical quenching of (1)O(2). The apparatus and experimental techniques are described in detail.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  9. Electronically Stabilized Copoly(Styrene-Acrylic Acid Submicrocapsules Prepared by Miniemulsion Copolymerization

    Directory of Open Access Journals (Sweden)

    Minkwan Kim

    2017-07-01

    Full Text Available This work reports the preparation and characterization of poly(styrene-acrylic acid (St/AA submicrocapsules by using the miniemulsion copolymerization method. AA was introduced to miniemulsion polymerization of St to increase the zeta potential and the resulting electrostatic stability of St/AA submicrocapsules. Phytoncide oil was adopted as the core model material. Miniemulsion copolymerization of St and AA was conducted at a fixed monomer concentration (0.172 mol with a varying monomer feed ratio [AA]/[St] (0.2, 0.25, 0.33, 0.5, and 1.0. Concentrations of initiator (azobisisobutyronitrile; 1.0 × 10−3, 2.0 × 10−3, 3.0 × 10−3, and 4.0 × 10−3 mol/mol of monomer and surfactant (sodium dodecyl sulfate; 0.6 × 10−3, 1.0 × 10−3, and 1.4 × 10−3 mol were also controlled to optimize the miniemulsion copolymerization of St and AA. Dynamic light scattering and microscopic analyses confirmed the optimum condition of miniemulsion copolymerization of St and AA. Long-term colloidal stability of aqueous St/AA submicrocapsule suspension was evaluated by using TurbiscanTM Lab. In this work, the optimum condition for miniemulsion copolymerization of St and AA was determined ([AA]/[St] = 0.33; [SDS] = 1.0 × 10−3 mol; [AIBN] = 2.0 × 10−3 mol/mol of monomer. St/AA submicrocapsules prepared at the optimum condition (392.6 nm and −55.2 mV of mean particle size and zeta potential, respectively showed almost no variations in backscattering intensity (stable colloids without aggregation.

  10. Experimental and theoretical study of hydrogen thiocarbonate for heterogeneous reaction of carbonyl sulfide on magnesium oxide.

    Science.gov (United States)

    Liu, Yongchun; He, Hong

    2009-04-09

    In situ diffuse reflectance infrared Fourier transform spectroscopy combined with derivative spectroscopy analysis, two-dimensional correlation spectroscopy analysis, and quantum chemical calculations were used to investigate the infrared absorbance assignment and the molecular structure of hydrogen thiocarbonate on magnesium oxide. The bands at 1283 and 1257 cm(-1), which had the typical characteristic of intermediate, were observed in experiments for the heterogeneous reaction of COS on MgO. On the basis of two-dimensional correlation spectroscopy analysis and quantum chemical calculations, the band at 1283 cm(-1) was assigned to the v(s) band of bridged thiocarbonate which formed on the two neighboring Mg atoms in the (100) face of MgO crystal, and the band at 1257 cm(-1) was the v(s) band of monodentate thiocarbonate on MgO. The v(as)(OCO) band of thiocarbonates was invisible in the experiment due to their weak absorbance and the interruption of surface carbonate. The formation mechanism of thiocarbonates is proposed, which occurred through a nucleophilic attack of preadsorbed COS by surface -OH groups followed by hydrogen atom transfer from the -OH group to the sulfur atom of preadsorbed COS. The activation energy for the intramolecular proton-transfer reaction of bridged thiocarbonate was calculated to be 18.52 kcal x mol(-1) at the B3LYP/6-31+G(d,p) level of theory.

  11. Experimental study of the {sup 22}Ne(p,{gamma}){sup 23}Na reaction and its implications for novae scenarios

    Energy Technology Data Exchange (ETDEWEB)

    Menzel, Marie-Luise

    2013-08-01

    The {sup 22}Ne(p,{gamma}){sup 23}Na reaction belongs to the catalytic neon-sodium cycle and has an important role in the explosive hydrogen burning. The neon-sodium cycle takes place at temperatures of T = 0.1 - 0.5 GK and is assumed to occur in different astrophysical systems: e.g. in novae, in super novae of type Ia and during the shell-burning of red giant branch stars. The implications of {sup 22}Ne(p,{gamma}){sup 23}Na and the neon-sodium cycle in a nova scenario have been studied by using the nuclear network code libnucnet at GSI in Darmstadt. A nova is an outburst of matter in a binary system consisting of a white dwarf and a red giant star. It is therefore a representative phenomenon for explosive hydrogen burning. For the calculation of the nucleosynthesis during the nova outburst, the code libnucnet requires the initial mass composition of the novae partners, the temperature and density profiles of the nova explosion and the thermonuclear reaction rates of the participating reactions. In the following, the code determined the flow and the final atomic abundance in the neon-sodium cycle during the entire nova process. Additionally, the influence of the temperature profile of the novae outburst as well as the thermonuclear reaction rate of the {sup 22}Ne(p,{gamma}){sup 23}Na reaction on the final atomic abundance in the outburst has been studied. A characteristic measure for the reactions in astrophysical environments is the thermonuclear reaction rate. The reaction rate of {sup 22}Ne(p,{gamma}){sup 23}Na has still strong uncertainties in the temperature range of T = 0.03 - 0.3 GK. These uncertainties are based on insufficient upper limits of the resonance strengths as well as the possible existence of tentative states that are populated in the energy range of E{sup lab}{sub p} = 30 - 300 keV. The research presented in this thesis is dedicated to the experimental study of the {sup 22}Ne(p,{gamma}){sup 23}Na reaction for an improved determination of the

  12. Experimental and theoretical studies of rate coefficients for the reaction O(3P)+CH3OH at high temperatures.

    Science.gov (United States)

    Lu, Chih-Wei; Chou, Shen-Long; Lee, Yuan-Pern; Xu, Shucheng; Xu, Z F; Lin, M C

    2005-06-22

    Rate coefficients of the reaction O((3)P) + CH(3)OH in the temperature range of 835-1777 K were determined using a diaphragmless shock tube. O atoms were generated by photolysis of SO(2) with a KrF excimer laser at 248 nm or an ArF excimer laser at 193 nm; their concentrations were monitored via atomic resonance absorption excited by emission from a microwave-discharged mixture of O(2) and He. The rate coefficients determined for the temperature range can be represented by the Arrhenius equation, k(T) = (2.29 +/- 0.18) x 10(-10) exp[-(4210 +/- 100)T] cm(3) molecule(-1) s(-1); unless otherwise noted, all the listed errors represent one standard deviation in fitting. Combination of these and previous data at lower temperature shows a non-Arrhenius behavior described as the three-parameter equation, k(T) = (2.74 +/- 0.07) x 10(-18)T(2.25 +/- 0.13) exp[-(1500 +/- 90)T] cm(3)molecule(-1) s(-1). Theoretical calculations at the Becke-3-Lee-Yang-Parr (B3LYP)6-311 + G(3df,2p) level locate three transition states. Based on the energies computed with coupled clusters singles, doubles (triples) [CCSD(T)]/6-311 + G(3df,2p)B3LYP6-311 + G(3df,2p), the rate coefficients predicted with canonical variational transition state theory with small curvature tunneling corrections agree satisfactorily with the experimental observations. The branching ratios of two accessible reaction channels forming OH + CH(2)OH (1a) and OH + CH(3)O (1b) are predicted to vary strongly with temperature. At 300 K, reaction (1a) dominates, whereas reaction (1b) becomes more important than reaction (1a) above 1700 K.

  13. A convenient method for experimental determination of yields and isomeric ratios in photonuclear reactions measured by the activation technique

    Energy Technology Data Exchange (ETDEWEB)

    Kolev, D. [Sofia Univ. (Bulgaria). Dept. of Physics; Dobreva, E. [Sofia Univ. (Bulgaria). Dept. of Physics; Nenov, N. [Sofia Univ. (Bulgaria). Dept. of Physics; Todorov, V. [A Higher Institute of Medicine, Sofia (Bulgaria)

    1995-03-15

    A generalized exact formula is derived for a determination of the experimental isomeric ratio in any incident particle activation. For the particular case, when the activity of the ground state results from the simultaneous decay of both states and can be conveniently measured, the appropriate modification of this formula is evaluated and applied to six photonuclear reactions induced by 43 MeV bremsstrahlung. The experimental isomeric yield ratios of ({gamma}, 3n) {sup 110m,g}In; ({gamma}, p) ({gamma}, pn), ({gamma}, 2n2p) {sup 117m,g}In; ({gamma}, n) {sup 164m,g}Ho and ({gamma}, 3n) {sup 162m,g}Ho are deduced. ((orig.)).

  14. Ethylene copolymerization: the influence of catalyst type on the copolymer formation; Copolimerizacao de etileno: influencia do tipo de catalisador no copolimero formado

    Energy Technology Data Exchange (ETDEWEB)

    Miranda, Marcia S. Lacerda; Dupont, Jairton; Galland, Griselda B. [Rio Grande do Sul Univ., Porto Alegre, RS (Brazil). Inst. de Quimica; Quijada, Raul [Chile Univ., Santiago (Chile). Dept. de Ingenieria Quimica

    1996-01-01

    The behaviour of catalytic systems based on zirconium compounds as Me{sub 2} Si Cp{sub 2} Zr C L{sub 2} (1) and cp{sub 2} Zr Cl{sub 2} (2) (C{sub p} ={eta}{sup 5}-cyclopentadienyl), in the copolymerization of ethylene with 1-hexene and 1-hexene and 1-octane have been investigated. It has been observed that the presence of the bridge between the cyclopentadienyl ligands has no effect on the catalytic activity for the ethylene-1-hexene copolymerization {sup 13} C NMR analysis showed that the copolymers obtained with the bridged catalyst presented higher incorporation of comonomer. Thermal analysis data and viscosity measurements proved the effect of the comonomer concentration on the structure and molecular weight of the polymer formed. Infrared results show that a possible termination reaction is the {beta}-elimination. reactivity ratio values calculated by Fineman-Ross and {sup 13} C NMR methods showed a close relation between them. values of r{sub 1} and r{sub 2} show that the metallocene and the alpha-olefin have a strong effect on the structure of the polymer. (author) 9 refs., 4 figs., 4 tabs.

  15. Preparation of Thermo-Responsive Poly(ionic liquid)s-Based Nanogels via One-Step Cross-Linking Copolymerization.

    Science.gov (United States)

    Zhang, Jing; Liu, Jingjiang; Zuo, Yong; Wang, Rongmin; Xiong, Yubing

    2015-09-18

    In this study, thermo-responsive polymeric nanogels were facilely prepared via one-step cross-linking copolymerization of ethylene glycol dimethacrylate/divinylbenzene and ionic liquid (IL)-based monomers, 1,n-dialkyl-3,3'-bis-1-vinyl imidazolium bromides ([CnVIm]Br; n = 6, 8, 12) in selective solvents. The results revealed that stable and blue opalescent biimidazolium (BIm)-based nanogel solutions could be obtained without any precipitation when the copolymerizations were conducted in methanol. Most importantly, these novel nanogels were thermo-response, and could reversibly transform to precipitation in methanol with temperature changes. Turbidity analysis and dynamic light scatting (DLS) measurement illustrated that PIL-based nanogel solutions presented the phase transform with upper critical solution temperature (UCST) in the range of 5-25 °C. The nanogels were characterized using Fourier transform infrared (FTIR), thermogravimetric analyses (TGA), and scanning electron microscopy (SEM). In addition, BIm-based nanogels could also be used as highly active catalysts in the cycloaddition reaction of CO₂ and epoxides. As a result, our attributes build a robust platform suitable for the preparation of polymeric nanomaterials, as well as CO₂ conversion.

  16. Preparation of superabsorbent by graft copolymerization of acrylic acid onto corn starch using K2S2O8 and rare earths as initiators

    Institute of Scientific and Technical Information of China (English)

    BAI Yong-ping; LI Wei-dong; FENG Li-qun; ZHAO chao

    2008-01-01

    K2S2O8 and rare earths (RE) were used as initiators to prepare superabsorbents by graft copolymeri-zation of acrylic acid (AA) onto corn starch. The effects of monomer concentration, initiator K2S2O8 concentra-tion, cross-linker concentration, reaction temperature and the concentration ratio of RE and K2S2O8 on the graft copolymerization were studied in terms of the water absorption capacity of superabsorbents. Results indicate that the optimum conditions obtained for the grafting of AA onto 5g starch are as follows: AA of 75. 773 g/L, K2S2O8 of 0.437 g/L, RE of 0.874 g/L, cross-linker of 0.381 g/L and temperature of 70℃. The maximum water absorption capacity obtained is 740 g/g. The new method of graft polymerization is easily proceeded and controlled. The graft copolymers were characterized by infra-red spectroscopy, scanning electron microscopy and TG. Results characterized by IR and SEM give strong evidence for grafting of AA onto corn starch, and those characterized by TG reveal that the grafting of AA improves the thermostability of corn starch.

  17. Novel star-type methoxy-poly(ethylene glycol) (PEG)-poly({epsilon}-caprolactone) (PCL) copolymeric nanoparticles for controlled release of curcumin

    Energy Technology Data Exchange (ETDEWEB)

    Feng Runliang; Zhu Wenxia; Song Zhimei, E-mail: zhimei_song@126.com [University of Jinan, Shandong Academy of Medical Science, Department of Pharmaceutical Engineering, School of Medicine and Life Sciences (China); Zhao Liyan [Hebei North University, Department of Pharmacy (China); Zhai Guangxi [Shandong University, Department of Pharmaceutics, College of Pharmacy (China)

    2013-06-15

    To improve curcumin's (CURs) water solubility and release property, a novel star methoxy poly(ethylene glycol)-poly({epsilon}-caprolactone) (MPEG-PCL) copolymer was synthesized through O-alkylation, basic hydrolysis and ring-opening polymerization reaction with MPEG, epichlorohydrin, and {epsilon}-caprolactone as raw materials. The structure of the novel copolymer was characterized by {sup 1}H NMR, FT-IR, and GPC. The results of FT-IR and differential scanning calorimeter of CUR-loaded nanoparticles (NPs) prepared by dialysis method showed that CUR was successfully encapsulated into the SMP12 copolymeric NPs with 98.2 % of entrapment efficiency, 10.91 % of drug loading, and 88.4 {+-} 11.2 nm of mean particle diameter in amorphous forms. The dissolubility of nanoparticulate CUR was increased by 1.38 Multiplication-Sign 10{sup 5} times over CUR in water. The obtained blank copolymer showed no hemolysis. A sustained CUR release to a total of approximately 56.13 % was discovered from CUR-NPs in 40 % of ethanol saline solution within 72 h on the use of dialysis method. The release behavior fitted the ambiexponent and biphasic kinetics equation. In conclusion, the copolymeric NPs loading CUR might serve as a potential nanocarrier to improve the solubility and release property of CUR.

  18. The Radiation Tail in (e,e'p) Reactions and Corrections to Experimental Data

    CERN Document Server

    Templon, J A; Florizone, R E J; Sarty, A J

    2000-01-01

    We present a direct calculation of the cross section for the reaction 3He(e,e'p) including the radiation tail originating from bremsstrahlung processes. This calculation is compared to measured cross sections. The calculation is carried out from within a Monte Carlo simulation program so that acceptance-averaging effects, along with a subset of possible energy losses, are taken into account. Excellent agreement is obtained between our calculation and measured data, after a correction factor for higher-order bremsstrahlung is devised and applied to the tail. Industry-standard radiative corrections fail miserably for these data, and we use the results of our calculation to dissect the failure. Implications for design and analysis of experiments in the Jefferson-Lab energy domain are discussed.

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

    Science.gov (United States)

    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.

  20. Experimental test of the non-reproducibility of cross sections in dissipative reactions

    CERN Document Server

    Dong Yu Chuan; Tian Wen Dong; Li Song Lin; Li Zhi Chang; Lu Xiu Qin; Zhao Kui; Fu Chang Bo; Liu Jian Cheng; Jiang Hua; Hu Gui Qing

    2002-01-01

    Two independent measurements of cross sections for the sup 1 sup 9 F + sup 9 sup 3 Nb dissipative heavy ion collisions have been performed at incident energies from 100 to 108 MeV in steps of 250 keV. In the two measurements, two independently prepared targets were used. All other experimental conditions were identical in both experiments. The data indicate that non-reproducibility of the non-self-averaging oscillation is yielded in the two measurements. This supports the recent theoretical predictions of spontaneous coherence, slow phase randomization and extreme sensitivity in highly excited complex quantum systems

  1. Experimental Study on Surface Reactions of Heavy Metal Ions With Quartz—Aqueous Ion Concentration Dependence

    Institute of Scientific and Technical Information of China (English)

    吴宏海; 吴大清; 等

    1999-01-01

    Adsorption of divalent metal ions,including Cu2+,Pb2+,Zn2+,Cd2+ and Ni2+,on quartz surface was measured as a function of metal ion concentration at 30℃under condi tions of solution pH=6.5 and ion strength I=0.1mol/L.Results of the experimental measuements can be described very well by adsorption isoterm dquations of Freudlich.The correlation coefficients(r)of adsorption isotherm lines are>0.96.Moreover,the exprimental data were interpreted on the basis of surface complexation model.Te experimental results showed that the monodentate-coordinated metal ion surface complex species(SOM+)are predominant over the bidentate-coordinated metal ion surface complex species[(SO)2M]formed only by the ions Cu2+,Zn2+ and Ni2+,And the relevant apparent surface complexation constants are lgKM=2.2-3.3 in order of KCd≥KPb>KZn>KNi≥KCu,and lgβM=5.8-6.8 in oder of βNi>βZn>βCu.Therefore,the reactive ability of the ions onto mineral surface of quartz follows the order of Cd>Pb>Zn>Ni>Cu under the above-mentioned solution conditions.The apparent surface complexation constants,influenced by the surface potential,surface species and hydrolysis of metal ions,depend mainly on the Born solvation coefficeient of the metal ions.

  2. Inspection of Starch Acrylamide Copolymerization by Lodine Colorimetric Spectrophotometry%碘显色分光光度法检验淀粉-丙烯酰胺共聚反应

    Institute of Scientific and Technical Information of China (English)

    谢跃生; 洪艳艳; 梁承慧; 苏清

    2015-01-01

    In accordance with the general synthetic method ,the copolymerization of starch and ac‐rylamide may be triggered by ammonium peroxydisulfate or by ammonium ceric nitrate .The iodine starch test of reaction product indicates that very significant graft copolymerization did not happen . The polyacrylamide was not linked on the long chain of starch molecules .A large number of products are not the copolymer .They are a mixture of starch and polyacrylamide .It is not established that the mechanism for opening the starch sugar ring initiating the grafting copolymerization .%按照一般的合成方法,以过硫酸铵或硝酸铈铵为引发剂进行直链淀粉与丙烯酰胺的共聚反应。产物的碘显色分光光度法测试结果表明,丙烯酰胺并没有在淀粉分子的长链上发生非常显著的接枝共聚反应,产物大部分是由淀粉与丙烯酰胺均聚物所形成的共混物,淀粉开环的接枝机理不成立。

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

    Science.gov (United States)

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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

  7. The Experimental Study of Nuclear Astrophysics Reaction Rate of 93Zr(n,γ)94Zr

    Science.gov (United States)

    Gan, L.; Li, Z. H.; Su, J.; Yan, S. Q.; Guo, B.; Du, X. C.; Wu, Z. D.; Zeng, S.; Jin, S. J.; Wang, Y. B.; Bai, X. X.; Zhang, W. J.; Sun, H. B.; Li, E. T.

    The slow neutron capture (s-) process plays a very important role in the nucleosynthesis, which produces about half of the elements heavier than iron. 94Zr is mainly from 93Zr(n,γ)94Zr in the s-process, and the direct component of the 93Zr(n,γ)94Zr capture reaction can be derived from the neutron spectroscopic factor of 94Zr. As the existing neutron spectroscopic factors of 94Zr vary from each other up to 60%, a new work should be adopted to measure it exactly. In the present work, the angular distributions of 94Zr(13C,13C)94Zr, 94Zr(12C,12C)94Zr and 94Zr(12C,13C)93Zr were obtained using the highprecision Q3D magnetic spectrograph. In addition, distorted-wave Born approximation (DWBA) calculations of the transfer differential cross sections were performed. The calculated result displays a good agreement with the experiment data, and a value of 2.60±0.20 for the neutron spectroscopic factor of 94Zr was extracted, and the direct capture cross section versus neutron energy of 93Zr(n,γ)94Zr for the ground state of 94Zr was obtained too.

  8. Experimental study of the $^{66}$Ni$(d,p)^{67}$Ni one-neutron transfer reaction

    CERN Document Server

    Diriken, J.; Andreyev, A.N.; 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.

    2015-01-01

    The quasi-SU(3) sequence of the positive parity $νg_{9/2}, d_{5/2}, s_{1/2}$ 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 $^{68}$Ni (Z=28,N=40) through the $^{66}$Ni($d,p$)$^{67}$Ni 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 $\\gamma$-array and T-REX particle-detection setup was used and a delayed coincidence technique was employed to investigate the 13.3-$\\mu$s isomer at 1007 keV in $^{67}$Ni. Excited states up to an excitation energy of 5.8 MeV have been populated. Feeding of the $νg_{9/2}$ (1007 keV) and $νd_{5/2}$ (2207 keV and 3277 keV) positive-parity neutron states and negative parity ($νpf$) states have been observed at low excitation energy. The extracted relativ...

  9. Experimental Investigation of CFRP Confined Columns Damaged by Alkali Aggregate Reaction

    Directory of Open Access Journals (Sweden)

    Siti Radziah Abdullah

    2012-10-01

    Full Text Available Fiber reinforced polymer is the most effective repair material in use to enhance the strength and ductility of deteriorated reinforced concrete columns. Often, fiber reinforced polymer (FRP provides passive confinement to columns until the dilation and cracking of concrete occurs. In the case of concrete suspected of Alkali Aggregate Reaction (AAR where concrete undergoes expansion, FRP wrap provides active confinement to the expanded concrete. In this study, the performance of carbon fiber reinforced polymer (CFRP wrapped columns damaged by AAR is evaluated based on the number of FRP layers and the time of the polymer application which provides two types of confinement: active or passive. The columns were tested under axial compression to evaluate the residual strength of the columns in comparison with unwrapped columns. The results reveal that the strength of the wrapped columns is enhanced with an increase in the number of CFRP layers. The strength of the columns under passive confinement is higher than the columns under active confinement. Under active confinement, early CFRP wrapping leads to improvement in the strength of the columns.

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

    Science.gov (United States)

    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.

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

    Directory of Open Access Journals (Sweden)

    Agnes Afrodite S. Albuquerque

    Full Text Available ABSTRACT 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

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

    Science.gov (United States)

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

    2016-01-01

    To examine if methylene blue (MB) can counteract or prevent protamine (P) cardiovascular effects. 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. 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. Reviewing these experimental results and our clinical experience, we suggest methylene blue safely prevents and treats hemodynamic protamine complications, from the endothelium function point of view.

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

    Science.gov (United States)

    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.

  14. ON THE KINETICS AND MECHANISM OF THE COPOLYMERIZATION OF ACRYLONITRILE WITH STYRENE IN THE PRESENCE OF COPPER CHLORIDE

    Institute of Scientific and Technical Information of China (English)

    Hiroko Sato; Hiroshi Tsuji; Hitoshi Sasaki; Shinichi Ikemura; Yasuhito Gotoh; Junzo Ishikawa; Sei-ichi Nishimoto

    2003-01-01

    The copolymerization of styrene (St) and acrylonitrile (AN) complexed with CuCl2 monomer by a free radical mechanism was performed using benzoyl peroxide as an initiator at 65℃ under N2 atmosphere for 150 min. The rate of polymerization (Rp) was found to increase linearly with the concentration (in mol/L) of CuCl2, AN and St through scaling relations. The activation energy of the copolymerization process in the presence and absence of CuCl2 was found to be 46.5 kJ/mol and 102 kJ/mol, respectively. The viscosity average molecular weight of the copolymer and the kp2/kt ratio were determired to further assess the accelerating effect of CuCl2 on the copolymerization process. The copolymerization process in the presence of CuCl2 has a radical complex mechanism.

  15. Sequential elution of multiply and singly phosphorylated peptides with polar-copolymerized mixed-mode RP18/SCX material.

    Science.gov (United States)

    Li, Xiuling; Guo, Zhimou; Sheng, Qianying; Xue, Xingya; Liang, Xinmiao

    2012-06-21

    Novel polar-copolymerized mixed-mode RP18/SCX material was developed for feasible phosphopeptide enrichment, in which multiply and singly phosphorylated peptides could be sequentially eluted and separated with high selectivity.

  16. Design and Synthesis of 4,4'-Disubstituted-[2,2']-Bipyridines for Catalyzing CO/Styrene Copolymerization with Palladium(Ⅱ)

    Institute of Scientific and Technical Information of China (English)

    郭锦棠; 郁培云; 王海霞; 赵海洋

    2015-01-01

    A series of 4,4'-disubstituted-[2,2']-bipyridines, featuring electron withdrawing/donating functional groups such as amino, chloro, nitro, ethoxycarbonyl, carboxy, methyl, methoxy and hydroxymethyl, have been syn-thesized and employed in the copolymerization of carbon monoxide(CO)and styrene. The available bipyridine and its derivatives were coordinated with palladium(Ⅱ)acetate for catalyzing the copolymerization of CO and styrene, and the concomitant polyketone was characterized by means of 13C NMR, FTIR, differential scanning calo-rimetry(DSC)and element analysis techniques concerning its structure and thermal performance. The effect of dif-ferent electron-donating and electron-withdrawing groups on catalyst performance and molecular weight of co-polymer was studied under certain experimental condition. It has been proved that the enhancement of electron donating and conjugative effects on bipyridine ligand will not only improve the catalytic activity of the composi-tion, but also increase the molecular weight of the as-prepared polyketone. The catalytic activity is the highest in hydroxymethyl substituted 2,2'-bipyridine ligand(1 356 gSTCO/(gPd · h)), when the molecular weight and polydispersity index of the polyketone are Mn=8 502,Mw=1 3440 and Mw/Mn=1.581, respectively.

  17. Infrared thermoimages display of body surface temperature reaction in experimental cholecystitis

    Institute of Scientific and Technical Information of China (English)

    Dong Zhang; Yuan-Gen Zhu; Shu-You Wang; Hui-Min Ma; Yan-Yan Ye; Wei-Xing Fu; Wei-Guo Hu

    2002-01-01

    AIM: To display the thermoirnages of the body surface inexperimental cholecystitis, to observe the body surfacetemperature reaction in visceral disorders, and to study if the theory of body surface-viscera correlation is true and the mechanism of temperature changes along the meridians. METHODS: By injecting bacteria ssuspension into the stricturebile duct and gallbladder, 21 rabbits were prepared as acutepyogenic cholangiocholecystitis models, with another 8rabbits prepared by the same process except withoutinjection of bacteria suspension as control. The body surfaceinfrared thermoimages were continuously observed on thehair shaven rabbit skin with AGA-782 thermovision 24 hbefore, 1-11 d after and (2,3 wk) 4 wk after the operation witha total of over 10 records of thermoimages.RESULTS: Twelve cases out of 21 rabbits with cholecystitisrevealed bi-lsteral longitudinal high temperature lines in itstrunk; with negative findings in the control group. The high-temperature line appeared on d l-d2, first in the right trunk,after the preparation of the model, about 7 d after the modelpreparation, the lines appeared at the left side too,persisting for 4 wk. The hyper-temperature line revealed 1.1-2.7 ℃ higher than before the model preparation, 0.7-2.5 ℃higher than the surrounding skin. The length of the hightemperature line might reach a half length of the body trunk,or as long as the whole body itself.CONCLUSION: The appearance of the longitudinal hightemperature lines st the lateral aspects of the trunk in theexperimental group is directly bound up with theexperimental animals pyogenic cholecystitis, with itsrunning course quite similar to that of the GallbladderChannel of Foot Shaoyang, but different to the zones ofhyperalgesia and site of referred pain in cholecystitis.

  18. Electric Field-Enhanced Catalytic Conversion of Methane: AN Experimental Study on the Effects of Corona Discharge on Methane Reactions

    Science.gov (United States)

    Marafee, Abdulathim M. J.

    The oxidative coupling of methane (OCM) is currently being actively studied for the production of higher hydrocarbons from natural gas. The present study concentrates on the oxidative conversion of methane in a high-pressure (one atmosphere), nonthermal plasma formed by corona discharge. Here, methyl radicals are formed by the reaction of methane with negatively-charged oxygen species created in the corona discharge. The results of methane conversion in the presence of both AC and DC corona discharges revealed that ethane and ethylene product selectivity is affected by electrode polarity, frequency, and oxygen partial pressure in the feed. Higher C_2 yields were obtained with the AC corona. All of the AC corona discharges specified here were initiated at room temperature (i.e., no oven or other heat source used), with temperature increases from 300 to 500^circC due to the exothermic gas discharge and exothermic reaction. A reaction mechanism is presented to explain the observed phenomena. The results suggest that AC and/or DC gas discharge techniques should be further studied for improved economics of methane conversion. The oxidative dehydrogenation of ethane in DC corona discharges was investigated. The atomic oxygen radicals initiated by corona discharges are thought to be active for the OXD of ethane. The selectivity to ethylene is affected by the reaction temperature, the DC applied voltage, voltage polarity, and the C_2H _6/O_2 ratio. The results of this study suggest the corona discharge process to be very efficient and selective in the oxidative dehydrogenation of ethane. The effects of DC corona discharge were examined in the presence of a typical OCM catalyst, Sr/La _2O_3. Experimental investigations have correspondingly been conducted, in which all reactive gases passed through a catalyst bed situated within the corona-induced plasma zone. The methane conversion and C_2 yield increased (with O_2 partial pressure) during the corona-enhanced catalytic

  19. Monomer reactivity ratios for fluoroacrylate and butyl methacrylate in miniemulsion copolymerizations initiated by potassium persulphate

    Institute of Scientific and Technical Information of China (English)

    Qing Hua Zhang; Zhen Huan Luo; Xiao Li Zhan; Feng Qiu Chen

    2009-01-01

    Miniemulsion copolymerization of butyl mathacrylate(BMA)with fluoroacrylate(HFMA,TFMA)was carded out at 70℃ by employing potassium persulphate(KPS)as initiator.Copolymer compositions at low conversion levels were determined by 1H NMR spectra techniques.The reactivity ratios were evaluated by employing Kellen-Tudos(K-T)methods,which yields the apparent reactivity ratios,rBMA=0.74,rHFMA=0.87 and rBMA=0.73,rTFMA=0.75,respectively,and Q-and e-values of HFMA and TFMA were calculated by the Alfrey-Price method.The results show that HFMA and TFMA are more active than BMA,and the cross-propagation rate constant is greater than the self-propagation one in these two copolymerizations.

  20. ELECTROCHEMICAL COPOLYMERIZATION OF DIBENZOFURAN AND 3-METHYLTHIOPHENE IN BORON TRIFLUORIDE DIETHYL ETHERATE

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    The copolymerization of dibenzofuran(DBF)and 3-methylthiophene(MET)was successfully achieved electrochemically by direct anodic oxidation of the monomer mixtures in boron trifluoride dietbyl etherate.The effects of applied polymerization potential and the monomer concentration ratios on the copolymerization were investigated by linear sweep voltammetry and cyclic voltammetry(CV).The structure of copolymer films were investigated by UV-Vis,infrared spectroscopy,thermal analysis.As-formed novel copolymers own both the advantages of poly(3-methylthiophene)and poly(dibenzofuran),that is,good redox activity,good thermal stability.Fluorescence spectra suggested that emission spectrum of copolymer films was blue-shifted in contrast to that of PDBF film.

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

    Science.gov (United States)

    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.

  2. Zirconium oxocluster/polymer hybrid nanoparticles prepared by photoactivated miniemulsion copolymerization

    Science.gov (United States)

    Benedetti, Cesare; Flouda, Paraskevi; Antonello, Alice; Rosenauer, Christine; Pérez-Pla, Francisco F.; Landfester, Katharina; Gross, Silvia; Muñoz-Espí, Rafael

    2017-09-01

    The photoactivated free radical miniemulsion copolymerization of methyl methacrylate (MMA) and the zirconium oxocluster Zr4O2(methacrylate)12 is used as an effective and fast preparation method for polymer/inorganic hybrid nanoparticles. The oxoclusters, covalently anchored to the polymer network, act as metal-organic cross-linkers, thus improving the thermomechanical properties of the resulting hybrid nanoparticles. Benzoin carbonyl organic compounds were used as photoinitiators. The obtained materials are compared in terms of cross-linking, effectiveness of cluster incorporation, and size distribution with the analogous nanoparticles produced by using conventional thermally induced free radical miniemulsion copolymerization. The kinetics of the polymerization process in the absence and in the presence of the oxocluster is also investigated.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  4. Selective Release of anti–TB Drugs Complex from Smart Copolymeric Bioactive nano–carriers

    Directory of Open Access Journals (Sweden)

    Alejandro Arredondo–Peñaranda

    2014-07-01

    Full Text Available Smart nano–copolymeric matrices have been employed to load and release anti tuberculosis (anti – TB drugs combinated complexes of Ethambutol (EMB, Isoniazid (INH, Rifampicin (RMP and Pyrazinamide (PZA. Copolymeric nanocarriers were synthesized using a microemulsion polymerization method previously reported. These nanocarriers can show selective swelling–collapse response under changes in local environments such a temperature, pH, solvent composition and electrical stimuli. The employ of these kinds of systems permits a controlled and selective delivery and release on specific human tissues. High Performance Liquid Chromatography technique was used to allow the detection of combinated mixtures of different active principles of anti–TB drugs using an acetonitrile mobile phase at 0.5 mL/min of flow rate whit a Spherisorb ODS2, C18 column. The results obtained suggest that the employ of smart nanohydrogels is a novel method in several tuberculosis therapies.

  5. Highly Active Copolymerization of Ethylene and N-Acetyl-O-(ω-Alkenyl-l-Tyrosine Ethyl Esters Catalyzed by Titanium Complex

    Directory of Open Access Journals (Sweden)

    Jing Wang

    2016-03-01

    Full Text Available A series of N-acetyl-O-(ω-alkenyl-l-tyrosine ethyl esters were synthesized by the reaction of vinyl bromides (4-bromo-1-butene, 6-bromo-1-hexene, 8-bromo-1-octene and 10-bromo-1-decene with N-acetyl-l-tyrosine ethyl ester. 1H NMR, elemental analysis, FT-IR, and mass spectra were performed for these N-acetyl-O-(ω-alkenyl-l-tyrosine ethyl esters. The novel titanium complex can catalyze the copolymerization of ethylene and N-acetyl-O-(ω-alkenyl-l-tyrosine ethyl esters efficiently and the highest catalytic activity was up to 6.86 × 104 gP·(molTi−1·h−1. The structures and properties of the obtained copolymers were characterized by FT-IR, (1H13C NMR, GPC, DSC, and water contact angle. The results indicated that the obtained copolymers had a uniformly high average molecular weight of 2.85 × 105 g·mol−1 and a high incorporation ratio of N-acetyl-O-(but-3-enyl-l-tyrosine ethyl ester of 2.65 mol % within the copolymer chain. The units of the comonomer were isolated within the copolymer chains. The insertion of the polar comonomer into a copolymer chain can effectively improve the hydrophilicity of a copolymer.

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

    Science.gov (United States)

    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.%.

  7. Copolymerization preparation of cationic cyclodextrin chiral stationary phases for drug enantioseparation in chromatography

    OpenAIRE

    sprotocols

    2015-01-01

    Authors: Ren-Qi Wang, Teng-Teng Ong, Ke Huang, Weihua Tang & Siu-Choon Ng ### Abstract We described a facile and effective protocol wherein radical copolymerization is employed to covalently bond cationic β-cyclodextrin (β-CD) onto silica particles with extended linkage, resulting in a chiral stationary phase (IMPCSP) that can be used for the enantioseparation of racemic drugs in both high-performance liquid chromatography (HPLC) and supercritical fluid chromatography (SFC). Start...

  8. Gelation in free-radical crosslinking copolymerization; fast transient fluorescence study

    OpenAIRE

    Ö. Pekcan; D. Kaya

    2002-01-01

    The fast transient fluorescence (FTRF) technique was used to study the sol-gel phase transition in free-radical crosslinking copolymerization (FCC) in two different monomeric systems. Pyrene (Py) was used as a fluorescence probe for the in situ polymerization experiments. The fluorescence lifetimes of Py from its decay traces were measured and used to monitor the gelation process. Monomer consumption profiles were determined during gelation process using Stern-Volmer model. Gelations...

  9. Calculation of Average Molecular Properties During Nonlinear, Living Copolymerization. Revision

    Science.gov (United States)

    1990-06-25

    considerable interest in making star molecules23 and controlled microgel particles24 via anionic polymerization of divinyl monomers. 19,23-26 These...predicted by eq. 66 with r3 adjusted to give their experimental gel point (see Figure 2). This may also be due to extensive cyclization or perhaps microgel

  10. Hydrogen-atom transfer reactions from ortho-alkoxy-substituted phenols: an experimental approach.

    Science.gov (United States)

    Amorati, Riccardo; Menichetti, Stefano; Mileo, Elisabetta; Pedulli, Gian Franco; Viglianisi, Caterina

    2009-01-01

    The role of intramolecular hydrogen bonding (HB) on the bond-dissociation enthalpy (BDE) of the phenolic O-H and on the kinetics of H-atom transfer to peroxyl radicals (k(inh)) of several 2-alkoxyphenols was experimentally quantified by the EPR equilibration technique and by inhibited autoxidation studies. These compounds can be regarded as useful models for studying the H-atom abstraction from 2-OR phenols, such as many lignans, reduced coenzyme Q and curcumin. The effects of the various substituents on the BDE(O-H) of 2-methoxy, 2-methoxy-4-methyl, 2,4-dimethoxyphenols versus phenol were measured in benzene solution as -1.8; -3.7; -5.4 kcal mol(-1), respectively. In the case of polymethoxyphenols, significant deviations from the BDE(O-H) values predicted by the additive effects of the substituents were found. The logarithms of the k(inh) constants in cumene were inversely related to the BDE(O-H) values, obeying a linear Evans-Polanyi plot with the same slope of other substituted phenols and a y-axis intercept slightly smaller than that of 2,6-dimethyl phenols. In the cases of phenols having the 2-OR substituent included in a five-membered condensed ring (i.e, compounds 9-11), both conformational isomers in which the OH group points toward or away from the oxygen in position 2 were detected by FTIR spectroscopy and the intramolecular HB strength was thus estimated. The contribution to the BDE(O-H) of the ortho-OR substituent in 9, corrected for intramolecular HB formation, was calculated as -5.6 kcal mol(-1). The similar behaviour of cyclic and non-cyclic ortho-alkoxy derivatives clearly showed that the preferred conformation of the OMe group in ortho-methoxyphenoxyl radicals is that in which the methyl group points away from the phenoxyl oxygen, in contrast to the geometries predicted by DFT calculations.

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

    CERN Document Server

    Johansen, J G; Borge, M J G; Cubero, M; Diriken, J; Elsevier, 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

    2013-01-01

    The bound states of $^{12}$Be have been studied through a $^{11}$Be$(d,p)^{12}$Be transfer reaction experiment in inverse kinematics. A 2.8 MeV/u beam of $^{11}$Be 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 $^{12}$Be. The $\\gamma$-ray detection enabled a clear identification of the four known bound states in $^{12}$Be, 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 DWBA calculations and have been compared to previous experimental and theoretical results.

  12. Acid and base catalyzed Davis-Beirut reaction: experimental and theoretical mechanistic studies and synthesis of novel 3-amino-2H-indazoles.

    Science.gov (United States)

    Avila, Belem; El-Dakdouki, Mohammad H; Nazer, Musa Z; Harrison, Jason G; Tantillo, Dean J; Haddadin, Makhluf J; Kurth, Mark J

    2012-11-28

    The Davis-Beirut reaction, which provides an efficient synthesis of 2H-indazoles and, subsequently, indazolones, is shown to proceed rapidly from o-nitrosobenzaldehyde and primary amines under both acid or base catalysis. Experimental and theoretical evidence in support of a reaction mechanism is provided in which o-nitrosobenzylidine imine is a pivotal intermediate in this N,N-bond forming heterocyclization reaction. The Davis-Beirut reaction is also shown to effectively synthesize a number of novel 3-amino-2H-indazole derivatives.

  13. A new advanced experimental setup for in-depth study of the interfacial reaction during reactive wetting

    Science.gov (United States)

    Frenznick, Sascha; Stratmann, Martin; Rohwerder, Michael

    2008-04-01

    Reactive wetting plays a crucial role in many technical processes, from soldering in microelectronics, production of metal/ceramic composites, to hot dip galvanizing in mass production of zinc coated steel sheet. In all these cases the wetting behavior of metal melts on different surfaces plays a crucial role in material joining and coating. In all these processes the formation of the interfacial reaction layer has to occur within as short a time as possible in order to ensure a fast overall production speed. As the interfacial layer determines the stability of the formed composites, detailed knowledge of its growth mechanisms is required for a directed process optimization. However, the investigation of the processes occurring at the buried interface between substrate and wetting phase is difficult, especially for the case of liquid metal wetting metallic or ceramic solid substrates at high temperatures. Here, a novel advanced technique for the investigation of high temperature wetting processes up to a temperature of 1100K is presented. It is based on the sessile drop technique but, in addition, allows spinning off the droplet at any chosen wetting time, thus providing direct access to the interfacial reaction layer. Since the experimental setup is integrated into a UHV compatible reaction chamber, not only excellent control of the composition of the atmosphere is ensured, but also direct transfer to surface analytical tools such as scanning electron microscope or electron spectroscopy for chemical analysis without intermediate exposure to air is realized. As will be shown for the case of hot dip galvanising of steel, this is an outstanding advance compared to existing methods.

  14. 丙烯酰胺/丙烯酸/甲基丙烯酸甲酯双水相共聚过程的成滴机理%Droplet formation mechanism of acrylamide/acrylic acid/methyl methacrylate aqueous two-phase copolymerization

    Institute of Scientific and Technical Information of China (English)

    蔡晓生; 单国荣

    2012-01-01

    Acrylamide (AM)/acrylic acid (AA )/methyl methacrylate (MMA) copolymer with the stabilizer poly (acrylic acid sodium) (PAANa) dispersed in the ammonium sulfate (AS) solution was prepared through aqueous two-phase copolymerization. By using dynamic light scattering (DLS), the droplet appearance and growth in the initial stage of the aqueous two-phase copolymerization was on-line detected, and the results showed that the copolymer droplet aggregated with each other at the initial stage. Therefore, the droplet size distribution became wide at first, and then turned to narrow again as the copolymerization proceeded. By using gas chromatography, the exact monomer residues were detected and the composition of the copolymer chain was calculated. The reaction could be divided into three stages. The AM and MMA segments were the main part of the copolymer chain at the first stage, at the second stage AM grew mainly into the copolymer chain, and the A A and AM segments were the main part of the copolymer chain at the third stage. Eventually, the droplet formation mechanism of the aqueous two-phase copolymerization of AM/AA/MMA with the stabilizer PAANa in AS aqueous solution was presented. The negative charge of the AA segment in the copolymer chain was considered as a significant factor in the stabilization of the aqueous two-phase system.

  15. Using Central Composite Experimental Design to Optimize the Degradation of Tylosin from Aqueous Solution by Photo-Fenton Reaction

    Directory of Open Access Journals (Sweden)

    Abd Elaziz Sarrai

    2016-05-01

    Full Text Available The feasibility of the application of the Photo-Fenton process in the treatment of aqueous solution contaminated by Tylosin antibiotic was evaluated. The Response Surface Methodology (RSM based on Central Composite Design (CCD was used to evaluate and optimize the effect of hydrogen peroxide, ferrous ion concentration and initial pH as independent variables on the total organic carbon (TOC removal as the response function. The interaction effects and optimal parameters were obtained by using MODDE software. The significance of the independent variables and their interactions was tested by means of analysis of variance (ANOVA with a 95% confidence level. Results show that the concentration of the ferrous ion and pH were the main parameters affecting TOC removal, while peroxide concentration had a slight effect on the reaction. The optimum operating conditions to achieve maximum TOC removal were determined. The model prediction for maximum TOC removal was compared to the experimental result at optimal operating conditions. A good agreement between the model prediction and experimental results confirms the soundness of the developed model.

  16. A comparison between experimental results and a mathematical model of the oxidation reactions induced by radiation of ferrous ions

    Energy Technology Data Exchange (ETDEWEB)

    Sanchez-Mejorada, G. [Departamento de Anatomia, Facultad de Medicina, Universidad Nacional Autonoma de Mexico, Ciudad Universitaria, Mexico 04510 D.F. (Mexico)], E-mail: millang@servidor.unam.mx; Frias, D. [Departamento de Ciencias Exatas e Tecnologicas, Universidad Estadual de Santa Cruz, Bahia (Brazil); Negron-Mendoza, A.; Ramos-Bernal, S. [Instituto de Ciencias Nucleares, Universidad Nacional Autonoma de Mexico, Ciudad Universitaria, Mexico 04510 D.F. (Mexico)

    2008-02-15

    The dependence of the response of chemical dosimeters as a function of the irradiation temperature is an important issue that has not yet been addressed within a mathematical modeling framework. The temperature dependence of the dose-response function has to be taken into account in practical applications, mainly in frozen food sterilization by radiation. Significant errors may occur if the dependence of the dosimeter response on the irradiation temperature is not taken into account properly. The experimental results obtained irradiating iron salt solutions at different temperatures below and above 0 deg. C show that the change in the valence of Fe{sup 2+} as a function of dose are linear for both liquid and frozen solutions. This led us to conclude that the iron salt solution seems suitable for low-temperature applications having a linear dose-response up to 600 Gy, despite a progressive decrease of sensitivity as temperature decreases. A nonlinear differential model for the kinetics of reactions induced by radiation in iron salt solutions was established. In the model a temperature correction factor was included in order to take into account abrupt changes observed in the kinetics of the chemical process when the irradiated solution's allotropic phase changes from liquid to solid (ice). Fitting the kinetic model to the experimental results at different temperatures we found the temperature correction factors.

  17. Enhanced Interfacial Adhesion in HDPE/HA Composites by Surface Modification of HA Particles via in situ Polymerization and Copolymerization

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    Hydroxyapatite ( HA )-reinforced high density polyethylene (HDPE) was developed as a bone replacement material. In order to enhance the interfacial bondiag between HA and polyethylene and improve the mechanical properties of HDPE/ HA composites, the surface of the micron-sized HA particles was modified by in situ polymerization of butyl acrylate ( BA ) and in situ copolynerization of vinyl triethoxyl silane (VTES) and BA ,then the modified HA particles were compounded with HDPE. The effects of the surface modification of HA on morphology and mechanical properties of HDPE/ HA composites were investigated. The experimental results show that the presence of HA particles does not inhibit the polymerization of BA . The poly( butyl acrylate) ( PBA ) segments on the HA surface enhance the compatibility between HA and HDPE, improve the dispersion of HA particles in HDPE matrix, and enhance the interfacial ndhesion between HA and matrix. Surface modifications, especially by in situ copolymerization of VTES and BA , significantly increase notch impact strengths and marginal stiffness and tensile strengths of HDPE/ HA composites. And it is found that there is a critical thickness of PBA coating on HA particles for optimum mechanical properties of HDPE / HA composites.

  18. Coupled transport, mixing and biogeochemical reactions in fractured media: experimental observations and modelling at the Ploemeur fractured rock observatory

    Science.gov (United States)

    Le Borgne, T.; Bochet, O.; Klepikova, M.; Kang, P. K.; Shakas, A.; Aquilina, L.; Dufresne, A.; Linde, N.; Dentz, M.; Bour, O.

    2016-12-01

    Transport processes in fractured media and associated reactions are governed by multiscale heterogeneity ranging from fracture wall roughness at small scale to broadly distributed fracture lengths at network scale. This strong disorder induces a variety of emerging phenomena, including flow channeling, anomalous transport and heat transfer, enhanced mixing and reactive hotspot development. These processes are generally difficult to isolate and monitor in the field because of the high degree of complexity and coupling between them. We report in situ experimental observations from the Ploemeur fractured rock observatory (http://hplus.ore.fr/en/ploemeur) that provide new insights on the dynamics of transport and reaction processes in fractured media. These include dipole and push pull tracer tests that allow understanding and modelling anomalous transport processes characterized by heavy-tailed residence time distributions (Kang et al. 2015), thermal push pull tests that show the existence of highly channeled flow with a strong control on fracture matrix exchanges (Klepikova et al. 2016) and time lapse hydrogeophysical monitoring of saline tracer tests that allow quantifying the distribution of transport length scales governing dispersion processes (Shakas et al. 2016). These transport processes are then shown to induce rapid oxygen delivery and mixing at depth leading to massive biofilm development (Bochet et al., in prep.). Hence, this presentation will attempt to link these observations made at different scales to quantify and model the coupling between flow channeling, non-Fickian transport, mixing and chemical reactions in fractured media. References: Bochet et al. Biofilm blooms driven by enhanced mixing in fractured rock, in prep. Klepikova et al. 2016, Heat as a tracer for understanding transport processes in fractured media: theory and field assessment from multi-scale thermal push-pull tracer tests, Water Resour. Res. 52Shakas et al. 2016, Hydrogeophysical

  19. 4'-CyanoPLP presents better prospect for the experimental detection of elusive cyclic intermediate radical in the reaction of lysine 5,6-aminomutase.

    Science.gov (United States)

    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.

  20. Graft copolymerization of acrylic acid and acrylamide onto chlorinated polyethylene using the suspension grafting technique%氯化聚乙烯接枝水溶性单体

    Institute of Scientific and Technical Information of China (English)

    冯东东; 何培新

    2001-01-01

    采用溶胀悬浮接枝共聚法,将水溶性单体丙烯酸(AA)、丙烯酰胺(AM)接枝到疏水性氯化聚乙烯(CPE)大分子链上,合成双亲性接枝共聚物.通过正交实验法探讨了反应条件(膨胀剂、单体、引发剂和分散剂用量以及反应时间、反应温度和分散介质用量)对接枝率及接枝效率的影响规律,并用傅立叶红外光谱对接枝物进行了表征.研究结果表明,采用水作分散介质,乙酸乙酯作膨胀剂的溶胀悬浮接枝体系,在回流温度和一定搅拌速度下,可实现CPE接枝水溶性单体AA、AM且接枝(效)率较高.最佳反应条件分别为:CPE-g-AA接枝体系:CPE/AA/BPO/EA/H2O=2/2/0.06/5/50(g/g/g/mL/mL),反应温度80℃;CPE-g-AM接枝体系:CPE/AM/BPO/EA/H2O=2/2/0.07/8/50(g/g/g/mL/mL),反应温度72℃.反应时间均为3h.%Graft copolymerization of acrylic acid(AA) and acrylic amide(AM)onto chlorinated polyethylene(CPE) by the oil-swellable suspension graft copolymerization technique was studied, benzoyl peroxide (BPO) was used as the free radical initiator and ethyl acetate (EA) as the sweller. Optimum reaction conditions to obtain maximum grafting were evaluated. The variable factors were temperature, initiator amount, volume of sweller, monomer amount, etc. The graft copolymer was characterized by infrared spectroscopy (IR). The results showed that the oil-swellable suspension graft copolymerization technique, in which EA as sweller, can improve the degree of grafting.

  1. 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.

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Cong [Argonne National Lab. (ANL), Argonne, IL (United States); Evans, Tabitha J. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Cheng, Lei [Argonne National Lab. (ANL), Argonne, IL (United States); Nimlos, Mark R. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Mukarakate, Calvin [National Renewable Energy Lab. (NREL), Golden, CO (United States); Robichaud, David J. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Assary, Rajeev S. [Argonne National Lab. (ANL), Argonne, IL (United States); Curtiss, Larry A. [Argonne National Lab. (ANL), Argonne, IL (United States)

    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.

  3. 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.

    Science.gov (United States)

    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.

  4. Specific detection of Neospora caninum oocysts in fecal samples from experimentally-infected dogs using the polymerase chain reaction.

    Science.gov (United States)

    Hill, D E; Liddell, S; Jenkins, M C; Dubey, J P

    2001-04-01

    Neospora caninum oocysts, passed in the feces of a definitive host (dog), were isolated, and genomic DNA was extracted. A polymerase cahin reaction (PCR) targeting the N. caninum-specific Nc 5 genomic sequence was performed using the isolated DNA. A synthesized competitor molecule containing part of the Nc 5 sequence was included in the assay as a check against false-negative PCR results and to quantify N. caninum oocyst DNA in fecal samples. A standard curve of the ratio of fluorescence intensity of PCR-amplified competitor to that of oocyst DNA was constructed to compare oocyst equivalents from fecal samples containing unknown numbers of N. caninum oocysts and to assess the sensitivity of the assay. The specificity of the assay was determined using the Nc 5-specific primers in PCR assays against other parasites likely to be found in canine feces. Genomic DNA sequences from the canine coccidians Hammondia heydorni, Cryptosporidium parvum, Sarcocystis cruzi, S. tenella, and Isospora ohioensis and the canine helminth parasites Strongyloides stercoralis, Toxocara canis, Dipylidium caninum, and Ancylostoma caninum were not amplified. In addition, genomic DNA sequences from oocysts of coccidian parasites that might contaminate dog feces, such as Hammondia hammondi, Toxoplasma gondii, or Eimeria tenella, were not amplified in the PCR assay. The assay should be useful in epidemiological surveys of both domestic and wild canine hosts and in investigations of oocyst biology in experimental infections.

  5. An experimental protocol for the establishment of dogs with long-term cellular immune reactions to Leishmania antigens

    Directory of Open Access Journals (Sweden)

    Márcia Cristina Aquino Teixeira

    2011-03-01

    Full Text Available Domestic dogs are considered to be the main reservoirs of zoonotic visceral leishmaniasis. In this work, we evaluated a protocol to induce Leishmania infantum/Leishmania chagasi-specific cellular and humoral immune responses in dogs, which consisted of two injections of Leishmania promastigote lysate followed by a subcutaneous inoculation of viable promastigotes. The primary objective was to establish a canine experimental model to provide positive controls for testing immune responses to Leishmania in laboratory conditions. After inoculation of viable promastigotes, specific proliferative responses of peripheral blood mononuclear cells (PBMCs to either Leishmania lysate or recombinant proteins, the in vitro production of interferon-γ by antigen-stimulated PBMCs and a significant increase in circulating levels of anti-Leishmania antibodies were observed. The immunized dogs also displayed positive delayed-type hypersensitivity reactions to Leishmania crude antigens and to purified recombinant proteins. An important finding that supports the suitability of the dogs as positive controls is that they remained healthy for the entire observation period, i.e., more than seven years after infection. Following the Leishmania antigen lysate injections, the infection of dogs by the subcutaneous route appears to induce a sustained cellular immune response, leading to an asymptomatic infection. This provides a useful model for both the selection of immunogenic Leishmania antigens and for immunobiological studies on their possible immunoprotective activities.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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. An experimental investigation of multiple sulfur isotope fractionations during heterogenous reactions between SO2 and activated carbon

    Science.gov (United States)

    Hamasaki, H.; Watanabe, Y.; Ohmoto, H.

    2010-12-01

    . We have recognized that the δ34S of SO2 in the system continuously decreased during the experiments from -0.6 to -1.4‰ (relative to the initial value) at 200 °C, and from -1.0 to -1.2 ‰ at 250 °C. The Δ33S of SO2 continued to decrease from 0 to -0.18 ‰ at 200 °C and 0.03 to -0.05 ‰ at 250 °C. Mass balance calculations suggest that the bulk S in activated carbon increased its δ34S value from 1.4 to 12.1 ‰ at 200 °C and 3.2 to 16.7 ‰ at 250 °C; and increased the Δ33S value from 0 to 0.18 ‰ at 200 °C and from 0.07 to 0.32 ‰ at 250 °C. Results of the sequential S extraction from the solid run products (activated C) indicate the total S content of 0.9 wt%, mostly in the forms of Cr-reductive S compounds (e.g., sulfites and polysulfides) and non Cr-reductive S compounds (e.g., organic sulfur, elemental sulfur, and sulfates). Our experimental results indicate that the adsorption of SO2, the reduction of S4+ to S0 (and/or Sx2-), and the oxidation of C0 to C4+ continued to occur during the reaction between SO2 and activated carbon at 200 °C and 250 °C, and that the redox reactions produced larger sulfur isotope effects (both in δ34S and Δ33S) compared to a simple adsorption process under our experimental conditions.

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

    Energy Technology Data Exchange (ETDEWEB)

    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

  10. Control of Grafting Density and Distribution in Graft Polymers by Living Ring-Opening Metathesis Copolymerization.

    Science.gov (United States)

    Lin, Tzu-Pin; Chang, Alice B; Chen, Hsiang-Yun; Liberman-Martin, Allegra L; Bates, Christopher M; Voegtle, Matthew J; Bauer, Christina A; Grubbs, Robert H

    2017-03-15

    Control over polymer sequence and architecture is crucial to both understanding structure-property relationships and designing functional materials. In pursuit of these goals, we developed a new synthetic approach that enables facile manipulation of the density and distribution of grafts in polymers via living ring-opening metathesis polymerization (ROMP). Discrete endo,exo-norbornenyl dialkylesters (dimethyl DME, diethyl DEE, di-n-butyl DBE) were strategically designed to copolymerize with a norbornene-functionalized polystyrene (PS), polylactide (PLA), or polydimethylsiloxane (PDMS) macromonomer mediated by the third-generation metathesis catalyst (G3). The small-molecule diesters act as diluents that increase the average distance between grafted side chains, generating polymers with variable grafting density. The grafting density (number of side chains/number of norbornene backbone repeats) could be straightforwardly controlled by the macromonomer/diluent feed ratio. To gain insight into the copolymer sequence and architecture, self-propagation and cross-propagation rate constants were determined according to a terminal copolymerization model. These kinetic analyses suggest that copolymerizing a macromonomer/diluent pair with evenly matched self-propagation rate constants favors randomly distributed side chains. As the disparity between macromonomer and diluent homopolymerization rates increases, the reactivity ratios depart from unity, leading to an increase in gradient tendency. To demonstrate the effectiveness of our method, an array of monodisperse polymers (PLA(x)-ran-DME(1-x))n bearing variable grafting densities (x = 1.0, 0.75, 0.5, 0.25) and total backbone degrees of polymerization (n = 167, 133, 100, 67, 33) were synthesized. The approach disclosed in this work therefore constitutes a powerful strategy for the synthesis of polymers spanning the linear-to-bottlebrush regimes with controlled grafting density and side chain distribution, molecular

  11. Reduced chemical reaction mechanisms: experimental and HCCI modelling investigations of autoignition processes of iso-octane in internal combustion engines

    OpenAIRE

    Machrafi, Hatim; Lombaert, K.; Cavadias, S; Guibert, P.; Amouroux, J

    2005-01-01

    A semi-reduced (70 species, 210 reactions) and a skeletal (27 species, 29 reactions) chemical reaction mechanism for iso-octane are constructed from a semi-detailed iso-octane mechanism (84 species, 412 reactions) of the Chalmers University of Technology in Sweden. The construction of the reduced mechanisms is performed by using reduction methods such as the quasi-steady-state assumption and the partial equilibrium assumption. The obtained reduced iso-octane mechanisms show, at the mentioned ...

  12. Hydration of swelling clay and bacteria interaction. An experimental in situ reaction study; Hydratation des argiles gonflantes et influence des bacteries. Etude experimentale de reaction in situ

    Energy Technology Data Exchange (ETDEWEB)

    Berger, J

    2008-01-15

    This study reports on the physical-chemical behaviour of swelling di-octahedral clays (smectites) and their interaction with aqueous solutions and bacteria (Shewanella putrefaciens). Experimental results are presented for compacted clays, hydrated under confined volume conditions, using a new type of reaction-cell (the 'wet-cell' of Warr and Hoffman, 2004) that was designed for in situ X-ray diffraction (XRD) measurement. For comparison, dispersed clay systems were studied using standard batch solutions subjected to varying degrees of agitation. The combination of time-dependent in situ XRD measurements with gravimetric measurements and calculated diffraction patterns using the CALCMIX software (Plancon and Drits, 1999) allowed to successful quantification of the dynamics of water uptake and storage. This analytical procedure combined with published water vapour adsorption data enabled determination of the abundance of structured water layers, developed in the interlayer space, and the amount of water contained in different storage sites (interlayers, surfaces and pore spaces). Qualitative information on surface area and textural organization was also estimated based on calculated changes in the average particle thickness and the organization of water layer structures (ordering). Abiotic smectite hydration experiments, using a range of natural and industrial bentonites (SWy-2, IBECO, MX80, TIXOTON), focused on defining the role of the interlayer cation, variable clay packing densities and the ionic strength of the infiltrating solution. The rate of smectite hydration, as expected, was seen to be highly dependent on the type of interlayer cation (enhanced for Ca as opposed to Na) and the ionic strength of solution (enhanced uptake rates with saline solutions, particularly as they infiltrate Na-smectite). A range of dynamic changes in micro textural state occurred as a function of packing density. These changes explain the differences in hydration behaviour

  13. Homo- and Copolymerization of Ethylene and Norbornene with Anilido–Imine Chromium Catalysts

    Directory of Open Access Journals (Sweden)

    Lixia Pei

    2016-03-01

    Full Text Available A series of anilido–imine chromium complexes have been used as precursors to catalyze homo- and copolymerization of ethylene and norbornene. The chromium complexes activated with methylalumoxane (MAO exhibit good activities for homopolymerization of ethylene (E to produce linear polyethylene and moderate activities for norbornene (N polymerization to afford vinyl-type polynorbornene. Ethylene–norbornene copolymers with high incorporation of norbornene can be also produced by these catalysts. 13C NMR and differential scanning calorimetry (DSC analyses show that the copolymers are random products, and –NNN– and –EEE– units can be observed in the microstructure of the copolymers.

  14. Experimental testing of skin reactions to insulin detemir in diabetes patients naïve to insulin detemir

    DEFF Research Database (Denmark)

    O'goshi, Kenichiro; Serup, Jørgen; Blaaholm, Bente

    2011-01-01

    a consistent pattern of inflammation with eosinophilia as typically observed in adverse skin reactions to a variety of medicines. Reactions were interpreted as non-specific biologic responses to the insulin different from direct toxic actions and classical allergic reaction patterns. Only one person registered...

  15. Hydration of swelling clay and bacteria interaction. An experimental in situ reaction study; Hydratation des argiles gonflantes et influence des bacteries. Etude experimentale de reaction in situ

    Energy Technology Data Exchange (ETDEWEB)

    Berger, J

    2008-01-15

    This study reports on the physical-chemical behaviour of swelling di-octahedral clays (smectites) and their interaction with aqueous solutions and bacteria (Shewanella putrefaciens). Experimental results are presented for compacted clays, hydrated under confined volume conditions, using a new type of reaction-cell (the 'wet-cell' of Warr and Hoffman, 2004) that was designed for in situ X-ray diffraction (XRD) measurement. For comparison, dispersed clay systems were studied using standard batch solutions subjected to varying degrees of agitation. The combination of time-dependent in situ XRD measurements with gravimetric measurements and calculated diffraction patterns using the CALCMIX software (Plancon and Drits, 1999) allowed to successful quantification of the dynamics of water uptake and storage. This analytical procedure combined with published water vapour adsorption data enabled determination of the abundance of structured water layers, developed in the interlayer space, and the amount of water contained in different storage sites (interlayers, surfaces and pore spaces). Qualitative information on surface area and textural organization was also estimated based on calculated changes in the average particle thickness and the organization of water layer structures (ordering). Abiotic smectite hydration experiments, using a range of natural and industrial bentonites (SWy-2, IBECO, MX80, TIXOTON), focused on defining the role of the interlayer cation, variable clay packing densities and the ionic strength of the infiltrating solution. The rate of smectite hydration, as expected, was seen to be highly dependent on the type of interlayer cation (enhanced for Ca as opposed to Na) and the ionic strength of solution (enhanced uptake rates with saline solutions, particularly as they infiltrate Na-smectite). A range of dynamic changes in micro textural state occurred as a function of packing density. These changes explain the differences in hydration behaviour

  16. Determining the transition-state structure for different SN2 reactions using experimental nucleophile carbon and secondary alpha-deuterium kinetic isotope effects and theory.

    Science.gov (United States)

    Westaway, Kenneth C; Fang, Yao-ren; MacMillar, Susanna; Matsson, Olle; Poirier, Raymond A; Islam, Shahidul M

    2008-10-16

    Nucleophile (11)C/ (14)C [ k (11)/ k (14)] and secondary alpha-deuterium [( k H/ k D) alpha] kinetic isotope effects (KIEs) were measured for the S N2 reactions between tetrabutylammonium cyanide and ethyl iodide, bromide, chloride, and tosylate in anhydrous DMSO at 20 degrees C to determine whether these isotope effects can be used to determine the structure of S N2 transition states. Interpreting the experimental KIEs in the usual fashion (i.e., that a smaller nucleophile KIE indicates the Nu-C alpha transition state bond is shorter and a smaller ( k H/ k D) alpha is found when the Nu-LG distance in the transition state is shorter) suggests that the transition state is tighter with a slightly shorter NC-C alpha bond and a much shorter C alpha-LG bond when the substrate has a poorer halogen leaving group. Theoretical calculations at the B3LYP/aug-cc-pVDZ level of theory support this conclusion. The results show that the experimental nucleophile (11)C/ (14)C KIEs can be used to determine transition-state structure in different reactions and that the usual method of interpreting these KIEs is correct. The magnitude of the experimental secondary alpha-deuterium KIE is related to the nucleophile-leaving group distance in the S N2 transition state ( R TS) for reactions with a halogen leaving group. Unfortunately, the calculated and experimental ( k H/ k D) alpha's change oppositely with leaving group ability. However, the calculated ( k H/ k D) alpha's duplicate both the trend in the KIE with leaving group ability and the magnitude of the ( k H/ k D) alpha's for the ethyl halide reactions when different scale factors are used for the high and the low energy vibrations. This suggests it is critical that different scaling factors for the low and high energy vibrations be used if one wishes to duplicate experimental ( k H/ k D) alpha's. Finally, neither the experimental nor the theoretical secondary alpha-deuterium KIEs for the ethyl tosylate reaction fit the trend found

  17. Theoretical and experimental study on the effects of particle size and temperature on the reaction kinetics of cubic nano-Cu2O

    Science.gov (United States)

    Tang, Huanfeng; Huang, Zaiyin; Xiao, Ming; Liang, Min; Chen, Liying; Tan, XueCai

    2017-09-01

    The activities, selectivities, and stabilities of nanoparticles in heterogeneous reactions are size-dependent. In order to investigate the influencing laws of particle size and temperature on kinetic parameters in heterogeneous reactions, cubic nano-Cu2O particles of four different sizes in the range of 40-120 nm have been controllably synthesized. In situ microcalorimetry has been used to attain thermodynamic data on the reaction of Cu2O with aqueous HNO3 and, combined with thermodynamic principles and kinetic transition-state theory, the relevant reaction kinetic parameters have been evaluated. The size dependences of the kinetic parameters are discussed in terms of the established kinetic model and the experimental results. It was found that the reaction rate constants increased with decreasing particle size. Accordingly, the apparent activation energy, pre-exponential factor, activation enthalpy, activation entropy, and activation Gibbs energy decreased with decreasing particle size. The reaction rate constants and activation Gibbs energies increased with increasing temperature. Moreover, the logarithms of the apparent activation energies, pre-exponential factors, and rate constants were found to be linearly related to the reciprocal of particle size, consistent with the kinetic models. The influence of particle size on these reaction kinetic parameters may be explained as follows: the apparent activation energy is affected by the partial molar enthalpy, the pre-exponential factor is affected by the partial molar entropy, and the reaction rate constant is affected by the partial molar Gibbs energy. [Figure not available: see fulltext.

  18. 4′-CyanoPLP presents better prospect for the experimental detection of elusive cyclic intermediate radical in the reaction of lysine 5,6-aminomutase

    Energy Technology Data Exchange (ETDEWEB)

    Maity, Amarendra Nath; Ke, Shyue-Chu, E-mail: ke@mail.ndhu.edu.tw

    2015-02-06

    Graphical abstract: 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, which is proposed to be a key intermediate in the reaction of pyridoxal-5′-phosphate dependent radical aminomutases. - Highlights: • 4′-CyanoI{sup ·} is the lowest energy radical intermediate in the reaction of 5,6-LAM. • 4′-CyanoPLP offers good prospect for the experimental observation of elusive I{sup ·}. • The calculated HFCCs would help to characterize 4′-cyanoI{sup ·} by EPR. - Abstract: 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{sup ·}), 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 {sup 14}N and {sup 13}C of cyano group using several basis sets to help the characterization of 4′-cyanoI{sup ·}.

  19. Detection of infectious bursal disease virus in various lymphoid tissues of experimentally infected specific pathogen free chickens by different reverse transcription polymerase chain reaction assays

    DEFF Research Database (Denmark)

    Kabell, Susanne; Handberg, Kurt; Kusk, Mette;

    2005-01-01

    transcription polymerase chain reaction (RT-PCR) assays, including two recently developed strain-specific assays, were employed for detection of ribonucleic acid (RNA) from three different IBDV strains in bursa tissue samples from experimentally infected specific pathogen free chickens. The virus strains...

  20. CHARGE-TRANSFER AND ENERGY-TRANSFER IN THE PHOTO-INDUCED COPOLYMERIZATION OF 2-VINYLNAPHTHALENE WITH MALEIC ANHYDRIDE

    Institute of Scientific and Technical Information of China (English)

    LI Tong; LUO Bin; LI Shanjun; CHU Guobei

    1990-01-01

    The initiation mechanism of the copolymerization of 2-vinylnaphthalene with maleic anhydride was studied under irradiation of 365 nm. The excited complex was formed from ( 1 ) the local excitation of 2-vinylnaphthalene followed by the charge-transfer interaction with maleic anhydride and ( 2 ) the excitation of the ground state charge-transfer complex, and then it collapsed to 1,4-tetramethylene biradical for initiation. A 1:1 alternating copolymer was formed in different monomer feeds. Addition of benzophenone could greatly enhance the rate of copolymerization through energy-transfer mechanism.

  1. EFFECT OF TEMPERATURE ON COPOLYMERIZATION PARAMETERS OF HYDROXYETHYL ACRYLATE AND METHYL METHACRYLATE

    Institute of Scientific and Technical Information of China (English)

    1998-01-01

    The copolymerization of 2-hydroxyethyl acrylate (HEA, M1) and methyl methacrylate (MMA, M2) in cyclohexanone was studied. The multiple experiments of solution copolymerization with low conversion were carried out at two sensitive composition feed points at 60, 80, 100, 120 and 140℃, respectively. The composition of the copolymers was analyzed by 1H-NMR. The reactivity ratios which were estimated by the Error-inVariable Method (EVM) of Mayo-Lewis equation were found to be r1 = 0.328, r2 = 1.781for 60℃; 0.375, 1.709 for 80℃; 0.406, 1.654 for 100℃; 0.439, 1.540 for 120℃ and 0.455,1.400 for 140℃, and the 95% joint confidence intervals of the reactivity ratios were also determined. According to r1 and r2, Arrhenius relations and the activity energy difference between the homo- and cross-propagation were calculated.

  2. Homogeneous Modification of Sugarcane Bagasse by Graft Copolymerization in Ionic Liquid for Oil Absorption Application

    Directory of Open Access Journals (Sweden)

    Ming-Jie Chen

    2016-01-01

    Full Text Available Sugarcane bagasse, lignocellulosic residue from the sugar industry, is an abundant and renewable bioresource on the earth. The application of ionic liquids in sugarcane bagasse biorefinery is gaining increasing interest. The homogeneous modification of sugarcane bagasse by free radical initiated graft copolymerization of acrylate monomers using 1-allyl-3-methylimidazolium chloride as solvent was performed. A variety of sugarcane bagasse graft copolymers with different weight percent gain were prepared via adjusting the monomer dosage. FT-IR studies confirmed the success in attaching the poly(acrylate side chains onto sugarcane bagasse. Oil absorbency studies suggested that the sugarcane bagasse graft copolymers were potential biobased materials for effective treatment of ester-based oils. SEM studies showed that the sugarcane bagasse graft copolymers displayed a dense morphology structure. Thermogravimetric analysis demonstrated that the thermal stability of sugarcane bagasse decreased after the homogeneous modification by the graft copolymerization. The present study provides an alternative strategy to convert sugarcane bagasse into a value-added functional biobased material.

  3. Reversion of pH-induced physiological drug resistance: a novel function of copolymeric nanoparticles.

    Directory of Open Access Journals (Sweden)

    Rutian Li

    Full Text Available AIMS: The extracellular pH of cancer cells is lower than the intracellular pH. Weakly basic anticancer drugs will be protonated extracellularly and display a decreased intracellular concentration. In this study, we show that copolymeric nanoparticles (NPs are able to overcome this "pH-induced physiological drug resistance" (PIPDR by delivering drugs to the cancer cells via endocytosis rather than passive diffussion. MATERIALS AND METHODS: As a model nanoparticle, Tetradrine (Tet, Pka 7.80 was incorporated into mPEG-PCL. The effectiveness of free Tet and Tet-NPs were compared at different extracellular pHs (pH values 6.8 and 7.4, respectively by MTT assay, morphological observation and apoptotic analysis in vitro and on a murine model by tumor volume measurement, PET-CT scanning and side effect evaluation in vivo. RESULTS: The cytotoxicity of free Tet decreased prominently (P<0.05 when the extracellular pH decreased from 7.4 to 6.8. Meanwhile, the cytotoxicity of Tet-NPs was not significantly influenced by reduced pH. In vivo experiment also revealed that Tet-NPs reversed PIPDR more effectively than other existing methods and with much less side effects. CONCLUSION: The reversion of PIPDR is a new discovered mechanism of copolymeric NPs. This study emphasized the importance of cancer microenvironmental factors in anticancer drug resistance and revealed the superiority of nanoscale drug carrier from a different aspect.

  4. An Experimental and Theoretical Study on the Kinetic Isotope Effect of C2H6 and C2D6 Reaction with OH

    KAUST Repository

    Khaled, Fathi

    2015-10-30

    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 for alkanes asymptotes to a value of 1.4 at high temperatures.

  5. Experimental Study on Impact-Induced Reaction Characteristics of PTFE/Ti Composites Enhanced by W Particles

    Directory of Open Access Journals (Sweden)

    Yan Li

    2017-02-01

    Full Text Available Metal/fluoropolymer composites are a category of energetic structural materials that release energy through exothermic chemical reactions initiated under highly dynamic loadings. In this paper, the chemical reaction mechanism of PTFE (polytetrafluoroethylene/Ti/W composites is investigated through thermal analysis and composition analysis. These composites undergo exothermic reactions at 510 °C to 600 °C, mainly producing TiFx. The tungsten significantly reduces the reaction heat due to its inertness. In addition, the dynamic compression properties and impact-induced reaction behaviors of PTFE/Ti/W composites with different W content prepared by pressing and sintering are studied using Split Hopkinson Pressure Bar and high speed photography. The results show that both the mechanical strength and the reaction degree are significantly improved with the increasing strain rate. Moreover, as W content increases, the mechanical strength is enhanced, but the elasticity/plasticity is decreased. The PTFE/Ti/W composites tend to become more inert with the increasing W content, which is reflected by the reduced reaction degree and the increased reaction threshold for the impact ignition.

  6. Experimental Study of Closed System in the Chlorine Dioxide-Iodide-Sulfuric Acid Reaction by UV-Vis Spectrophotometric Method

    Science.gov (United States)

    Li, Na; Shi, Laishun; Wang, Xiaomei; Guo, Fang; Yan, Chunying

    2011-01-01

    The mole ratio r(r = [I−]0/[ClO2]0) has great influence on ClO2-I−-H2SO4 closed reaction system. By changing the initiate concentration of potassium iodide, the curve of absorbance along with the reaction time was obtained at 350 nm and 297 nm for triiodide ion, and 460 nm for iodine. The changing point of the absorbance curve's shape locates at r = 6.00. For the reaction of ClO2-I− in the absence of H2SO4, the curve of absorbance along with the reaction time can be obtained at 350 nm for triiodide ion, 460 nm for iodine. The mole ratio r is equal to 1.00 is the changing point of the curve's shape no matter at which wavelength to determine the reaction. For the reaction of ClO2-I−-H+ in different pH buffer solution, the curve of absorbance along with the reaction time was recorded at 460 nm for iodine. When r is greater than 1.00, the transition point of the curve's shape locates at pH 2.0, which is also the point of producing chlorite or chloride for chlorine dioxide at different pH. When r is less than 1.00, the transition point locates at pH 7.0. PMID:21808646

  7. Experimental Study of Closed System in the Chlorine Dioxide-Iodide-Sulfuric Acid Reaction by UV-Vis Spectrophotometric Method

    Directory of Open Access Journals (Sweden)

    Na Li

    2011-01-01

    Full Text Available The mole ratio r(r=[I−]0/[ClO2]0 has great influence on ClO2-I−-H2SO4 closed reaction system. By changing the initiate concentration of potassium iodide, the curve of absorbance along with the reaction time was obtained at 350 nm and 297 nm for triiodide ion, and 460 nm for iodine. The changing point of the absorbance curve's shape locates at r=6.00. For the reaction of ClO2-I− in the absence of H2SO4, the curve of absorbance along with the reaction time can be obtained at 350 nm for triiodide ion, 460 nm for iodine. The mole ratio r is equal to 1.00 is the changing point of the curve's shape no matter at which wavelength to determine the reaction. For the reaction of ClO2-I−-H+ in different pH buffer solution, the curve of absorbance along with the reaction time was recorded at 460 nm for iodine. When r is greater than 1.00, the transition point of the curve's shape locates at pH 2.0, which is also the point of producing chlorite or chloride for chlorine dioxide at different pH. When r is less than 1.00, the transition point locates at pH 7.0.

  8. RAFT Polymerization of Styrene and Maleimide in the Presence of Fluoroalcohol: Hydrogen Bonding Effects with Classical Alternating Copolymerization as Reference

    Directory of Open Access Journals (Sweden)

    Fangjun Yao

    2017-03-01

    Full Text Available The impacts of hydrogen bonding on polymerization behavior has been of interest for a long time; however, universality and in-depth understanding are still lacking. For the first time, the effect of hydrogen bonding on the classical alternating-type copolymerization of styrene and maleimide was explored. N-phenylmaleimide (N-PMI/styrene was chosen as a model monomer pair in the presence of hydrogen bonding donor solvent 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP, which interacted with N-PMI via hydrogen bonding. Reversible addition-fragmentation chain transfer polymerization (RAFT technique was used to guarantee the “living” polymerization and thus the homogeneity of chain compositions. In comparison with the polymerization in nonhydrogen bonding donor solvent (toluene, the copolymerization in HFIP exhibited a high rate and a slight deviation from alternating copolymerization tendency. The reactivity ratios of N-PMI and St were revealed to be 0.078 and 0.068, respectively, while the reactivity ratios in toluene were 0.026 and 0.050. These interesting results were reasonably explained by using computer simulations, wherein the steric repulsion and electron induction by the hydrogen bonding between HFIP and NPMI were revealed. This work first elucidated the hydrogen bonding interaction in the classical alternating-type copolymerization, which will enrich the research on hydrogen bonding-induced polymerizations.

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

    Science.gov (United States)

    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).

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  12. Thiol-functionalized copolymeric polyesters by lipase-catalyzed esterification and transesterification of 1,12-dodecanedioic acid and its diethyl ester, respectively, with 1-thioglycerol.

    Science.gov (United States)

    Fehling, Eberhard; Bergander, Klaus; Klein, Erika; Weber, Nikolaus; Vosmann, Klaus

    2010-10-01

    Copolymeric polyoxoesters containing branched-chain methylenethiol functions, i.e., poly(1,12-dodecanedioic acid-co-1-thioglycerol) and poly(diethyl 1,12-dodecanedioate-co-1-thioglycerol), were formed by lipase-catalyzed polyesterification and polytransesterification of 1,12-dodecanedioic acid and diethyl 1,12-dodecanedioate, respectively, with 1-thioglycerol (3-mercaptopropane-1,2-diol) using immobilized lipase B from Candida antarctica (Novozym 435) in vacuo without drying agent in the reaction mixture. After 360-480 h, both polyoxoesters were purified by extraction from the reaction mixtures followed by solvent fractionation. The precipitate of poly(1,12-dodecanedioic acid-co-1-thioglycerol) demonstrated a M(W) of ~170,000 Da, whereas a M(W) of ~7,100 Da only was found for poly(diethyl 1,12-dodecanedioate-co-1-thioglycerol). Both polycondensates were analyzed by GPC/SEC, alkali-catalyzed transmethylation, NMR- and FTIR-spectrometry.

  13. Highly regio-and stereo-selective copolymerization of CO2 with racemic propylene oxide catalyzed by unsymmetrical (S,S,S)-salenCo(Ⅲ) complexes

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    A novel unsymmetrical (S,S,S)-salen ligand bearing a derived chiral-BINOL was synthesized by the reaction of the condensation product of (1S,2S)-1,2-diaminocyclohexane mono(hydrogen chloride) with 3-adamanyl-5-tert-butyl-2-hydroxybenzalde-hyde and 3-formoyl-2-hydroxy-2’-alkyloxy-1,1’-binaphthyl,which originated from (S)-1,1’-bi-2-naphthol via a four-step reaction.The cobalt complexes of this ligand,in conjunction with a nucleophilic cocatalyst,exhibited excellent activity in catalyzing asymmetric,regio-and stereo-selective copolymerization of CO2 and racemic propylene oxide.The highest record of kinetic resolution coefficient (Krel) was obtained with the use of binary catalyst system consisting of (S,S,S)-salenCo(III) complex 1c and bulky bis(triphenylphosphine)-iminium chloride (PPNCl).The resulting poly(propylene carbonate)s have more than 99% carbonate linkages and more than 98% head-to-tail content.

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

    Science.gov (United States)

    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.

  15. Copolymerization of Ethylene with Dicyclopentadiene Using a Constrained Geometry Cyclopentadienyl-phenoxytitanium Catalyst

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    The copolymerization of ethylene with dicyclopentadiene ( DCP ) in the presence of a constrained geometry tetramethylcyclopentadi-enyl-phenoxytitanium catalyst [ 2,4 -t Bu2 -6 - ( 2,3,4,5 -Me4 -Cp ) -PhO ] TiCl2, combined with Al( iBu)3/Ph3C+ B( C6F5 )-4 cocatalyst system was studied. The copolymers that were formed were characterized by 1H and 13C NMR, differential scanning calorimetry (DSC), SEM, and X-ray diffraction (XRD) analyses. The results of the analysis indicate that the copolymers of ethylene with dicyclopentadiene are amorphous and display two or more melting temperatures in their DSC diagams. Moreover, the morphologies of the copolymers are quite different from that of polyethylenes.

  16. Copolymerization of Ethylene and Vinyl Amino Acidic Ester Catalyzed by Titanium and Zirconium Complexes

    Directory of Open Access Journals (Sweden)

    Jing Wang

    2015-10-01

    Full Text Available A series of titanium and zirconium complexes with ligands based on di-isopropyl phosphorus-phenylamine and their derivatives were synthesized and characterized. These catalysts were utilized to catalyze the copolymerization of ethylene with N-acetyl-O-(dec-9-enyl-L-tyrosine ethyl ester with high catalytic activity of 6.63 × 104 g P (mol Ti−1 h−1 after activation by methylaluminoxane (MAO. The effects of ligand structure, metal atoms (Ti, Zr and polymerization conditions were investigated in detail. The obtained polymers were characterized by 13C-NMR, DSC, FT-IR, and GPC. The results showed that the obtained copolymer had a high comonomer incorporation rate of 2.56 mol % within the copolymer chain. The melting temperature of the copolymer was up to 138.9 °C, higher than that of the obtained homopolyethylene.

  17. ALTERNATING COPOLYMERIZATION OF CYCLOHEXENE OXIDE AND CARBON DIOXIDE UNDER COBALT PORPHYRIN CATALYST

    Institute of Scientific and Technical Information of China (English)

    Yu-sheng Qin; Li-jie Chen; Xian-hong Wang; Xiao-jiang Zhao; Fo-song Wang

    2011-01-01

    Cobalt porphyrin complexes (TPPComx) (TPP =5,10,15,20-tetraphenyl-porphyrin; X =halide) in combination with bis(triphenylphosphine) iminium chloride (PPNC1) were used for the copolymerization of cyclohexene oxide and CO2.The highest turnover frequency of 67.2 h-1 was achieved after 13 h at 20℃,and the obtained poly(1,2-cyclohexylene carbonate) (PCHC) showed number average molecular weight (Mn) of 10 × 103.Though the obtained PCHC showed atactic structure,the m-centered tetrads content reached 58.1% at CO2 pressure of 1.0 MPa,and decreased to 51.9% at CO2 pressure of 6.0 MPa,indicating that it was inclined to form atactic polymer at high CO2 pressure.

  18. Enzymatic ring-opening copolymerization of trimethylene carbonate and ethylene ethyl phosphate

    Institute of Scientific and Technical Information of China (English)

    FENG; Jun; (冯俊); ZHUO; Renxi; (卓仁禧); HE; Feng; (贺枫)

    2003-01-01

    Enzymatic ring-opening copolymerization of trimethylene carbonate (TMC) and ethylene ethyl phosphate (EEP) are performed in bulk at 100℃ using porcine pancreas lipase (PPL) or candida rugosa lipase (CL) as catalyst. The factors affecting the yield and molecular weights such as catalyst concentration, polymerization time and monomer feed ratio are investigated. The random copolymers obtained have molecular weight ranging from 3200 to 10200. The glass transition temperature (Tg) of the copolymers decreases from 28 to 41.7℃, with the increase of the EEP content in the feed from zero to 5∶10. Degradation tests show that the degradability of the copolymers is improved by introduction of the EEP unit into the copolymer chain.

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

    Science.gov (United States)

    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. Copyright © 2015 Elsevier B.V. All rights reserved.

  20. Improved detection of amylase activity by sodium dodecyl sulfate-polyacrylamide gel electrophoresis with copolymerized starch.

    Science.gov (United States)

    Martínez, T F; Alarcón, F J; Díaz-López, M; Moyano, F J

    2000-08-01

    An improved method, based on sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) for detection of amylase activity is described. This method will allow better characterization of certain amylases than that obtained by the Davis technique. The main features of the technique are: (i) identification of amylase bands and molecular mass determination are possible in the same gel; (ii) the hydrolysis of copolymerized substrate during electrophoretic separation is prevented using very low temperatures instead of inactivating agents such as chelating agents; and (iii) the technique is applicable to reveal amylase activity in a wide range of biological samples. The method is not useful for enzymes sensitive to SDS and for high molecular mass amylases.

  1. An experimental kinetic study and products research of the reactions of O3 with a series of unsaturated alcohols

    Science.gov (United States)

    Chen, Yi; Wang, Jing; Zhao, Sanping; Tong, Shengrui; Ge, Maofa

    2016-11-01

    The gas-phase reactions of unsaturated alcohols with O3 were investigated in FEP Teflon film chamber at 298 K and 760 torr of atmosphere pressure. The rate constants of the reactions of C6-C8 alkenols with O3 were determined using both the absolute and the relative rate method, and the measured values were (5.96 ± 0.35) × 10-17 cm3 molecule-1 s-1 for (Z)-3-hexen-1-ol, (5.12 ± 0.30) × 10-17 cm3 molecule-1 s-1 for (Z)-3-hepten-1-ol, and (5.66 ± 0.52) × 10-17 cm3 molecule-1 s-1 for (Z)-3-octen-1-ol, respectively. The gas-phase products of these reactions mentioned above were detected using proton-transfer-reaction mass spectrum (PTR-MS). HOCH2CH2CHO, CH2CH2CHO, HCHO and CH3CHO were identified as the main gas products for (Z)-3-hexen-1-ol. HOCH2CH2CHO and CH3(CH2)2CHO dominated the gaseous products for (Z)-3-hepten-1-ol. And for (Z)-3-octen-1-ol, CH3(CH2)3CHO, CH3(CH2)2CHO and HOCH2CH2CHO were the main gaseous products. The SOA yields were monitored at the same time, which were 0.184 ± 0.013, 0.213 ± 0.017, 0.232 ± 0.021 for (Z)-3-hexen-1-ol, (Z)-3-hepten-1-ol and (Z)-3-octen-1-ol, respectively. The possible reaction mechanisms were proposed and discussed. The kinetic data presented here has been used to estimate their atmosphere lifetimes and the reaction reactivity. The atmosphere implication of these reactions has also been discussed.

  2. STUDY ON REGULARITIES OF GRAFT COPOLYMERIZATION OF ACRYLIC ACID ONTO FUNGAL CELL WALL%米根霉细胞壁结构性多糖与丙烯酸接枝共聚反应研究

    Institute of Scientific and Technical Information of China (English)

    张诚; 孟琴; 吕德伟

    2001-01-01

    For the aim of getting macromolecular flocculant,we studied the copolymerization of acrylic acid onto Rhi.oryzae cell wall structural polysaccharide by the initiation of ceric ammonium nitrate.The effect of concentration of initiator and monomer,reaction temperature and reaction time on grafting percentage was investigated.To Rhi.oryzae cell wall structural polysaccharide the maximal grafting percentage of 135.5% was achieved at [Ce+4]=5mmol/L,[AA]=1mol/L,T=60℃,t=3h.Then choosing organic dyes as the flocculated substances,by comparing with the chitosan,polyacrylamide and Rhi.oryzae cell wall structural polysaccharide before grafting,we studied the flocculent capability of Rhi.oryzae cell wall structural polysaccharide after grafting acrylic acid.The grafting product had excellent flocculent effect on basic and neutral dyes.

  3. Experimental setup and procedure for the measurement of the {sup 7}Be(n,α)α reaction at n-TOF

    Energy Technology Data Exchange (ETDEWEB)

    Cosentino, L. [INFN Laboratori Nazionali del Sud, Catania (Italy); Musumarra, A. [INFN Laboratori Nazionali del Sud, Catania (Italy); Dipartimento di Fisica e Astronomia DFA, Università di Catania (Italy); Barbagallo, M. [INFN Sezione di Bari (Italy); Pappalardo, A. [INFN Laboratori Nazionali del Sud, Catania (Italy); Colonna, N.; Damone, L. [INFN Sezione di Bari (Italy); Piscopo, M. [INFN Laboratori Nazionali del Sud, Catania (Italy); Finocchiaro, P., E-mail: FINOCCHIARO@LNS.INFN.IT [INFN Laboratori Nazionali del Sud, Catania (Italy); Maugeri, E.; Heinitz, S.; Schumann, D.; Dressler, R.; Kivel, N. [Paul Scherrer Institut, Nuclear Energy and Safety Research Department, 5232 Villigen (Switzerland); Aberle, O. [CERN, Geneva (Switzerland); Andrzejewski, J. [Uniwersytet Łódzki, Lodz (Poland); Audouin, L. [Institut de Physique Nucléaire, CNRS-IN2P3, Univ. Paris-Sud, Université Paris-Saclay, 91406 Orsay Cedex (France); Ayranov, M. [European Commission, DG-Energy (Luxembourg); Bacak, M. [Atominstitut der Österreichischen Universitäten, Technische Universität Wien (Austria); Barros, S. [C2TN-Instituto Superior Tecníco, Universidade de Lisboa (Portugal); Balibrea-Correa, J. [Centro de Investigaciones Energeticas Medioambientales y Tecnológicas (CIEMAT), Madrid (Spain); and others

    2016-09-11

    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 {sup 7}Be(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 {sup 7}Be 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.

  4. Synthesis of PNVP-Based Copolymers with Tunable Thermosensitivity by Sequential Reversible Addition–Fragmentation Chain Transfer Copolymerization and Ring-Opening Polymerization

    Directory of Open Access Journals (Sweden)

    Yi-Shen Huang

    2017-06-01

    Full Text Available Through the reversible addition–fragmentation chain transfer (RAFT copolymerization of 3-ethyl-1-vinyl-2-pyrrolidone (C2NVP and N-vinylpyrrolidone (NVP, a series of well-defined P(C2NVP-co-NVP copolymers were synthesized (Mn = ca. 8000 to 16,000 and Mw/Mn <1.5 by using a difunctional chain transfer agent, S-(1-methyl-4-hydroxyethyl acetate O-ethyl xanthate (MHEX. Copolymerizing kinetics and different monomer ratio in feeds were conducted to study the apparent monomer reaction rate and reactivity ratios of NVP and C2NVP, which indicated similar reaction rates and predominantly ideal random copolymers for the two monomers. The Tgs of the obtaining P(C2NVP-co-NVP copolymers significantly corresponded to not only molecular weights MWs but also copolymer compositions. These copolymers presented characteristic lower critical solution temperatures (LCST behavior. We then studied the cloud points (CPs of the copolymers with varying MWs and compositions. With different MWs, the CPs were linearly decreased from ca. 51 to 45 °C. With different compositions, the CPs of the copolymers decreased from ca. 48 to 29 °C with C2NVP content (i.e., from 60.8 to 89.9 mol %. Fitting the CPs by the theoretical equation, the result illustrated that the introduction of more hydrophobic units of C2NVP suppressed the hydrophilic interaction between the polymer chain and water. We then successfully proceeded the chain extension through the ring-opening polymerization (ROP of ε-caprolactone (CL to the synthesis of a novel P(C2NVP-co-NVP-b-PCL amphiphilic block copolymer (Mn,NMR = 14,730 and Mw/Mn = 1.59. The critical micelle concentration (CMC of the block copolymer had a value of ca. 1.46 × 10−4 g/L. The block copolymer micelle was traced by dynamic light scattering (DLS, obtaining thermosensitive behaviors with a particle size of ca. 240 nm at 25 °C and ca. 140 nm at 55 °C, respectively.

  5. Selective oxidation of alcohols with alkali metal bromides as bromide catalysts: experimental study of the reaction mechanism.

    Science.gov (United States)

    Moriyama, Katsuhiko; Takemura, Misato; Togo, Hideo

    2014-07-03

    A bromide-catalyzed oxidation of alcohols was developed which proceeded in the presence of an alkali metal bromide and an oxidant under mild conditions. The reaction involved an organic-molecule-free oxidation using KBr and Oxone and a Brønsted acid assisted oxidation using KBr and aqueous H2O2 solution to provide a broad range of carbonyl compounds in high yields. Moreover, the bromide-catalyzed oxidation of primary alcohols enabled the divergent synthesis of carboxylic acids and aldehydes under both reaction conditions in the presence of TEMPO. A possible catalytic mechanism was suggested on the basis of various mechanistic studies.

  6. Experimental Plan of the 25Mg(p, γ)26Al Resonance Capture Reaction at Jinping Underground Laboratory

    Science.gov (United States)

    Li, Z. H.; Su, J.; Li, Y. J.; Guo, B.; Yan, S. Q.; Wang, Y. B.; Lian, G.; Zeng, S.; Zhang, Q. W.; He, G. Z.; Gan, L.; Zhou, C.; Liu, W. P.; Li, K. A.; Yu, X. Q.; Tang, X. D.; He, J. J.; Qian, Y. Z.

    The observation of 26Al is an useful tool for γ-ray astronomy and in studies of galactic chemical evolution. The most likely mechanism for 26A1 nucleosynthesis is in the hydrogen burning MgAl cycle, and the 26A1 production from the 25Mg(p, γ)26Al reaction at the important temperature range below T = 0.2 is still not well known. We present a proposal to measure the resonance strength of 58 keV resonance level of the 25Mg(p, γ)26Al reaction, and the effective counting rate is estimated for the direct measurement at Jinping underground laboratory.

  7. Combined experimental and theoretical studies of regio- and stereoselectivity in reactions of β-isoxazolyl- and β-imidazolyl enamines with nitrile oxides

    Directory of Open Access Journals (Sweden)

    Ilya V. Efimov

    2016-11-01

    Full Text Available Reactions of β-azolyl enamines and nitrile oxides were studied by both experimental and theoretical methods. (E-β-(4-Nitroimidazol-5-yl, (5-nitroimidazol-4-yl and isoxazol-5-yl enamines smoothly react regioselectively at room temperature in dioxane solution with aryl, pyridyl, and cyclohexylhydroxamoyl chlorides without a catalyst or a base to form 4-azolylisoxazoles as the only products in good yields. The intermediate 4,5-dihydroisoxazolines were isolated as trans isomers during the reaction of (E-β-imidazol-4-yl enamines with aryl and cyclohexylhydroxamoyl chlorides. Stepwise and concerted pathways for the reaction of β-azolyl enamines with hydroxamoyl chlorides were considered and studied at the B3LYP/Def2-TZVP level of theory combined with D3BJ dispersion correction. The reactions of benzonitrile oxide with both E- and Z-imidazolyl enamines have been shown to proceed stereoselectively to form trans- and cis-isoxazolines, respectively. The preference of E-isomers over Z-isomers, driven by the higher stability of the former, apparently controls the stereoselectivity of the investigated cycloaddition reaction with benzonitrilе oxide. Based on the reactivity of azolyl enamines towards hydroxamoyl chlorides, a novel, effective catalyst-free method was elaborated to prepare 4-azolyl-5-substituted isoxazoles that are otherwise difficult to obtain.

  8. Recovery Act: An Integrated Experimental and Numerical Study: Developing a Reaction Transport Model that Couples Chemical Reactions of Mineral Dissolution/Precipitation with Spatial and Temporal Flow Variations.

    Energy Technology Data Exchange (ETDEWEB)

    Saar, Martin O. [ETH Zurich (Switzerland); Univ. of Minnesota, Minneapolis, MN (United States); Seyfried, Jr., William E. [Univ. of Minnesota, Minneapolis, MN (United States); Longmire, Ellen K. [Univ. of Minnesota, Minneapolis, MN (United States)

    2016-06-24

    A total of 12 publications and 23 abstracts were produced as a result of this study. In particular, the compilation of a thermodynamic database utilizing consistent, current thermodynamic data is a major step toward accurately modeling multi-phase fluid interactions with solids. Existing databases designed for aqueous fluids did not mesh well with existing solid phase databases. Addition of a second liquid phase (CO2) magnifies the inconsistencies between aqueous and solid thermodynamic databases. Overall, the combination of high temperature and pressure lab studies (task 1), using a purpose built apparatus, and solid characterization (task 2), using XRCT and more developed technologies, allowed observation of dissolution and precipitation processes under CO2 reservoir conditions. These observations were combined with results from PIV experiments on multi-phase fluids (task 3) in typical flow path geometries. The results of the tasks 1, 2, and 3 were compiled and integrated into numerical models utilizing Lattice-Boltzmann simulations (task 4) to realistically model the physical processes and were ultimately folded into TOUGH2 code for reservoir scale modeling (task 5). Compilation of the thermodynamic database assisted comparisons to PIV experiments (Task 3) and greatly improved Lattice Boltzmann (Task 4) and TOUGH2 simulations (Task 5). PIV (Task 3) and experimental apparatus (Task 1) have identified problem areas in TOUGHREACT code. Additional lab experiments and coding work has been integrated into an improved numerical modeling code.

  9. The development and experimental validation of a reduced ternary kinetic mechanism for the auto-ignition at HCCI conditions, proposing a global reaction path for ternary gasoline surrogates

    Energy Technology Data Exchange (ETDEWEB)

    Machrafi, Hatim; Cavadias, Simeon; Amouroux, Jacques [UPMC Universite Paris 06, LGPPTS, Ecole Nationale Superieure de Chimie de Paris, 11, rue de Pierre et Marie Curie, 75005 Paris (France)

    2009-02-15

    To acquire a high amount of information of the behaviour of the Homogeneous Charge Compression Ignition (HCCI) auto-ignition process, a reduced surrogate mechanism has been composed out of reduced n-heptane, iso-octane and toluene mechanisms, containing 62 reactions and 49 species. This mechanism has been validated numerically in a 0D HCCI engine code against more detailed mechanisms (inlet temperature varying from 290 to 500 K, the equivalence ratio from 0.2 to 0.7 and the compression ratio from 8 to 18) and experimentally against experimental shock tube and rapid compression machine data from the literature at pressures between 9 and 55 bar and temperatures between 700 and 1400 K for several fuels: the pure compounds n-heptane, iso-octane and toluene as well as binary and ternary mixtures of these compounds. For this validation, stoichiometric mixtures and mixtures with an equivalence ratio of 0.5 are used. The experimental validation is extended by comparing the surrogate mechanism to experimental data from an HCCI engine. A global reaction pathway is proposed for the auto-ignition of a surrogate gasoline, using the surrogate mechanism, in order to show the interactions that the three compounds can have with one another during the auto-ignition of a ternary mixture. (author)

  10. Kinetic, structural, and reaction engineering studies of inorganic-organic sol-gel copolymers

    Science.gov (United States)

    Rankin, Stephen Edward

    stress at the free surface---problems which may be addressed with design calculations. Finally, this thesis extends quantitative kinetic modeling to copolymerization of pairs of alkoxysilanes. More kinetic parameters must be determined for these systems. To do so, the extent of copolymerization is determined indirectly by the dependence on composition of reaction rates in a semibatch reactor. These copolymerization models allow optimization of copolymer homogeneity and molecular structure by reactor design.

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

    Science.gov (United States)

    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)

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

    CERN Document Server

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

    2016-01-01

    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 40 MeV up to 50 MeV. 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 37-50 MeV 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 TALYS1.6 nuclear model code as listed in the on-line library TENDL-2014.

  13. Experimentally induced states of mind determine abstinent smokers' level of craving in reaction to smoking-cues

    Directory of Open Access Journals (Sweden)

    Arie Dijkstra

    2015-06-01

    Conclusions: The present studies provide experimental evidence that levels of craving can be determined by momentary states of mind. This theoretical perspective can be integrated in existing conditioning and social cognitive learning perspectives on craving and substance use.

  14. Examination and experimental constraints of the stellar reaction rate factor $N_A < \\sigma v >$ of the $^{18}$Ne($\\alpha$,$p$)$^{21}$Na reaction at temperatures of X-Ray Bursts

    CERN Document Server

    Mohr, P

    2013-01-01

    The $^{18}$Ne($\\alpha$,$p$)$^{21}$Na reaction is one key for the break-out from the hot CNO-cycles to the $rp$-process. Recent papers have provided reaction rate factors $N_A $ 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 $N_A$ 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 by Matic {\\it et al.}\\ at low temperatures and significantly below at higher temperatures whereas it is about a factor of five higher than the lower rate factor recently published by Salter {\\it et al.}

  15. Kinetics and mechanism of the reaction of OH with the trimethylbenzenes--experimental evidence for the formation of adduct isomers.

    Science.gov (United States)

    Bohn, Birger; Zetzsch, Cornelius

    2012-10-28

    The reversible gas-phase addition of OH radicals to the trimethylbenzenes was investigated in pulsed experiments utilizing VUV flash-photolysis resonance-fluorescence of H(2)O in the temperature range of 275-340 K. Triexponential OH decays were observed in the presence of the trimethylbenzenes, indicating the participation of more than one adduct species. Analytical solutions for the system of differential equations with two adduct isomers were derived, and the OH decay curves were evaluated based on this reaction model. This led to significant improvements of fit qualities and notable changes in OH rate constants compared to a previous model with a single adduct species. The detailed analysis was confined to 1,3,5-trimethylbenzene where reversible formation of two OH-aromatic ortho- and ipso-adduct isomers is feasible in accordance with the extended reaction model. Only after inclusion of additional isomerization reactions, consistent thermochemical data were obtained from the fitted rate constants. Reaction enthalpies of -83 ± 7 kJ mol(-1) and -35 ± 22 kJ mol(-1) were derived for the formation of one adduct isomer and the isomerization into the other, respectively. Based on literature data, the more and less stable adducts were assigned to ipso- and ortho-adduct isomers, respectively. The potential isomerization precluded the determination of primary yields of adduct isomers but formation of the ipso-adduct in any case is a minor process. For the rate constants of the OH + 1,3,5-trimethylbenzene reaction an Arrhenius expression k(OH) = 1.32 × 10(-11) cm(3) s(-1) exp(450 ± 50 K/T) was obtained. Based on the same approach, the rate constants of the OH reactions with 1,2,3-trimethylbenzene and 1,2,4-trimethylbenzene were derived as k(OH) = 3.61 × 10(-12) cm(3) s(-1) exp(620 ± 80 K/T) and k(OH) = 2.73 × 10(-12) cm(3) s(-1) exp(730 ± 70 K/T), respectively.

  16. Silica-grafted diethylzinc and a silsesquioxane-based zinc alkyl complex as catalysts for the alternating oxirane-carbon dioxide copolymerization

    NARCIS (Netherlands)

    Duchateau, Robbert; van Meerendonkt, Wouter J.; Huijser, Saskia; Staal, Bastiaan B. P.; van Schilt, Marcus A.; Gerritsen, Gijsbert; Meetsma, Auke; Koning, Cor E.; Kemmere, Maartje F.; Keurentjes, Jos T. F.

    2007-01-01

    A novel zinc silsesquioxane complex ([(c-C5H9)(7)Si7O11(OSiMePh2)](2)Zn4Me4 (1)) has been used as a model compound for silica-grafted zinc catalysts in the copolymerization of cyclohexene oxide and CO2. Complex 1 exists as a dimer in the solid state and is moderately active in the copolymerization,

  17. Application of Et3NHCl-AlCl3 Ionic Liquid as an Initiator in Cationic Copolymerization of 1, 3-Pentadiene with Styrene

    Institute of Scientific and Technical Information of China (English)

    Yuan Yuan WANG; Hui SUN; Juan LI; Dong JIANG; Li Yi DAI

    2006-01-01

    The random copolymer poly (1, 3-pentadiene-co-styrene) formed through cationic copolymerization using the triethylamine hydrochloride and hydrous aluminium chloride (Et3NHC1-A1C13) room temperature ionic liquid as initiating agent in toluene was analyzed using IR spectra in conjunction with gel permeation chromatography (GPC). The room temperature ionic liquid was found to have high initiatic activity for copolymerization.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  20. Synthesis of Polyketone by Copolymerization of Styrene and CO Using Carbon Nanotube-Complex Pd2+Catalyst

    Institute of Scientific and Technical Information of China (English)

    郭锦棠; 肖淼; 王海霞; 胡光

    2014-01-01

    The dipping method was devised to deposit Pd onto carbon nanotube as supported catalyst (Pd/CNT) for the copolymerization of carbon monoxide (CO) and styrene(ST) towards the formation of polyketone (PK). The Pd/CNT was characterized by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). The construction and crystallization property of PK were evaluated by Fourier transform infrared spectroscopy (FTIR), 13C-nuclear magnetic resonance(NMR) and XRD, respectively. The catalyst showed excellent activity and reusability in promoting the fabrication of PK. It can be recycled 14 times with the highest total catalytic activity of 4 239.64 gPK/(gPd·h) at Pd content of 8.63wt%. The results indicate that the prepared catalyst is effective to catalyze the copolymerization of CO and styrene.

  1. Ethylene homo- and copolymerization chain-transfers: A perspective from supported (nBuCp)2ZrCl2 catalyst active centre distribution

    Indian Academy of Sciences (India)

    Muhammad Atiqullah; Mamdouh A Al-Harthi; Siripon Anantawaraskul; Abdul-hamid M Emwas

    2015-04-01

    Polymerization chain termination reactions and unsaturation of the polymer backbone end are related. Therefore, in this study, the parameters resulting from the modelling of the active centre distribution of the supported catalyst—silica/MAO/(nBuCp)2ZrCl2—were applied to evaluate the active-centredependent ethylene homo- and copolymerization rates, as well as the corresponding chain termination rates. This approach, from a microkinetic mechanistic viewpoint, elucidates better the 1-hexene-induced positive comonomer effect and chain transfer phenomenon. The kinetic expressions, developed on the basis of the proposed polymerization mechanisms, illustrate how the active site type-dependent chain transfer phenomenon is influenced by the different apparent termination rate constants and momoner concentrations. The active centrespecific molecular weight Mni (for the above homo- and copolymer), as a function of chain transfer probability, pCTi, varied as follows: log(pCTi) = log(mwru)−log(Mni) where mwru is the molecular weight of the repeat unit. The physical significance of this finding has been explained. The homo- and copolymer backbones showed all the three chain end unsaturations (vinyl, vinylidene, and trans-vinylene). The postulated polymerization mechanisms reveal the underlying polymer chemistry. The results of the present study will contribute to develop in future supported metallocene catalysts that will be useful to synthesize polyethylene precursors having varying chain end unsaturations, which can be eventually used to prepare functional polyethylenes.

  2. RING-OPENING POLYMERIZAION OF 2,2-DIMETHYLTRIMETHYLENE CARBONATE INITIATED BY IN SITU GENERATED, TETRAHYDROSALEN STABLIZED YTTRIUM BOROHYDRIDE COMPLEX AND RANDOM COPOLYMERIZATION WITH ε-CAPROLACTONE

    Institute of Scientific and Technical Information of China (English)

    Jing Huang; Jian-fang Yu; Han-jian Yu; Wei-lin Sun; Zhi-quan Shen

    2011-01-01

    The poly(2,2-dimethyltrimethylene carbonate) (PDTC) with one hydroxyl and one formate tenninal fimctions was synthesized by in situ generated, tetrahydrosalen stabilized yttrium borohydride complex. The influences of monomer/initiator molar ratio, temperature and reaction time on polymerization of DTC were investigated. Under the condition: [DTC]/[I] = 500, 55℃, toluene: 0.5 mL, DTC: 0.6 g, PDTC with Mn = 15600 and PDI = 2.15 was obtained.Through 1H-NMR and 13C-NMR analyses, the structure of PDTC was characterized and a coordination-insertion mechanism was proposed. In addition, the random copolymerization of DTC and caprolactone (CL) initiated by rare-earth borohydride compound was studied. The microstructure of PDTC-co-PCL includes four diads: DTC-CL, CL-CL, DTC-DTC and CLDTC, which were determined by the specific signals in 1H-NMR spectra. Based on the typical signals of the formate (δ=8.08) and hydroxyl (δ = 3.34) end groups of PDTC-co-PCL, a mechanism involving DTC monomer inserts before CL during the initiation process was presumed. Furthermore, the thermal properties of amorphous copolymer were characterized by differential scanning calorimetry (DSC). The results support the random structure of PDTC-co-PCL.

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

    Science.gov (United States)

    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…

  4. Experimental effects of dynamics and thermodynamics in nuclear reactions on the symmetry energy as seen by the CHIMERA 4 π detector

    Energy Technology Data Exchange (ETDEWEB)

    De Filippo, E.; Pagano, A. [INFN, Catania (Italy)

    2014-02-15

    Heavy-ion collisions have been widely used in the last decade to constrain the parameterizations of the symmetry energy term of the nuclear equation of state (EOS) for asymmetric nuclear matter as a function of baryonic density. In the Fermi energy domain one is faced with variations of the density within a narrow range of values around the saturation density ρ{sub 0}=0.16 fm{sup -3} down towards sub-saturation densities. The experimental observables which are sensitive to the symmetry energy are constructed starting from the detected light particles, clusters and heavy fragments that, in heavy-ion collisions, are generally produced by different emission mechanisms at different stages and time scales of the reaction. In this review the effects of dynamics and thermodynamics on the symmetry energy in nuclear reactions are discussed and characterized using an overview of the data taken so far with the CHIMERA multi detector array. (orig.)

  5. Diagnosis of enzootic pneumonia in Danish cattle: reverse transcription-polymerase chain reaction assay for detection of bovine respiratory syncytial virus in naturally and experimentally infected cattle

    DEFF Research Database (Denmark)

    Larsen, Lars Erik; Tjørnehøj, Kirsten; Viuff, B.;

    1999-01-01

    A reverse transcription-polymerase chain reaction (RT-PCR) assay was developed for detection of bovine respiratory syncytial virus (BRSV) in lung tissue of naturally and experimentally infected cattle. Primers were selected from the gene coding the F fusion protein, which is relatively conserved...... among BRSV isolates. The RT-PCR assay was highly specific, it yielded positive reactions only when performed on BRSV-infected cell cultures or tissues. The detection limit of the RT-PCR assay was assessed as 5 TCID50. BRSV was detected in tissues of the respiratory tract and in the tracheobroncheal....... (7%), and Pasteurella haemolytica (7%) were the most common bacterial agents found in the lungs. BRSV was identified using a conventional antigen enzyme-linked immunosorbent assay (ELISA) in 23 (17%) animals. The established BRSV-specific RT-PCR assay yielded positive results for the same 23 animals...

  6. Experimental investigation on moving chemical reaction boundary theory for weak-acid-strong-base system with background electrolyte KCl in large concentration.

    Science.gov (United States)

    Cao, C X; Zhou, S L; Qian, Y A; He, Y Z; Yang, L; Qu, Q S; Chen, W K

    2001-07-13

    In this report, the moving chemical reaction boundary (MCRB) was formed with the weak acid of acetic acid (HAc) and the strong alkali of NaOH, coupled with the excess of background electrolyte KCl. The experiments were compared with the predictions by the moving chemical reaction boundary equation (MCRBE). It is very interesting that (1) the experimental results are in good agreement with the predictions with the original MCRBE if the MCRB is an anodic moving boundary, (2) however, the experiments are extremely far away from the predictions with the original MCRBE if a cathodic moving boundary. Hence, the original MCRBE must be corrected under the later situation of cathodic moving MCRB. The corrected MCRBE was well quantitatively proved to be valid for the cathodic moving MNRB formed with the same electrolytes of HAc, NaOH and KCl.

  7. Diagnosis of enzootic pneumonia in Danish cattle: reverse transcription-polymerase chain reaction assay for detection of bovine respiratory syncytial virus in naturally and experimentally infected cattle

    DEFF Research Database (Denmark)

    Larsen, Lars Erik; Tjørnehøj, Kirsten; Viuff, B.

    1999-01-01

    A reverse transcription-polymerase chain reaction (RT-PCR) assay was developed for detection of bovine respiratory syncytial virus (BRSV) in lung tissue of naturally and experimentally infected cattle. Primers were selected from the gene coding the F fusion protein, which is relatively conserved...... among BRSV isolates. The RT-PCR assay was highly specific, it yielded positive reactions only when performed on BRSV-infected cell cultures or tissues. The detection limit of the RT-PCR assay was assessed as 5 TCID50. BRSV was detected in tissues of the respiratory tract and in the tracheobroncheal....... (7%), and Pasteurella haemolytica (7%) were the most common bacterial agents found in the lungs. BRSV was identified using a conventional antigen enzyme-linked immunosorbent assay (ELISA) in 23 (17%) animals. The established BRSV-specific RT-PCR assay yielded positive results for the same 23 animals...

  8. Cationic Ring Opening Copolymerization of 1,3-Dioxolane with Styrene by Montmorillonite Maghnite-H+Catalyst

    OpenAIRE

    Nabil Hamam; Mohammed Issam Ferrahi; Mohammed Belbachir

    2016-01-01

    In the present work, the copolymerization of 1,3-Dioxolane (DXL) with Styrene (St) catalyzed by Maghnite-H+ a montmorillonite sheet silicate clay exchanged with protons, was investigated. The cationic ring opening polymerization was initiated by Maghnite-H+ in bulk. The copolymer obtained was characterized by 1H-NMR, DSC and IR spectroscopy. The studies done, such as the effect of the amount of catalyser on the syntheses of poly (DXL -co- Styrene).

  9. Cationic Ring Opening Copolymerization of 1,3-Dioxolane with Styrene by Montmorillonite Maghnite-H+Catalyst

    Directory of Open Access Journals (Sweden)

    Nabil Hamam

    2016-06-01

    Full Text Available In the present work, the copolymerization of 1,3-Dioxolane (DXL with Styrene (St catalyzed by Maghnite-H+ a montmorillonite sheet silicate clay exchanged with protons, was investigated. The cationic ring opening polymerization was initiated by Maghnite-H+ in bulk. The copolymer obtained was characterized by 1H-NMR, DSC and IR spectroscopy. The studies done, such as the effect of the amount of catalyser on the syntheses of poly (DXL -co- Styrene.

  10. The development of a state-of-the-art experimental setup demonstrated by the investigation of fuel cell reactions in alkaline electrolyte

    Energy Technology Data Exchange (ETDEWEB)

    Wiberg, Gustav Karl Henrik

    2010-10-04

    The objectives of this work can be separated into three different topics: the design and development of a state-of-the art electrochemical experiment setup, which is then followed by two separate experimental studies in alkaline electrolyte. These studies demonstrate the capabilities of the experimental setup, and each focus on separate model catalysts. The first study investigated the influence of Pt oxide formation on the measured catalytic activity of FC relevant reactions on polycrystalline Pt in alkaline electrolyte. The second study focused on the characterisation of the ORR for a non-platinum catalyst, in this case Ag, by adapting the established thin-film RDE methodology employed for characterising Pt based electrocatalysts. A state-of-the-art electrochemical experimental setup comprises of a largely automated setup that allows meticulous control over experimental parameters such as potential, temperature, purging gas and solution convection. In order to realise such a setup, both experimental hardware and software were developed. In particular, a custom built analogue potentiostat optimised for single working electrode measurements was constructed. The potentiostat features R{sub sol}-compensation which can be monitored online due to its fully analogue design, allowing the precise current and potential relationship to be measured. In addition, the experimental throughput was enhanced by fabricating a modular add-on device, the MWE, which allows simultaneous electrochemical measurement on up to 8 parallel working electrodes. The MWE device is compatible with any single channel potentiostat, enhancing existing instrumentation. Several Teflon cells were designed for electrochemical investigations in acid and alkaline electrolytes, and were adapted to work using either the RDE or MWE. A gas changer was also assembled, which enabled computer controlled switching of electrolyte purge gas. Furthermore, in order to control the potentiostat and the accessory

  11. Multi-body simulation of a canine hind limb: model development, experimental validation and calculation of ground reaction forces

    Directory of Open Access Journals (Sweden)

    Wefstaedt Patrick

    2009-11-01

    Full Text Available Abstract Background Among other causes the long-term result of hip prostheses in dogs is determined by aseptic loosening. A prevention of prosthesis complications can be achieved by an optimization of the tribological system which finally results in improved implant duration. In this context a computerized model for the calculation of hip joint loadings during different motions would be of benefit. In a first step in the development of such an inverse dynamic multi-body simulation (MBS- model we here present the setup of a canine hind limb model applicable for the calculation of ground reaction forces. Methods The anatomical geometries of the MBS-model have been established using computer tomography- (CT- and magnetic resonance imaging- (MRI- data. The CT-data were collected from the pelvis, femora, tibiae and pads of a mixed-breed adult dog. Geometric information about 22 muscles of the pelvic extremity of 4 mixed-breed adult dogs was determined using MRI. Kinematic and kinetic data obtained by motion analysis of a clinically healthy dog during a gait cycle (1 m/s on an instrumented treadmill were used to drive the model in the multi-body simulation. Results and Discussion As a result the vertical ground reaction forces (z-direction calculated by the MBS-system show a maximum deviation of 1.75%BW for the left and 4.65%BW for the right hind limb from the treadmill measurements. The calculated peak ground reaction forces in z- and y-direction were found to be comparable to the treadmill measurements, whereas the curve characteristics of the forces in y-direction were not in complete alignment. Conclusion In conclusion, it could be demonstrated that the developed MBS-model is suitable for simulating ground reaction forces of dogs during walking. In forthcoming investigations the model will be developed further for the calculation of forces and moments acting on the hip joint during different movements, which can be of help in context with the in

  12. Change urgent adaptation reaction cardiorespiratory system under the influence of experimental program of the training means in sport dance

    Directory of Open Access Journals (Sweden)

    Lee Bo

    2010-09-01

    Full Text Available Possibilities of increase of function of cardiorespiratory system of dancers are rotined. 24 sportsmen took part in research (12 pair. Directions of strengthening the function of aerobic energy-supply, optimizations of physiological properties of the cardiorespiratory system of organism, are set. The terms of increase of the special capacity are formed. The terms of activation of function of indemnification of increasing acidemia changes and developing on this basis fatigue are offered. Application of the program of trainings facilities specifies on the increase of kinetics and stability of reaction of frequency of heart-throbs.

  13. Experimental studies of the kinetics of small polyatomic free radicals in combustion reactions; Moniatomisten radikaalien kinetiikka palamisreaktioissa, kokeellinen tutkimus

    Energy Technology Data Exchange (ETDEWEB)

    Seetula, J. [Helsinki Univ. (Finland). Lab. of Physical Chemistry

    1996-12-01

    The kinetics of the reactions of CH{sub 2}Cl, CHClBr, CH{sub 3}CCl{sub 2} and CCl{sub 3}, with Cl{sub 2} has been investigated in a tubular reactor coupled to a photoionization mass spectrometer. The radicals of interest, R, were generated homogeneously in the reactor by pulse 248 nm exciplex laser photolysis. The decay of R was monitored as a function of Cl{sub 2} concentration under pseudo-first-order condition to determine the rate constant as a function of temperature pressure. The reactions were studied separately over a temperature range up to a temperature of 873 K. The rate constants of CH{sub 2}Cl, CHClBr and CH{sub 3}CCl{sub 2} radicals determined were fitted to three-parameter Arrhenius-type expression (with units of cm{sup 3} molecule{sup -1} s{sup -1}): k(CH{sub 2}Cl) = 1.05x10{sup -16} x (T){sup 1.4} x exp(-357 J mol{sup -1} / RT), k(CHClBr) = 5.83x10{sup -20} x (T){sup 2.3} x exp(-300 J mol{sup -1}/ RT) and k(CH{sub 3}CCl{sub 2}) 1.10x10{sup -}2{sup 6} x (T){sup 4.3} x exp(15000 J mol{sup -1}/ RT). The rate constants CCl{sub 3} radical were fitted to a two-parameter Arrhenius expression (units in cm{sup 3} molecule{sup -1} s{sup -1}): k(CCl{sub 3}) = (8.1 +- 6.7)10{sup -l3} exp[-(25.0 +- 8.7) kJ mol{sup -1}/ RT]. An Arrhenius expression for the reaction of Cl+CCl{sub 4} -> <- CCl{sub 3}+Cl{sub 2} is also obtained from the kinetics of the reaction of CCl{sub 3} radical with Cl{sub 2} combined with the known heat of formation and entropy values of CCl{sub 3} free radical to be as follows (in units cm{sup 3} molecule{sup -1-}5 s{sup -1}): k(Cl+CCl{sub 4}) = (3.9 + 3.2)10{sup -10} exp[-(71 + 9) kJ mol{sup -1}/ RT]. The error limits stated are l{sigma}+Student`s t and base on statistical uncertainties only. (author)

  14. Metal-Free Alternating Copolymerization of CO2with Epoxides: Fulfilling “Green” Synthesis and Activity

    KAUST Repository

    Zhang, Dongyue

    2016-08-16

    Polycarbonates were successfully synthesized for the first time through the anionic copolymerization of epoxides with CO2, under metal-free conditions. Using an approach based on the activation of epoxides by Lewis acids and of CO, by appropriate cations, well-defined alternating copolymers made of CO, and propylene oxide (PO) or cyclohexene oxide (CHO) were indeed obtained. Triethyl borane was the Lewis acid chosen to activate the epoxides, and onium halides or onium alkoxides involving either ammonium, phosphonium, or phosphazenium cations were selected to initiate the copolymerization. In the case of PO, the carbonate content of the poly(propylene carbonate) formed was in the range of 92-99% and turnover numbers (TON) were close to 500; in the case of CHO perfectly alternating poly(cyclohexene carbonate) were obtained and TON values were close to 4000. The advantages of such a copolymerization system are manifold: (i) no need for multistep catalyst/ligand synthesis as in previous works; (ii) no transition metal involved in the copolymer synthesis and therefore no coloration of the samples isolated; and (iii) no necessity for postsynthesis purification.

  15. Detection and strain differentiation of infectious bronchitis virus in tracheal tissues from experimentally infected chickens by reverse transcription-polymerase chain reaction. Comparison with an immunohistochemical technique

    DEFF Research Database (Denmark)

    Handberg, Kurt; Nielsen, O.L.; Pedersen, M.W.;

    1999-01-01

    Oligonucleotide pairs were constructed for priming the amplification of fragments of nucleocapsid (N) protein and spike glycoprotein (S) genes of avian infectious bronchitis virus (IBV) by reverse transcription-polymerase chain reaction (RT-PCR). One oligonucleotide pair amplified a common segment......3896 and 793B strains of IBV, respectively, Groups of specific pathogen free chickens were experimentally inoculated with the Massachusetts (H120, M41), the D1466 and the 793B strains of IBV, and tracheal tissue preparations were made from each bird for RT-PCR and for immunohistochemistry (IHC) up to 3...

  16. Preparation of sulphonate-containing core/shell latex particles via seeded emulsion copolymerization

    Institute of Scientific and Technical Information of China (English)

    Ji Shuai Wang; Wei Deng; Yun Shen Chen; Cheng You Kan

    2010-01-01

    In this study,P(St-MAA)seed latex particles were first prepared via soap-free emulsion polymerization of styrene(St)and methacrylic acid(MAA),then the seed particles were allowed to swell with St at room temperature,and the P(St-MAA)/P(St-NaSS)core/shell latex particles were then synthesized via seeded emulsion copolymerization of St and sodium styrene sulphonate(NaSS)using AIBN as initiator in the presence of N,N'-methylenebisacrylamide(BAA,water-soluble crosslinker).Results showed that the polymerization could be carried out smoothly when the ratio of BAA to total monomers was less than 3 mol%,the narrow dispersed P(St-MAA)seed particles with the diameter of 150 nm and the P(St-MAA)/P(St-NaSS)core/shell latexes with the particle size of about 200 nm were synthesized.When the 25/75 mole ratio of NaSS/(St+MAA)and 2 mol% of BAA were used in the seeded emulsion polymerization,the resulted P(St-MAA)/P(St-NaSS)latex product showed a low weight loss after water extraction,and the NaSS unit content in the whole particle and in the shell reached 11.7 mol% and 34.6 mol%,respectively.

  17. Ionic Liquid-Complex Pd/C System as Catalyst for Copolymerization of CO and Styrene

    Institute of Scientific and Technical Information of China (English)

    王海霞; 郭锦棠; 胡光; 冯亚凯; 武瑞涛

    2014-01-01

    The copolymerization of CO and styrene catalyzed by Pd/C toward the formation of polyketones (PK)was studied in the N-valeronitrile-N'-methylimidazolium hexafluorophosphate ([C4CNmim]+PF6-) medium. The synthe-sized PK was characterized by Fourier transform infrared(FTIR), elemental analysis, 13C-nuclear magnetic resonance (13C-NMR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and gel permeation chro-matography (GPC). The supported ionic liquid film on the surface of Pd/C catalyst can prevent the products from covering the hole of active carbon due to its chemical stability and weak coordination ability with metal ions, and thus efficiently improve the catalytic activity. The effects of different amounts of ionic liquid on the catalytic activity and reusability of the catalyst and the molecular weight of PK were discussed. When the usage of ionic liquid is 10wt%(0.1 g ionic liquid/1 g active carbon carrier) and the theoretical content of Pd2+is 5wt%(0.05 g Pd2+/1 g active car-bon carrier), the highest catalytic activity 2 963.64 gSTCO/(gPd·h) is achieved with the molecular weight and polydispersity index of PK as Mn=9 684, Mw=13 452 and Mw/Mn=1.389.

  18. Graft Copolymerization of Methyl Methacrylate Monomer onto Starch and Natural Rubber Latex Initiated by Gamma Irradiation

    Directory of Open Access Journals (Sweden)

    S. Iskandar

    2011-04-01

    Full Text Available To obtain the degradable plastic, the graft copolymerization of methyl methacrylate onto starch and natural rubber latex was conducted by a simultaneous irradiation technique. Gamma-ray from cobalt-60 source was used as the initiator. The grafted copolymer of starch-polymethyl methacrylate and the grafted copolymer of natural rubber-polymethyl methacrylate were mixed in the blender, and dried it in the oven. The dried grafted copolymer mixture was then molded using hydraulic press machine. The effect of irradiation dose, composition of the grafted copolymer mixture, film forming condition and recycle effect was evaluated. The parameters observed were tensile strength, gel fraction and soil burial degradability of grafted copolymer mixture. It was found that the tensile strength of grafted copolymer mixture increased by -ray irradiation. Increasing of the grafted copolymer of natural rubber-polymethyl methacrylate content, the gel fraction and tensile strength of the grafted copolymer mixture increased. The tensile strength of the grafted copolymer mixture was increased from 18 MPa to 23 MPa after recycled (film forming reprocessed 3 times. The grafted copolymer mixture was degraded completely after soil buried for 6 months

  19. Fluorinated polymides for interlayer dielectric applications: Tailoring of properties via copolymerization

    Energy Technology Data Exchange (ETDEWEB)

    Auman, B.C. [Du Pont Electronic Materials, Wilmington, DE (United States); McKerrow, A.J.; Ho, P.S. [Univ. of Texas, Austin, TX (United States)] [and others

    1996-10-01

    Over the past several years DuPont has been exploring new, rod-like fluorinated polyimides for interlayer dielectric (ILD) applications. It has been shown that copolymerization is a versatile method for tailoring properties of these rigid polyimides. Initial product offerings from DuPont showed an excellent balance of properties for ILD applications. These materials, however, due to their highly rod-like structure and very low in-plane coefficient of thermal expansion (CTE), actually yielded negative thermal stresses on silicon at the 1 {mu}m thicknesses typical of interlayer dielectrics. More flexible materials with higher CTE typically yield positive stress values which can be undesirably quite high. The dielectric constant of these highly rod-like fluorinated polyimides was also somewhat anisotropic, again due to the rod-like nature and resulting high in-plane orientation of these polyimides. Since a thermal stress on silicon near zero and a more isotropic dielectric constant are likely the most desirable states for an ILD, the highly rod-like polyimide was further optimized by incorporation of a more flexible fluorinated comonomer, 6FDA, at various levels to increase CTE and balance dielectric constant. The various properties of this series of fluorinated polyimides were investigated. The results have shown that it is indeed possible to obtain near zero stress on silicon while attaining more isotropic dielectric constant via structure optimization.

  20. Template-Directed Copolymerization, Random Walks along Disordered Tracks, and Fractals

    Science.gov (United States)

    Gaspard, Pierre

    2016-12-01

    In biology, template-directed copolymerization is the fundamental mechanism responsible for the synthesis of DNA, RNA, and proteins. More than 50 years have passed since the discovery of DNA structure and its role in coding genetic information. Yet, the kinetics and thermodynamics of information processing in DNA replication, transcription, and translation remain poorly understood. Challenging issues are the facts that DNA or RNA sequences constitute disordered media for the motion of polymerases or ribosomes while errors occur in copying the template. Here, it is shown that these issues can be addressed and sequence heterogeneity effects can be quantitatively understood within a framework revealing universal aspects of information processing at the molecular scale. In steady growth regimes, the local velocities of polymerases or ribosomes along the template are distributed as the continuous or fractal invariant set of a so-called iterated function system, which determines the copying error probabilities. The growth may become sublinear in time with a scaling exponent that can also be deduced from the iterated function system.

  1. Molecular Imprinted Membrane with High Flux by Surface Photo-grafting Copolymerization

    Institute of Scientific and Technical Information of China (English)

    李爽; 张凤宝; 张国亮; 王燕

    2005-01-01

    Molecular imprinted polymer membranes (MIM) combine the merits of molecular imprint and membrane technology. In this work, a very thin of imprinted polymer that can specifically and selectively absorb the basic template (adenine) was grafted on the surface of polyvinylidene fluoride membrane by photo-grafting copolymerization. Because the molecular imprinted polymer is grafted on the surface of the matrix membrane without blocking the membrane pores, the resultant MIMs have high flux as microfiltration membrane (0.26 mol·m-2·h-1 of template and flux for distilled water was 3.6 ml·mim-1·cm-2 at 0.8 MPa). Moreover, the MIMs can absorb/desorb template molecules rapidly. Usually, it only takes several minutes for MIMs to absorb more than 75% of the template (adenine) in aqueous solution. And the influences of the type and amount of the functional monomers, the amount of the cross-linker on the absorption capability are discussed to determine the optimal preparation conditions。

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

    Science.gov (United States)

    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.

  3. Swelling behaviors,tensile properties and thermodynamic interactions in APS/HEMA copolymeric hydrogels

    Institute of Scientific and Technical Information of China (English)

    LIN Zhihui; WU Wenhui; WANG Jianquan; JIN Xin

    2007-01-01

    A series of hydrogels was synthesized from hydrophobic allyl phenyl sulfone (APS) and hydrophilic 2-hydroxyethyl methacrylate (HEMA) by bulk flee radical copolymerization.The effects of APS content and temperature were studied on network parameters such as efiective crosslink density(ve),molar mass between crosslinks(Mc) and polymer-water interaction parameter (χ) of hydrogels.The increase in APS content was shown to enhance hydrophobic bonding within hydrogel.1eading to the decrease in equilibrium water content(EWC)and the increase in volume fraction of polymer in hydrogel(φ2),tensile strength and Young'S modulus.At the same time,the increases in (Ve) and φ and the decrease in Mc were also observed.When the temperature is increased from 273 to 343 K,the hydrogel A/H3 undergoes decreasing in EWC and increasing in φ2 and χ values.The thermodynamic analysis indicated that the swelling process is an exothermic process.

  4. Experimentally constrained (p ,γ )89Y and (n ,γ )89Y reaction rates relevant to p -process nucleosynthesis

    Science.gov (United States)

    Larsen, A. C.; Guttormsen, M.; Schwengner, R.; Bleuel, D. L.; Goriely, S.; Harissopulos, S.; Bello Garrote, F. L.; Byun, Y.; Eriksen, T. K.; Giacoppo, F.; Görgen, A.; Hagen, T. W.; Klintefjord, M.; Renstrøm, T.; Rose, S. J.; Sahin, E.; Siem, S.; Tornyi, T. G.; Tveten, G. M.; Voinov, A. V.; Wiedeking, M.

    2016-04-01

    The nuclear level density and the γ -ray strength function have been extracted for 89Y by using the Oslo method on 89Y(p ,p'γ )89Y coincidence data. The γ -ray strength function displays a low-energy enhancement consistent with previous observations in this mass region (Mo-9893). Shell-model calculations support the conclusion that the observed enhancement is due to strong, low-energy M 1 transitions at high excitation energies. The data were further used as input for calculations of the 88Sr(p ,γ )89Y and 88Y(n ,γ )89Y cross sections with the talys reaction code. Comparison with cross-section data, where available, as well as with values from the BRUSLIB library, shows a satisfying agreement.

  5. Semi-refined κ-carrageenan: Part 1. Chemical modification of semi-refined κ-carrageenan via graft copolymerization method, optimization process and characterization of its super absorbent hydrogel.

    Directory of Open Access Journals (Sweden)

    Jamaluddin Mohd. Daud

    2015-06-01

    Full Text Available This study was carried out for the preparation of super absorbent polymer hydrogel from semi-refined κ-carrageenan originated from Kappaphycusalvarezii (Doty Doty ex P. Silva through graft copolymerization method with acrylic acid. The reaction was carried out in an aqueous solution in the presence of N,N-methylene bis-acrylamide as a crosslinker and ammonium persulphate as an initiator. The effect of the amount of cross linker, monomer, initiator and alkali on the swelling capacity of the hydrogel was investigated for optimum conditions.After preparing the desired hydrogel according to optimum conditions, the hydrogel was characterized by FTIR spectroscopy, SEM microscopy and swelling capacity measurement.

  6. The first experimental confirmation of the fractional kinetics containing the complex-power-law exponents: Dielectric measurements of polymerization reactions

    Science.gov (United States)

    Nigmatullin, R. R.; Arbuzov, A. A.; Salehli, F.; Giz, A.; Bayrak, I.; Catalgil-Giz, H.

    2007-01-01

    For the first time we achieved incontestable evidence that the real process of dielectric relaxation during the polymerization reaction of polyvinylpyrrolidone (PVP) is described in terms of the fractional kinetic equations containing complex-power-law exponents. The possibility of the existence of the fractional kinetics containing non-integer complex-power-law exponents follows from the general theory of dielectric relaxation that has been suggested recently by one of the authors (R.R.N). Based on the physical/geometrical meaning of the fractional integral with complex exponents there is a possibility to develop a general theory of dielectric relaxation based on the self-similar (fractal) character of the reduced (averaged) microprocesses that take place in the mesoscale region. This theory contains some essential predictions related to existence of the non-integer power-law kinetics and the results of this paper can be considered as the first confirmation of existence of the kinetic phenomena that are described by fractional derivatives with complex-power-law exponents. We want to stress here that with the help of a new complex fitting function for the complex permittivity it becomes possible to describe the whole process for real and imaginary parts simultaneously throughout the admissible frequency range (30 Hz-13 MHz). The fitting parameters obtained for the complex permittivity function for three temperatures (70, 90 and 110 °C) confirm in general the picture of reaction that was known qualitatively before. They also reveal some new features, which improve the interpretation of the whole polymerization process. We hope that these first results obtained in the paper will serve as a good stimulus for other researches to find the traces of the existence of new fractional kinetics in other relaxation processes unrelated to the dielectric relaxation. These results should lead to the reconsideration and generalization of irreversibility and kinetic phenomena that

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

    Science.gov (United States)

    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

  8. Experimental and Quantum Mechanics Investigations of Early Reactions of Monomethylhydrazine with Mixtures of NO2 and N2O4

    Science.gov (United States)

    2013-02-15

    implemented in Jaguar [22], using a dielectric constant of 80.37 and a spherical cavity of radius 1.40A for water. We con- sider that the solvation...were carried out with Jaguar 7.6 [23]. The UCCSD(T) calculation was done with NWChem [24,25]. 3. Experimental results 3.1. Summary of spectroscopic...1994) 11875– 11882. [23] Jaguar , Schrodinger, LLC, New York, NY, 2007. [24] M. Valiev, E.J. Bylaska, N. Govind, K. Kowalski, T.P. Straatsma, H.J.J. Van

  9. Experimental measurements of the O15(alpha,gamma)Ne19 reaction rate vs. observations of type I X-ray bursts

    CERN Document Server

    Fisker, J L; Görres, J; Wiescher, M; Cooper, R L; Fisker, Jacob Lund; Tan, Wanpeng; Goerres, Joachim; Wiescher, Michael; Cooper, Randall L.

    2007-01-01

    Neutron stars in close binary star systems often accrete matter from their companion stars. Thermonuclear ignition of the accreted material in the atmosphere of the neutron star leads to a thermonuclear explosion which is observed as an X-ray burst occurring periodically between hours and days depending on the accretion rate. The ignition conditions are characterized by a sensitive interplay between the continuously accreting fuel supply and depletion by nuclear burning via the hot CNO cycles. Therefore the ignition depends critically on the hot CNO breakout reaction O15(alpha,gamma)Ne19 that regulates the flow between the beta-limited hot CNO cycle and the rapid proton capture process. Until recently, the O15(alpha,gamma)Ne19 reaction rate was not known experimentally and the theoretical estimates carried significant uncertainties. In this paper we report on the astrophysical consequences of the first measurement of this reaction rate on the thermonuclear instability that leads to type I X-ray bursts on accr...

  10. Influence of a dexamethasone-eluting covered stent on tissue reaction: an experimental study in a canine bronchial model

    Energy Technology Data Exchange (ETDEWEB)

    Shin, Ji Hoon; Song, Ho-Young; Choi, Gi Bok; Kim, Tae-Hyung; Suh, Ji-Yeon [University of Ulsan College of Medicine, Department of Radiology, Asan Medical Center, Seoul (Korea); Seo, Tae-Seok [Gachon Medical School, Department of Radiology, Gil Medical Center, Inchon (Korea); Yuk, Soon Hong [Hannam University, Department of Polymer Science and Engineering, College of Engineering, Daejeon (Korea); Kim, Young-Hwa [Soonchunhyang University Chonan Hospital, Department of Radiology, Chonan (Korea); Cho, Yong-Mee [University of Ulsan College of Medicine, Department of Pathology, Asan Medical Center, Seoul (Korea)

    2005-06-01

    This study was designed to evaluate the feasibility and efficacy of a dexamethasone (DXM)-eluting, covered, self-expanding metallic stent to reduce tissue reaction following stent placement in a canine bronchial model. We placed a DXM-eluting, polyurethane-covered, self-expanding metallic stent (drug stent, DS) and a polyurethane-covered, self-expanding metallic stent (control stent, CS) alternately in each left main bronchus and left lower lobe bronchus in 12 dogs. The stents were 20 mm in diameter and length when fully expanded. The dose of DXM was approximately 36.7 mg in each DS, but was absent in the CS. The dogs were euthanased 1 week (n=4), 2 weeks (n=4) or 4 weeks (n=4) after stent placement. Histologic findings, such as epithelial erosion/ulcer or granulation tissue thickness, were obtained from the mid-portion of the bronchus, where the stent had been placed, and evaluated between DS and CS. There were no procedure-related complications or malpositioning of any of the bronchial stents. Stent migration was detected in one dog just before euthanasia 1 week following stent placement. Stent patency was maintained until euthanasia in all dogs. Epithelial erosion/ulcer (%) was significantly less in the DS (mean{+-}standard deviation, 46.88{+-}23.75) than in the CS (73.75{+-}14.08) (P=0.026) for all time-points. There was a decrease in epithelial erosion/ulcer as the follow-up period increased in both DS and CS. The granulation tissue thickness (mm) was less in DS (2.63{+-}2.05) than in CS (3.49{+-}2.95), although the difference was not significant (P=0.751) for all time-points. There was a tendency toward an increase in granulation tissue thickness and chronic lymphocytic infiltration as the follow-up period increased in both DS and CS. In conclusion, DXM-eluting, covered, self-expanding metallic stent seems to be effective in reducing tissue reaction secondary to stent placement in a canine bronchial model. (orig.)

  11. Detection of Paragonimus heterotremus eggs in experimentally infected cats by a polymerase chain reaction-based method.

    Science.gov (United States)

    Intapan, Pewpan M; Wongkham, Chaisiri; Imtawil, Kanokwan J; Pumidonming, Wilawan; Prasongdee, Thidarat K; Miwa, Masanao; Maleewong, Wanchai

    2005-02-01

    A polymerase chain reaction (PCR) procedure for the detection of Paragonimus heterotremus eggs in stool samples was developed and compared with Stoll's egg count method. The primers were designed on the basis of a previously constructed pPH-13-specific DNA probe, which produced an approximate 0.5-kb amplified product. This PCR method could detect as few as 5 eggs in 0.6 g of artificially inoculated feces of a healthy control cat or as little as 1 x 10(-4) ng of P. heterotremus genomic DNA. The assay had 100% sensitivity in all infected cats. The method did not yield an approximate 0.5-kb product with DNA from other parasites such as Gnathostoma spinigerum, Trichinella spiralis, Fasciola gigantica, Echinostoma malayanum, Opisthorchis viverrini, Dirofilaria immitis, and Taenia saginata; exceptions were Paragonimus siamensis and Paragonimus westermani. In addition, no genomic DNA from Escherichia coli, Burkholderia pseudomallei, Acinetobacter anitratus, Mycobacterium tuberculosis, Staphylococcus aureus, beta-Streptococcus grA, and Proteus mirabilis or from the vertebrate and invertebrate hosts of P. heterotremus was amplified in the PCR assay. This assay has great potential for application in clinical epidemiological studies.

  12. Psychometric properties of reaction time based experimental paradigms measuring anxiety-related information-processing biases in children.

    Science.gov (United States)

    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.

  13. Experimental cross-sections for proton induced nuclear reactions on mercury up to 65 MeV

    Science.gov (United States)

    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.

  14. The effects of stress concentrations on reaction progress: an example from experimental growth of magnesio-aluminate spinel at corundum - periclase interfaces under uniaxial load

    Science.gov (United States)

    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

  15. Experimental studies on the neutron emission spectrum and induced radioactivity of the sup 7 Li(d,n) reaction in the 20-40 MeV region

    CERN Document Server

    Baba, M; Hagiwara, M; Sugimoto, M; Miura, T; Kawata, N; Yamadera, A; Orihara, H

    2002-01-01

    To improve the data accuracy of the neutron emission spectrum of the sup 7 Li(d,n) reaction and the radioactivity ( sup 7 Be, sup 3 H, etc.) accumulated in the sup 7 Li target in IFMIF, we have measured the neutron emission spectrum and the radioactivity of sup 7 Be induced in the lithium target for 25 MeV deuterons at the Tohoku University AVF cyclotron (K=110) facility. Neutron spectra were measured with the time-of-flight (TOF) method at four laboratory angles by using a beam swinger system and a well collimated TOF channel. Induced radioactivity was measured by detecting the gamma-rays from sup 7 Be with a pure Ge detector. Experimental results are compared with other experimental data. The present result of neutron emission spectra are in qualitative agreement with other experimental data but that of sup 7 Be production was much larger than expected by the recent codes. Measurement will be extended to several incident energies up to 40 MeV.

  16. Experimental studies on the neutron emission spectrum and induced radioactivity of the {sup 7}Li(d,n) reaction in the 20-40 MeV region

    Energy Technology Data Exchange (ETDEWEB)

    Baba, M. E-mail: babam@cyric.tohoku.ac.jp; Aoki, T.; Hagiwara, M.; Sugimoto, M.; Miura, T.; Kawata, N.; Yamadera, A.; Orihara, H

    2002-12-01

    To improve the data accuracy of the neutron emission spectrum of the {sup 7}Li(d,n) reaction and the radioactivity ({sup 7}Be, {sup 3}H, etc.) accumulated in the {sup 7}Li target in IFMIF, we have measured the neutron emission spectrum and the radioactivity of {sup 7}Be induced in the lithium target for 25 MeV deuterons at the Tohoku University AVF cyclotron (K=110) facility. Neutron spectra were measured with the time-of-flight (TOF) method at four laboratory angles by using a beam swinger system and a well collimated TOF channel. Induced radioactivity was measured by detecting the gamma-rays from {sup 7}Be with a pure Ge detector. Experimental results are compared with other experimental data. The present result of neutron emission spectra are in qualitative agreement with other experimental data but that of {sup 7}Be production was much larger than expected by the recent codes. Measurement will be extended to several incident energies up to 40 MeV.

  17. EFFECTS OF REACTION AND PROCESSING PARAMETERS ON ETHYLENE POLYMERIZATION USING DIFFERENT ZIEGLER-NATTA CATALYSTS:EMPLOYMENT OF TAGUCHI EXPERIMENTAL DESIGN AND RESPONSE SURFACE METHOD

    Institute of Scientific and Technical Information of China (English)

    Mohammad Najafi; Vahid Haddadi-Asl

    2007-01-01

    Different Ziegler-Natta catalysts were employed to polymerize ethylene.To investigate the influences of reaction parameters,namely Al/Ti molar ratio,hydrogen and processing parameters,I.e.ethylene pressure and temperature,a Taguchi experimental design was worked out.An L27 orthogonal array was chosen to take the above-mentioned parameters and relevant interactions into account.Response surface method was the tool used to analyze the experimental design results.Al/Ti,ethylene pressure and temperature were selected as experimental design factors.and catalyst activity and polymerization yield were the response parameters.Increasing pressure,due to an increment in monomer accessibility,and rising Al/Ti,because of higher reduction in the catalysts,cause an increase in both polymerization yield and catalyst activity.Nonetheless,a higher temperature,thanks to reducing ethylene solubility in the slurry medium and partially catalyst destruction.lead to a reduction in both response parameters.A synergistic eflfect was also observed between temperature and pressure.All catalyst activities will reduce in the presence of hydrogen.Molecular weight also shows a decline in the presence of hydrogen as a transfer agent.However,the polydispersity index remains approximately intact.Using SEM,various morphologies,owing to different catalyst morphologies,were seen for the polyethylene.

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

    Science.gov (United States)

    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. Copyright © 2015 Elsevier Ltd. All rights reserved.

  19. Experimental study of the pathogenesis of moyamoya disease: histological changes in the arterial wall caused by immunological reactions in monkeys.

    Directory of Open Access Journals (Sweden)

    Terai Y

    2003-10-01

    Full Text Available Moyamoya disease is a progressive vascular disorder of unknown etiology. Theories of inflammatory and immunologic mechanisms have been proposed as the pathogeneses. We have designed a new method of administering N-acetylmuramyl-L-alanyl-D-isoglutamine (MDP for experimental induction of moyamoya disease using an intravascular interventional technique combined with rod-shaped embolic materials made from lactic acid-glycolic acid copolymer. The embolic materials containing MDP were repeatedly injected into the right internal carotid artery of monkeys in the embolic group. Intravenous injections of MDP solution alone were performed in the intravenous group. Histological examination of the arteries demonstrated reduplication and lamination of the internal elastic laminae, which corresponded with findings of moyamoya disease in both groups. These histological changes occurred not only in the intracranial arteries on the embolization side, but also in the contralateral intracranial and even extracranial arteries. The changes were more prominent in the intravenous group than in the embolic group. We conclude that the systemic humoral factors induced by MDP in this study may be important in the pathogeneses of moyamoya disease. Our observations suggest that moyamoya disease is a systemic vascular disease and has an etiologic factor affecting both intracranial and extracranial arteries

  20. Manganese(III) Schiff base complexes: chemistry relevant to the copolymerization of epoxides and carbon dioxide.

    Science.gov (United States)

    Darensbourg, Donald J; Frantz, Eric B

    2007-07-23

    Schiff base complexes of the form (acacen)Mn(III)X (acacen = N,N'-bis(acetylacetone)-1,2-ethylenediimine), where X = OAc, Cl, or N(3), have been evaluated for their ability to couple CO(2) and cyclohexene oxide in the presence of a variety of cocatalysts to provide cyclic or polycarbonates. These complexes proved to be ineffective at catalyzing this process; however, valuable information related to the coordination chemistry of these manganese Schiff bases was elucidated. Of importance, mechanistic findings as revealed by comprehensive studies involving structurally related (salen)CrX and (salen)CoX complexes strongly support the requirement of six-coordinate metal species for the effective copolymerization of CO(2) and epoxides. In the case of these Mn(III) complexes, it was determined that in chloroform or toluene solution a five-coordinate species was greatly favored over a six-coordinate species even in the presence of 20 equiv or more of various Lewis bases. Significantly epoxide monomers such as propylene oxide and cyclohexene oxide displayed no tendency to bind to these (acacen)MnX derivatives, even when used as solvents. Only in the case of excessive quantities of heterocyclic amines such as pyridine, DMAP, and DBU was spectral evidence of a six-coordinate Mn derivative observed in solution. X-ray crystal structures are provided for many of the complexes involved in this study, including the one-dimensional polymeric structures of [(acacen)MnOAc x 2H(2)O](n), [(acacen)MnN(3)](n) (mu(1,3)-N(3)), and a rare mixed bridging species [(acacen)MnN(3)](n) (mu(1,3)-N(3)/mu(1,1)-N(3)). In addition, a structure was obtained in which the unit cell contains both a (acacen)MnN(3)(DMAP) and a (acacen)MnN(3) species.

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

    Directory of Open Access Journals (Sweden)

    Zhengde Tan

    2013-01-01

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

  2. POE-PEG-POE triblock copolymeric microspheres containing protein. II. Polymer erosion and protein release mechanism.

    Science.gov (United States)

    Wan, J P; Yang, Y Y; Chung, T S; Tan, D; Ng, S; Heller, J

    2001-07-10

    The first paper of this series presented the fabrication and characterization of POE-PEG-POE triblock copolymeric microspheres containing protein. In this paper, we focus on the polymer erosion and the mechanism of protein release. Fourteen-week in vitro behaviors of POE-PEG-POE microspheres loaded with bovine serum albumin (BSA) have been monitored. SEM micrographs reveal that after 14-week incubation in PBS buffer, pH 7.4, 37 degrees C, the polymeric particles remain spherical despite mass loss of almost 90%. On the other hand, molecular weight undergoes a high initial loss of 38% and 44% during the first 2-week incubation for POE-PEG(5%)-POE and POE-PEG(10%)-POE, respectively. Then, it keeps relatively unchanged over 12 weeks. However, POE-PEG(20%)-POE copolymer provides a better compatibility between the POE and PEG blocks. Hydrolysis is homogeneous through the polymer backbone. Thus, its molecular weight remains relatively constant and mass loss shows quite sustained over the 14-week in vitro release. The similar phenomena are observed in the polydispersity index of the degrading copolymers. SDS-PAGE of the encapsulated BSA within the POE-PEG(5%)-POE microspheres displays that the structural integrity of BSA is intact for at least 8 weeks due to a mild environment provided by the copolymer. In addition, XPS and FTIR are utilized to investigate protein behaviors in the degrading microspheres. Protein release from the POE-PEG-POE microspheres shows a biphasic pattern, characterized by an initial stage followed by a non-detectable release. The non-release phase is dominated by either slow polymer degradation or dense microsphere matrix structures. The microsphere formulation is optimized and a sustained protein release over 2 weeks is achieved by using POE-PEG(20%)-POE at a high protein loading.

  3. The development of a state-of-the-art experimental setup demonstrated by the investigation of fuel cell reactions in alkaline electrolyte

    Energy Technology Data Exchange (ETDEWEB)

    Wiberg, Gustav Karl Henrik

    2010-10-04

    The objectives of this work can be separated into three different topics: the design and development of a state-of-the art electrochemical experiment setup, which is then followed by two separate experimental studies in alkaline electrolyte. These studies demonstrate the capabilities of the experimental setup, and each focus on separate model catalysts. The first study investigated the influence of Pt oxide formation on the measured catalytic activity of FC relevant reactions on polycrystalline Pt in alkaline electrolyte. The second study focused on the characterisation of the ORR for a non-platinum catalyst, in this case Ag, by adapting the established thin-film RDE methodology employed for characterising Pt based electrocatalysts. A state-of-the-art electrochemical experimental setup comprises of a largely automated setup that allows meticulous control over experimental parameters such as potential, temperature, purging gas and solution convection. In order to realise such a setup, both experimental hardware and software were developed. In particular, a custom built analogue potentiostat optimised for single working electrode measurements was constructed. The potentiostat features R{sub sol}-compensation which can be monitored online due to its fully analogue design, allowing the precise current and potential relationship to be measured. In addition, the experimental throughput was enhanced by fabricating a modular add-on device, the MWE, which allows simultaneous electrochemical measurement on up to 8 parallel working electrodes. The MWE device is compatible with any single channel potentiostat, enhancing existing instrumentation. Several Teflon cells were designed for electrochemical investigations in acid and alkaline electrolytes, and were adapted to work using either the RDE or MWE. A gas changer was also assembled, which enabled computer controlled switching of electrolyte purge gas. Furthermore, in order to control the potentiostat and the accessory

  4. Research progress of catalysts for copolymerization of CO2 and epoxides%二氧化碳与环氧化合物共聚反应催化剂的研究进展

    Institute of Scientific and Technical Information of China (English)

    秦刚; 范利丹; 曹少魁; 卜站伟; 陈涛; 易奎

    2013-01-01

    Chemical fixation of CO2 is a very attractive subject not only from carbon resource utilization, but also from increasing environmental concerns. In this paper, the significance and methods of CO2 participation in chemical reactions are introduced. Carbon dioxide-based polycarbonates is compared with bisphenol-A polycarbonates, and the emphasis is highly efficient catalyst in copolymerization of CO2 and epoxides to produce aliphatic polycarbonates. Recent progress of the catalysts for copolymerization of CO2 and epoxides is reviewed, and their advantages and disadvantages are discussed. The difficulties in future research are pointed out. The copolymerization product has wide application prospect due to its biodegradability and carbon oxide as raw material.%二氧化碳综合利用对于减轻温室效应和开发有机化工新碳源都具有重要价值.本文简要介绍了二氧化碳化学转化的研究意义,总结了其参与化学反应的主要途径,对比了二氧化碳基聚碳酸酯与双酚A型聚碳酸酯,指出开发催化二氧化碳与环氧化合物共聚反应的高效催化剂是该领域研究的重点.重点综述了二氧化碳与环氧化合物共聚各类催化剂的研究进展,并探讨了其优缺点.分析得出该研究领域进一步发展面临的主要问题是催化剂效率和共聚产物的性能与应用.产品由于具有生物降解性且其原料为储量丰富的二氧化碳,因而具有广阔的应用前景.

  5. Population dynamics and host reactions in young foxes following experimental infection with the minute intestinal fluke, Haplorchis pumilio

    Directory of Open Access Journals (Sweden)

    Nissen Sofie

    2013-01-01

    Full Text Available Abstract Background Infections with fish-borne zoonotic trematodes (FZT including the minute intestinal fluke, Haplorchis pumilio, are highly prevalent in Southeast Asia. However, little is known about the infection dynamics and clinical symptoms in the final hosts which include a range of animal species and man. We aimed to generate such information using an experimental model with H. pumilio in foxes. Method Eight commercially bred foxes were each orally infected with 2000 H. pumilio metacercariae. Another three foxes served as uninfected controls. Faecal examination for eggs was performed twice weekly. The body weight was measured, standard haematological and biochemical analysis were performed regularly. All foxes were euthanized at day 56 post infection (p.i.. Adult worms were quantified and location in the small intestine noted. Results Anorexia was observed in all infected foxes starting day 12 p.i. and lasting for approximately a week. A weight loss was noticed in the infected group in weeks 3–6 p.i. Five of eight infected foxes excreted H. pumilio eggs day 9 p.i. onwards, the remaining three started on day 13 p.i. Mean (± SD faecal egg counts showed an initial peak at day 16–20 with a maximum of 1443 ± 1176 eggs per gram of faeces (epg, where after a stable egg output around 4–500 epg was seen. Worm burdens ranged between 116–2070 adult flukes with a mean (± SD worm recovery of 948 ± 666. The majority of worms were found in the lower part of the jejunum. Total white blood cell and lymphocyte counts were significant lower in the infected group from first week p.i. onwards and throughout the study period. A significantly lower level of eosinophils was found in week 2 p.i. and transient anaemia was seen in week 2 and 4 p.i. Conclusion This study showed a short prepatency period, an initial peak in egg excretion, establishment of infection in all animals with predilection site in the lower jejunum and a marked but

  6. Detection of egg drop syndrome 1976 virus by polymerase chain reaction and study of its persistence in experimentally infected layer birds.

    Science.gov (United States)

    Kumar, N S; Kataria, J M; Koti, M; Dhama, K; Toroghi, R

    2003-01-01

    Polymerase chain reaction (PCR) assay was developed for the detection of Egg drop syndrome 1976 (EDS-76) virus in tissues, namely in the uterus, spleen and buffy coat. It was also used to study the persistence of the virus in tissues of experimentally infected layer birds. The PCR assay could detect as little as 10 fg of purified EDS-76 viral DNA. It also amplified the DNA of Fowl adenovirus serotypes 4 (FAV-4) and 8 (FAV-8). The virus persisted in the uterus up to day 21 post infection (p.i.). Detection of EDS-76 viral DNA in the buffy coat could be useful for studying the occurrence of the respective disease in layer bird flocks.

  7. Comparison between specific and multiplex reverse transcription-polymerase chain reaction for detection of hepatitis A virus, poliovirus and rotavirus in experimentally seeded oysters

    Directory of Open Access Journals (Sweden)

    C Coelho

    2003-06-01

    Full Text Available Outbreaks of gastroenteritis have occurred among consumers of raw or undercooked shellfish harvested from faecally polluted waters. A multiplex reverse transcription-polymerase chain reaction (RT-PCR was applied for the simultaneous detection of hepatitis A virus (HAV, poliovirus (PV and simian rotavirus (RV-SA11 and compared with specific primers for each genome sequence. Three amplified DNA products representing HAV (192 bp, PV (394 bp and RV (278 bp were identified when positive controls were used. However, when tested on experimentally contaminated raw oysters, this method was not able to detect the three viruses simultaneously. This is probably due to the low concentration of viral RNAs present in oyster extract which were partially lost during the extracts preparation.

  8. 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

    Science.gov (United States)

    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.

  9. On the relevance of the H2 + O reaction pathway for the surface formation of interstellar water - A combined experimental and modeling study

    CERN Document Server

    Lamberts, Thanja; Fedoseev, Gleb; Ioppolo, Sergio; Chuang, Ko-Ju; Linnartz, Harold

    2014-01-01

    The formation of interstellar water has been commonly accepted to occur on the surfaces of icy dust grains in dark molecular clouds at low temperatures (10-20 K), involving hydrogenation reactions of oxygen allotropes. As a result of the large abundances of molecular hydrogen and atomic oxygen in these regions, the reaction H2 + O has been proposed to contribute significantly to the formation of water as well. However, gas phase experiments and calculations, as well as solid-phase experimental work contradict this hypothesis. Here, we use precisely executed temperature programmed desorption (TPD) experiments in an ultra-high vacuum setup combined with kinetic Monte Carlo simulations to establish an upper limit of the water production starting from H2 and O. These reactants are brought together in a matrix of CO2 in a series of (control) experiments at different temperatures and with different isotopological compositions. The amount of water detected with the quadrupole mass spectrometer upon TPD is found to o...

  10. Influence of experimental parameters on sonochemistry dosimetries: KI oxidation, Fricke reaction and H{sub 2}O{sub 2} production

    Energy Technology Data Exchange (ETDEWEB)

    Merouani, Slimane [Laboratory of Environmental Engineering, Department of Process Engineering, Faculty of Engineering, University of Annaba, P.O. Box 12, 23000 Annaba (Algeria); Hamdaoui, Oualid, E-mail: ohamdaoui@yahoo.fr [Laboratory of Environmental Engineering, Department of Process Engineering, Faculty of Engineering, University of Annaba, P.O. Box 12, 23000 Annaba (Algeria); Saoudi, Fethi; Chiha, Mahdi [Laboratory of Environmental Engineering, Department of Process Engineering, Faculty of Engineering, University of Annaba, P.O. Box 12, 23000 Annaba (Algeria)

    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 ({center_dot}OH), hydrogen peroxide (H{sub 2}O{sub 2}) and hydroperoxyl radicals (HOO{center_dot}). 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{sub 2}O{sub 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{sub 2}O{sub 2} formation were acoustic power, solution temperature and pH. For the three tested dosimetries, the sonochemical efficiency was independent of liquid volume.

  11. Experimental constraints on the γ-ray strength function in 90Zr using partial cross sections of the Y89(p,γZr90 reaction

    Directory of Open Access Journals (Sweden)

    L. Netterdon

    2015-05-01

    Full Text Available Partial cross sections of the Y89(p,γZr90 reaction have been measured to investigate the γ-ray strength function in the neutron–magic nucleus 90Zr. For five proton energies between Ep=3.65 MeV and Ep=4.70 MeV, partial cross sections for the population of seven discrete states in 90Zr have been determined by means of in-beam γ-ray spectroscopy. Since these γ-ray transitions are dominantly of E1 character, the present measurement allows an access to the low-lying dipole strength in 90Zr. A γ-ray strength function based on the experimental data could be extracted, which is used to describe the total and partial cross sections of this reaction by Hauser–Feshbach calculations successfully. Significant differences with respect to previously measured strength functions from photoabsorption data point towards deviations from the Brink–Axel hypothesis relating the photo-excitation and de-excitation strength functions.

  12. Modulating Bandgap and HOCO/LUCO Energy of Semiconducting Polymer by Copolymerization or Incorporation of Electron Withdrawing/Releasing Groups

    Institute of Scientific and Technical Information of China (English)

    YAN Liu-ming; LU Wen-cong

    2007-01-01

    The modulation of bandgap and HOCO/LUCO energies of conjugated polymers by copolymerization or by incorporation of electron withdrawing/releasing groups is studied. The study was conducted by band structure calculation applying density functional theory with generalized gradient approximation. The polymers and copolymers were modeled as 1D infinite system with periodical boundary condition along the molecular direction. It is concluded that the bandgap and HOCO/LUCO energies of conjugated polymers depend on both electron withdrawing/releasing effects and non-bonding interaction between a side group and the conjugated systems.

  13. STABILITY OF EMULSIFIER-FREE EMULSION COPOLYMERIZATION OF METHYL METHACRYLATE/ BUTYL ACRYLATE/SODIUM MONO(ETHYL POLYOXYETHYLENE) MALEATE

    Institute of Scientific and Technical Information of China (English)

    Mao-gen Zhang; Zhi-xue Weng; Zhi-ming Huang; Zu-ren Pan

    1999-01-01

    A series of new water-soluble bifunctional comonomers having both carboxyl and alkyl polyoxyethylene groups, such as sodium mono(ethyl polyoxyethylene) maleate (ZE series) with various molecular weights of polyoxyethylene ethyl ether, were synthesized and characterized. The effects of the structural factor, the amount and feeding mode of the comonomers, the initiator concentration and polymerization temperature on the stability of emulsifier-free emulsion copolymerization of methyl methacrylate (MMA) and butyl acrylate (BA) in the presence of a small amount of ZE with potassium persulfate as initiator were investigated. Stable, almost monodispersed MMA/BA/ZE emulsifier-free latex particles were prepared.

  14. Temperature dependence of stable carbon kinetic isotope effect for the oxidation reaction of ethane by OH radicals: Experimental and theoretical studies

    Science.gov (United States)

    Piansawan, T.; Saccon, M.; Vereecken, L.; Gensch, I.; Kiendler-Scharr, A.

    2017-08-01

    The stable carbon kinetic isotope effect (KIE) of ethane photooxidation by OH radicals was deduced by employing both laboratory measurements and theoretical calculations. The investigations were designed to elucidate the temperature dependence of KIE within atmospherically relevant temperature range. The experimental KIE was derived from laboratory compound-specific isotope analyses of ethane with natural isotopic abundance exposed to OH at constant temperature, showing ɛ values of 7.16 ± 0.54‰ (303 K), 7.45 ± 0.48‰ (288 K), 7.36 ± 0.28‰ (273 K), 7.61 ± 0.28‰ (263 K), 8.89 ± 0.90‰ (253 K), and 9.42 ± 2.19‰ (243 K). Compared to previous studies, a significant improvement of the measurement precision was reached at the high end of the investigated temperature range. The KIE was theoretically determined as well, in the temperature range of 150 K to 400 K, by calculating the reaction rate coefficients of 12C and singly 13C substituted ethane isotopologues applying chemical quantum mechanics together with transition state theory. Tunneling effect and internal rotations were also considered. The agreement between experimental and theoretical results for rate coefficients and KIE in an atmospherically relevant temperature range is discussed. However, both laboratory observations and computational predictions show no significant temperature dependence of the KIE for the ethane oxidation by OH radicals.

  15. Ethylene homo- and copolymerization chain-transfers: A perspective from supported (n BuCp) 2 ZrCl 2 catalyst active centre distribution

    KAUST Repository

    Atiqullah, Muhammad

    2015-04-01

    Polymerization chain termination reactions and unsaturation of the polymer backbone end are related. Therefore, in this study, the parameters resulting from the modelling of the active centre distribution of the supported catalyst - silica/MAO/(nBuCp)2ZrCl2 - were applied to evaluate the active-centre-dependent ethylene homo- and copolymerization rates, as well as the corresponding chain termination rates. This approach, from a microkinetic mechanistic viewpoint, elucidates better the 1-hexene-induced positive comonomer effect and chain transfer phenomenon. The kinetic expressions, developed on the basis of the proposed polymerization mechanisms, illustrate how the active site type-dependent chain transfer phenomenon is influenced by the different apparent termination rate constants and momoner concentrations. The active centre-specific molecular weight M ni (for the above homo- and copolymer), as a function of chain transfer probability, p CTi, varied as follows: log (p C Ti) = log (mwru) - log (Mn i), where mw ru is the molecular weight of the repeat unit. The physical significance of this finding has been explained. The homo- and copolymer backbones showed all the three chain end unsaturations (vinyl, vinylidene, and trans-vinylene). The postulated polymerization mechanisms reveal the underlying polymer chemistry. The results of the present study will contribute to develop in future supported metallocene catalysts that will be useful to synthesize polyethylene precursors having varying chain end unsaturations, which can be eventually used to prepare functional polyethylenes. [Figure not available: see fulltext.] © 2015 Indian Academy of Sciences.

  16. Mussel-inspired one-step copolymerization to engineer hierarchically structured surface with superhydrophobic properties for removing oil from water.

    Science.gov (United States)

    Huang, Shouying

    2014-10-08

    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.

  17. INFLUENCE OF DIALKYLZINC IN RARE-EARTH TERNARY CATALYST ON THE COPOLYMERIZATION OF CARBON DIOXIDE AND PROPYLENE OXIDE

    Institute of Scientific and Technical Information of China (English)

    Dong Xie; Xian-hong Wang; Xiao-jiang Zhao; Fo-song Wang

    2005-01-01

    Rare-earth ternary catalysts Y(CC13COO)3-ZnR2-glycerin were prepared for the copolymerization of carbon dioxide and propylene oxide (PO), where dialkylzincs (ZnR2) were diethylzinc, di(n-propyl)zinc, ali(n-butyl)zinc, di(i-propyl)zinc, di(i-butyl)zinc, di(s-butyl)zinc,respectively. The Y(CCl3COO)3-ZnR2-glycerin catalysts displayed the highest catalytic activity at the molar ratio of Y(CCl3COO)3:ZnR2:glycerin = 1:20:10. In the same copolymerization condition,catalysts containing dialkylzincs with branched alkyl group showed lower catalytic activity than that with primary alkyl group. For those catalysts including dialkylzincs with primary alkyl group, their catalytic activity decreases with increasing number of carbon atom in the alkyl group with the following sequence: Y(CCl3COO)3-ZnEt2-glycerin > Y(CCl3COO)3-Zn(n-Pr)2-glycerin>Y(CCl3COO)3-Zn(n-Bu)2-glycerin. However, the alkyl group in the dialkylzinc does not influence the insertion of PO into the propagation chain end.

  18. Comparison of (n,2n) and (n,3n) reaction cross sections for fission products in JENDL-3.2 with available experimental and other evaluated cross section data

    Energy Technology Data Exchange (ETDEWEB)

    Manokhin, Vassily N. [Russian Nuclear Data Center, Institute of Physics and Power Engineering (Russian Federation); Odano, Naoteru; Hasegawa, Akira [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

    2001-07-01

    In this report, results of comparison of (n,2n) and (n,3n) reaction cross sections for 155 nuclei (Ge-Tb) in JENDL-3.2 with available experimental data, various evaluated data, and those estimated from systematics are summarized to assess validity of cross sections for threshold reactions for fission product nuclei in JENDL-3.2. Plots for comparisons are compiled and issues in cross section data in JENDL-3.2 are also discussed. (author)

  19. Laboratory studies of H2SO4/H2O binary homogeneous nucleation from the SO2+OH reaction: evaluation of the experimental setup and preliminary results

    Directory of Open Access Journals (Sweden)

    F. R. Kameel

    2008-04-01

    Full Text Available We have developed a new laboratory nucleation setup to study binary homogeneous nucleation (BHN of sulphuric acid and water (H2SO4/H2O. Here we provide a detailed evaluation of this new experimental setup and also discuss our preliminary results by comparing with other laboratory studies. H2SO4 is produced from the SO2+OH →HSO3 reaction and OH radicals are produced from water vapor UV absorption. The residual H2SO4 concentrations ([H2SO4] are measured at the end of the fast flow nucleation reactor with a chemical ionization mass spectrometer. The measured BHN rates (J ranged from 0.02 and 550 cm−3 s−1 at the residual [H2SO4] from 108 to 1010 cm−3, a temperature of 288 K and relative humidity (RH from 6 to 23%; J increased with increasing [H2SO4] and RH. J also showed a power dependence on [H2SO4] with the exponential power of 3 to 8. These results are consistent with other laboratory studies under similar [H2SO4] and RH, but different from atmospheric field observations which showed that particle number concentrations are often linearly dependent on [H2SO4]. Both particle sizes and number concentrations increased with increasing [H2SO4], RH, and nucleation time, consistent with the predictions from nucleation theories. Particle growth rates were estimated between 28 to 127 nm h−1, much higher than those seen from atmospheric field observations, because of the higher [H2SO4] used in our study. While these experimental results demonstrate a validation of our laboratory setup, there are also technical difficulties associated with nucleation studies, including wall loss and H2SO4 measurements.

  20. The geochemical reactions resulting from CO{sub 2} injection into the Midale Formation, Weyburn oilfield : a laboratory experimental and modelling study

    Energy Technology Data Exchange (ETDEWEB)

    Azaroual, M.; Durst, P.; Czernichowski-Lauriol, I. [Bureau de Recherches Geologiques et Minieres, Orleans (France); Olsen, D.; Stentoft, N.; Springer, N. [Geological Survey of Denmark and Greenland (Denmark); Rochelle, C.A.; Pearce, J.; Bateman, K.; Birchall, D. [British Geological Survey, Nottingham (United Kingdom)

    2005-07-01

    One aspect of the International Energy Agency's (IEA) Weyburn CO2 Monitoring and Storage Project is the identification of geochemical changes that occur following the injection of carbon dioxide (CO{sub 2}) into the Midale Formation of the Weyburn Field in southern Saskatchewan. This paper summarized the fluid chemical and mineralogical changes noted during laboratory experiments on Midale core from the Weyburn Field. The reactions between injected CO{sub 2}, Midale lithologies and porewaters under temperatures and pressures representative of in-situ conditions were explored. The laboratory studies involved closed system batch experiments reacting samples of Midale reservoir rocks and cap rock with synthetic saline reservoir porewaters. Flow experiments were also performed based on both core flood approaches and column experiments. The duration of experiments ranged from 1 week to 6 months. Changes in fluid chemistry, mineralogy, porosity and permeability were measured. The results were then used to verify predictions from geochemical modelling activities. Experimental and theoretical studies of the effects of CO{sub 2} injection into the Midale lithologies showed variable amounts of carbonate mineral dissolution, some precipitation of gypsum, inhibition of anhydrite dissolution, and slow reactivity of alumino-silicate minerals. These indications helped develop an hypothesis and approaches to simulate the long term evolution of a one dimensional model representing CO{sub 2} injection into the host Midale Marly formation. . 3 refs., 4 figs.

  1. Technical note: Monte Carlo genetic algorithm (MCGA for model analysis of multiphase chemical kinetics to determine transport and reaction rate coefficients using multiple experimental data sets

    Directory of Open Access Journals (Sweden)

    T. Berkemeier

    2017-06-01

    Full Text Available We present a Monte Carlo genetic algorithm (MCGA for efficient, automated, and unbiased global optimization of model input parameters by simultaneous fitting to multiple experimental data sets. The algorithm was developed to address the inverse modelling problems associated with fitting large sets of model input parameters encountered in state-of-the-art kinetic models for heterogeneous and multiphase atmospheric chemistry. The MCGA approach utilizes a sequence of optimization methods to find and characterize the solution of an optimization problem. It addresses an issue inherent to complex models whose extensive input parameter sets may not be uniquely determined from limited input data. Such ambiguity in the derived parameter values can be reliably detected using this new set of tools, allowing users to design experiments that should be particularly useful for constraining model parameters. We show that the MCGA has been used successfully to constrain parameters such as chemical reaction rate coefficients, diffusion coefficients, and Henry's law solubility coefficients in kinetic models of gas uptake and chemical transformation of aerosol particles as well as multiphase chemistry at the atmosphere–biosphere interface. While this study focuses on the processes outlined above, the MCGA approach should be portable to any numerical process model with similar computational expense and extent of the fitting parameter space.

  2. Technical note: Monte Carlo genetic algorithm (MCGA) for model analysis of multiphase chemical kinetics to determine transport and reaction rate coefficients using multiple experimental data sets

    Science.gov (United States)

    Berkemeier, Thomas; Ammann, Markus; Krieger, Ulrich K.; Peter, Thomas; Spichtinger, Peter; Pöschl, Ulrich; Shiraiwa, Manabu; Huisman, Andrew J.

    2017-06-01

    We present a Monte Carlo genetic algorithm (MCGA) for efficient, automated, and unbiased global optimization of model input parameters by simultaneous fitting to multiple experimental data sets. The algorithm was developed to address the inverse modelling problems associated with fitting large sets of model input parameters encountered in state-of-the-art kinetic models for heterogeneous and multiphase atmospheric chemistry. The MCGA approach utilizes a sequence of optimization methods to find and characterize the solution of an optimization problem. It addresses an issue inherent to complex models whose extensive input parameter sets may not be uniquely determined from limited input data. Such ambiguity in the derived parameter values can be reliably detected using this new set of tools, allowing users to design experiments that should be particularly useful for constraining model parameters. We show that the MCGA has been used successfully to constrain parameters such as chemical reaction rate coefficients, diffusion coefficients, and Henry's law solubility coefficients in kinetic models of gas uptake and chemical transformation of aerosol particles as well as multiphase chemistry at the atmosphere-biosphere interface. While this study focuses on the processes outlined above, the MCGA approach should be portable to any numerical process model with similar computational expense and extent of the fitting parameter space.

  3. Mechanism of reaction in NaAlCl4 molten salt batteries with nickel felt cathodes and aluminum anodes. 2: Experimental results and comparison with model calculations

    Science.gov (United States)

    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.

  4. First Experimental Constraints on the Interference of 3/2+ Resonances in the 18F(p, ?)15O Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Chae, Kyung Yuk [ORNL; Bardayan, Daniel W [ORNL; Blackmon, Jeff C [ORNL; Gregory, Darren R [ORNL; Guidry, Mike W [ORNL; Johnson, Micah [ORNL; KOZUB, RAYMOND L [ORNL; Livesay, Jake [ORNL; Ma, Zhanwen [ORNL; Nesaraja, Caroline D [ORNL; Pain, Steven D [ORNL; Paulauskas, Stanley V [ORNL; Porter-Peden, Matthew D [ORNL; Shriner, Jr., John F [ORNL; Smith, Nathan A [ORNL; Smith, Michael Scott [ORNL; Thomas, Jeffrey S [ORNL

    2006-06-01

    The interference effects among J{sup {pi}}=3/2+ resonances in the {sup 18}F+p system have not been previously measured. R-matrix calculations show that the cross sections above the E{sub c.m.}=665 keV resonance are sensitive to the interference between the E{sub c.m.}=8, 38, and 665 keV resonances. An excitation function for the {sup 1}H({sup 18}F,{alpha}){sup 15}O reaction has been measured in the energy range of E{sub c.m.}=663-877 keV using radioactive 18F beams at the Holifield Radioactive Ion Beam Facility (HRIBF). By comparing the observed cross sections with the R-matrix calculations, we provide the first experimental constraints on the interference. Upper limits on proton widths ({Gamma}{sub p}) of the E{sub c.m.}=827 and 842 keV resonances have been set as well.

  5. Investigations on vinylene carbonate. IV. Radiation induced graft copolymerization of vinylene carbonate and N-vinyl-N-methylacetamide onto polyethylene films

    NARCIS (Netherlands)

    Chen, Guohua; Does, van der Leen; Bantjes, Adriaan

    1992-01-01

    Graft copolymerization of binary mixtures of vinylene carbonate (VCA) and N-vinyl-N-methylacetamide (VIMA) onto low density polyethylene (LDPE) films was studied by the mutual γ-irradiation technique. Sufficient amounts of functionally active VCA groups could be grafted onto the surface and the hydr

  6. COPOLYMERIZATION AND DETERMINATION OF MONOMER REACTIVITY RATIOS OF DL-LACTIDE WITH 3-BENZYLOXYMETHYL-1,4-DIOXANE-2,5-DIONE

    Institute of Scientific and Technical Information of China (English)

    Ji-yuan Yang; Jian Yu; Mei Li; Zhong-wei Gu; Xin-de Feng

    2002-01-01

    The copolymerization of DL-LA and 3-BMG was carried out in bulk with stannous 2-ethylhexanoate as the catalyst. A series of copolymers with pendant protected groups were obtained and characterized by 1H-NMR and GPC to be rBMG = 1.96 and rLA = 0.37, respectively.

  7. 共聚改性水性聚氨酯的研究进展%Progress of copolymerization modification of waterborne polyurethanes

    Institute of Scientific and Technical Information of China (English)

    张探; 王晓莉; 卢曼怡; 熊晓; 孔志祥; 张洋; 管蓉

    2015-01-01

    共聚改性水性聚氨酯 WPU 可以有效的提高其耐热性、耐水性和力学性能,并且能够很好的将共聚材料与WPU的优点结合起来。本文重点介绍了环氧树脂、丙烯酸酯、有机硅和有机氟共聚改性WPU的研究进展,并对共聚改性WPU的发展现状进行了分析和展望。()%The copolymerization modification of waterborne polyurethanes combining the advantages of copolymerized materials and waterborne polyurethanes(WPU) can improve their heat resistance, water resistance and mechanical properties. This paper introduced the progress of copolymerization modification of waterborne polyurethanes epoxy resin, acrylate, silicone and organic fluorine with at home and abroad in recent years. Finally, current development situation and the trend of copolymerization modification waterborne polyurethanes were analyzed and prospected.

  8. 分散聚合制备聚苯乙烯聚氧乙烯两亲聚合物微球%SYNTHESIS OF POLYSTYRENE/POLY(ETHYLENE OXIDE) AMPHIPHILIC MICROSPHERES BY DISPERSION COPOLYMERIZATION

    Institute of Scientific and Technical Information of China (English)

    李卫; 丁小斌; 林晓琴; 张文传; 邓金根; 彭宇行; 李蓓; 陈新滋

    2001-01-01

    Poly(ethylene oxide)macromonomer was prepared by the reaction of poly(ethylene glycol)and vinyl benzyl chloride with the help of NaH.Through dispersion copolymerization of poly(ethylene oxide)macromonomer and styrene carried out in the media of ethanol/water, amphiphilic microspheres ranging from 0.5~1.5μm were prepared. The resulted amphiphilic microspheres were characterized by scanning electron microscope, IR etc, and the formation of copolymer was confirmed by IR spectra of amphiphilic microspheres and solubility of amphiphilic microspheres in the media of benzene. The factors which affected the diameter and diameter distribution of microspheres, including concentration of monomer, concentration of dispersant and composition of the media of reaction, were systematically investigated.%聚乙二醇在NaH的作用下和对氯甲基苯乙烯反应制得聚氧乙烯大分子单体,然后在乙醇/水的介质中通过聚氧乙烯大分子单体和苯乙烯的分散共聚制得粒径范围在0.5~1.5μm,粒径分布接近单分散的两亲聚合物微球.对影响微球粒径和粒径分布的各个因素进行了研究.

  9. 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.

    Science.gov (United States)

    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. Copyright © 2016 Elsevier B.V. All rights reserved.

  10. 油酸盐用于淀粉接枝AM-AA反相乳液共聚反应乳化剂%EFFECT OF OLEATES AS EMULSIFIERS ON GRAFT COPOLYMERIZATION OF AM-AA ON STARCH IN INVERSE EMULSION

    Institute of Scientific and Technical Information of China (English)

    曹亚峰; 杨锦宗; 刘兆丽

    2004-01-01

    The effect of oleates as emulsifiers on graft copolymerization of starch with acrylamide (AM) and acrylic acid (AA) in the inverse emulsion system is studied in this paper . The effect of the kinds of emulsifiers,the proportion of mixed emulsifiers, the dosage of emulsifiers as well as the preparation methods of water-in-oil emulsion on monomer conversion, grafting ratio, and specific viscidity is discussed. The result indicates that calcium oleate or magnesium oleate as the emulsifier is better than sodium oleate or potassium oleate, and the mixture of oleic acid and its salt is better than any single compound. It is also concluded that monomer conversion reaches 99.7 % and grafting ratio reaches 98.4% when m(oleic acid)/m (oleate sodium) is 60/40, m(starch)/m (monomers) is 1/1 (among the monomers m (AM)/m (AA) is 4/1), v(oil phase)/v(waterphase) is 1.2/1, initiator concentration is 2.4×10-4mol·L-1, reaction temperature is 45-50℃,and reaction time is 6 hours. When mixed emulsifers concentration is 6%, the intrinsic viscidity reaches 1100ml·g-1.

  11. In situ UV-visible spectroelectrochemical studies on the copolymerization of diphenylamine with ortho-methoxy aniline

    Science.gov (United States)

    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.

  12. ELECTROCHEMICAL COPOLYMERIZATION OF 3-(4-FLUOROPHENYL)THIOPHENE AND 3-METHYLTHIOPHENE IN BORON TRIFLUORIDE DIETHYL ETHERATE

    Institute of Scientific and Technical Information of China (English)

    Jing-kun Xu; Zhen-hong Wei; Qiang Xiao; Shou-zhi Pu

    2006-01-01

    The copolymer poly(3-(4-fluorophenyl)thiophene-co-3-methylthiophene) was successfully prepared from mixtures of 3-(4-fluorophenyl)thiophene (FPT) and 3-methylthiophene (MeT) via electrochemical oxidation in boron trifluoride diethyl etherate (BFEE) and its mixed electrolytes with acetonitrile (ACN). The influence of monomer concentration ratios on the copolymerization was investigated by using linear sweep voltammetry and cyclic voltammetry. The structure and morphology of these copolymer films were elucidated by UV-Vis, infrared spectroscopy, elemental analysis, thermal analysis and scanning electron microscopy (SEM), respectively. The results showed that the molar ratio of FPT and MeT units, when copolymer was electrodeposited from feed ratio of FPT:MeT = 1:2, was about 1.08:1. In addition, the introduction of ACN into BFEE has little effect on the properties of as-formed copolymers.

  13. REDUCING NONSELECTIVE PROTEIN ADSORPTION AND CELL ADHESION ON POLYACRYLONITRILE FILMS BY COPOLYMERIZATION OF ACRYLONITRILE WITH α-ALLYL GLUCOSIDE

    Institute of Scientific and Technical Information of China (English)

    Rui-qiang Kou; Chao Qu; Zhi-kang Xu; You-yi Xu; Ke Yao

    2003-01-01

    In this work, the surface properties of novel sugar-containing polymers, α-allyl glucoside (AG)/acrylonitrile (AN)copolymers, were studied by contact angle, protein adsorption and cell adhesion measurements. It was found that the contact angle of the copolymer films decreased from 68° to 30° with the increase of AG content in the copolymer. The adsorption amount of bovine serum albumin (BSA) and the adhesive macrophage onto the film surface also decreased significantly with increasing α-allyl glucoside content from 0 to 42 wt% in the copolymer. These preliminary results reveal that both the hydrophilicity and the biocompatibility of polyacrylonitrile-based membranes could be improved by copolymerizing acrylonitrile with vinyl carbohydrates.

  14. Effect of Nano-clay on Rheological and Extrusion Foaming Process of a Block-Copolymerized Polypropylene

    Directory of Open Access Journals (Sweden)

    Wang Mingyi

    2016-01-01

    Full Text Available The effects of nano-clay and the corresponding coupling agent maleic anhydride grafted polypropylene (PP-g-MAH on thermal properties, rheological properties and extrusion foaming process of a block-copolymerized polypropylene (B-PP were studied. Supercritical CO2 (SC CO2 was used as the foaming agent with a concentration of 5wt%. Each step of foamed B-PP/ PP-g-MAH/ nano-clay composites processing is addressed, including mixing of the composites, manufacture of the composites, foaming process of the composites and characterization of the cell structure. The results showed that incorporation of nano-clay and PP-g-MAH caused reduced melt strength and complex viscosity of B-PP. However, the heterogeneous nucleation induced by nano-clay and PP-g-MAH improved the maximum foaming expansion ratio and cell-population density of B-PP foam.

  15. Synthesis and Characterization of Well-Defined Soluble Alq3- and Znq2-Functionalized Polymers via RAFT Copolymerization

    Directory of Open Access Journals (Sweden)

    Chengchao Wang

    2010-01-01

    Full Text Available The reversible addition-fragmentation chain transfer (RAFT copolymerizations of 2-((8-hydroxyquinolin-5-ylmethoxyethyl methacrylate (HQHEMA with styrene (St or methyl methacrylate (MMA were successfully carried out in the presence of 2-cyanoprop-2-yl dithionaphthalenoate (CPDN. The polymerization behaviors showed the typical living natures by the first-order polymerization kinetics, the linear dependence of molecular weights of the polymers on the monomer conversions with the relatively narrow molecular weight distributions (Mw/Mn, and the successful chain extension experiments. The soluble polymers having tris(8-hydroxyquinolinealuminum (Alq3 and bis(8-hydroxyquinoline znic(II (Znq2 side chains were obtained via complexation of the polymers with aluminium isopropoxide or zinc acetate in the presence of monomeric 8-hydroxyquinoline, which had strong fluorescent emission at 520 nm. The obtained polymers were characterized by GPC, NMR, UV-vis, and fluorescent spectra.

  16. Preparation of hybrid thiol-acrylate emulsion-templated porous polymers by interfacial copolymerization of high internal phase emulsions.

    Science.gov (United States)

    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.

  17. A Recyclable Nanoparticle-Supported Rhodium Catalyst for Hydrogenation Reactions

    Directory of Open Access Journals (Sweden)

    Maria Michela Dell’Anna

    2010-05-01

    Full Text Available Catalytic hydrogenation under mild conditions of olefins, unsaturated aldeydes and ketones, nitriles and nitroarenes was investigated, using a supported rhodium complex obtained by copolymerization of Rh(cod(aaema [cod: 1,5-cyclooctadiene, aaema–: deprotonated form of 2-(acetoacetoxyethyl methacrylate] with acrylamides. In particular, the hydrogenation reaction of halonitroarenes was carried out under 20 bar hydrogen pressure with ethanol as solvent at room temperature, in order to minimize hydro-dehalogenation. The yields in haloanilines ranged from 85% (bromoaniline to 98% (chloroaniline.

  18. Experimental study of the astrophysically important 23Na(α ,p )26Mg and 23Na(α ,n )26Al reactions

    Science.gov (United States)

    Avila, M. L.; Rehm, K. E.; Almaraz-Calderon, S.; Ayangeakaa, A. D.; Dickerson, C.; Hoffman, C. R.; Jiang, C. L.; Kay, B. P.; Lai, J.; Nusair, O.; Pardo, R. C.; Santiago-Gonzalez, D.; Talwar, R.; Ugalde, C.

    2016-12-01

    The 23Na(α ,p )26Mg and 23Na(α ,n )26Al reactions are important for our understanding of the 26Al abundance in massive stars. The aim of this work is to report on a direct and simultaneous measurement of these astrophysically important reactions using an active target system. The reactions were investigated in inverse kinematics using 4He as the active target gas in the detector. We measured the excitation functions in the energy range of about 2 to 6 MeV in the center of mass. We have found that the cross sections of the 23Na(α ,p )26Mg and the 23Na(α ,n )26Al reactions are in good agreement with previous experiments and with statistical-model calculations. The astrophysical reaction rate of the 23Na(α ,n )26Al reaction has been reevaluated and it was found to be larger than the recommended rate.

  19. 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 65 MeV

    CERN Document Server

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

    2016-01-01

    Activation cross-sections data of longer-lived products of proton induced nuclear reactions on dysprosium were extended up to 65 MeV 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 36-65 MeV 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.

  20. 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.

    Science.gov (United States)

    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. Copyright © 2015. Published by Elsevier Ltd.

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

    Energy Technology Data Exchange (ETDEWEB)

    Patin, Joshua Barnes [Univ. of California, Berkeley, CA (United States)

    2002-01-01

    The study of the reactions between heavy ions and 208Pb, 209Bi, 238U, and 248Cm 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 238U(18O,xn)256-xFm, 238U(22Ne,xn)260-xNo, and 248Cm(15N,xn)263-xLr 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 48Pb(238Ca,xn)256-xNo, 208Pb(50Ti,xn)258-xRf, 208Pb(51V,xn)259-xDb, 50Bi(238Ti,xn)259-xDb, and 209Bi(51V,xn)260-xSg 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.

  2. Chemical transport reactions

    CERN Document Server

    Schäfer, Harald

    2013-01-01

    Chemical Transport Reactions focuses on the processes and reactions involved in the transport of solid or liquid substances to form vapor phase reaction products. The publication first offers information on experimental and theoretical principles and the transport of solid substances and its special applications. Discussions focus on calculation of the transport effect of heterogeneous equilibria for a gas motion between equilibrium spaces; transport effect and the thermodynamic quantities of the transport reaction; separation and purification of substances by means of material transport; and

  3. A combined experimental and computational study of the catalytic dehydration of glycerol on microporous zeolites: an investigation of the reaction mechanism and acrolein selectivity.

    Science.gov (United States)

    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.

  4. Impact modification of poly(caprolactam) by copolymerization with a low molecular weight polybutadiene

    NARCIS (Netherlands)

    Borggreve, R.J.M.; Gaymans, R.J.

    1988-01-01

    Caprolactam and a reactive, low molecular weight polybutadiene were polymerized in an autoclave, followed by post-condensation in the solid state. The rubber concentration was varied (0–30 wt%). The morphology of the reaction products was studied by transmission electron microscopy. In the materials

  5. On the impedance of galvanic cells XIX. The potential dependence of the faradaic impedance in the case of an irreversible electrode reaction; experimental verification for the redox couple Eu3+/Eu2+ In 1 M NaClO4 and The mechanism of the Zn2+/Zn(Hg) reaction in KCl

    NARCIS (Netherlands)

    Timmer, B.; Sluyters-Rehbach, M.; Sluyters, J.H.

    1967-01-01

    An experimental verification of the theory for the potential dependence of the faradaic impedance in the case of irreversible electrode reactions, described in part XVIII, is presented for the Eu3+/Eu2+ couple in 1 M NaClO4 at a D.M.E. It is shown that two peaks occur in an a.c. polarogram, if both

  6. Investigating Experimental Effects within the Framework of Structural Equation Modeling: An Example with Effects on Both Error Scores and Reaction Times

    Science.gov (United States)

    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…

  7. Homo-polymerization of α-Olefins and Co-polymerization of Higher α-Olefins with Ethylene in the Presence of CpTiCl2(OC6H4X-p/MAO Catalysts (X = CH3, Cl

    Directory of Open Access Journals (Sweden)

    Z. Wieczorek

    2005-07-01

    Full Text Available Cyclopentadienyl-titanium complexes containing –OC6H4X ligands (X = Cl,CH3 activated with methylaluminoxane (MAO were used in the homo-polymerizationof ethylene, propylene, 1-butene, 1-pentene, 1-butene, and 1-hexene, and also in co-polymerization of ethylene with the α-olefins mentioned. The -X substituents exhibitdifferent electron donor-acceptor properties, which is described by Hammett’s factor (σ.The chlorine atom is electron acceptor, while the methyl group is electron donor. Thesecatalysts allow the preparation of polyethylene in a good yield. Propylene in the presenceof the catalysts mentioned dimerizes and oligomerizes to trimers and tetramers at 25oCunder normal pressure. If the propylene pressure was increased to 7 atmospheres,CpTiCl2(OC6H4CH3/MAO catalyst at 25oC gave mixtures with different contents ofpropylene dimers, trimers and tetramers. At 70oC we obtained only propylene trimer.Using the catalysts with a -OC6H4Cl ligand we obtained atactic polymers with Mw182,000 g/mol (at 25oC and 100,000 g/mol (at 70oC. The superior activity of theCpTiCl2(OC6H4Cl/MAO catalyst used in polymerization of propylene prompted us tocheck its activity in polymerization of higher α-olefins (1-butene, 1-pentene, 1-hexeneand in co-polymerization of these olefins with ethylene. However, when homo-polymerization was carried out in the presence of this catalyst no polymers wereobtained. Gas chromatography analysis revealed the presence of dimers. The activity ofthe CpTiCl2(OC6H4Cl/MAO catalyst in the co-polymerization of ethylene with higher α-olefins is limited by the length of the co-monomer carbon chain. Hence, the highest catalyst activities were observed in co-polymerization of ethylene with propylene (here a lower pressure of the reagents and shorter reaction time were applied to obtain catalytic activity similar to that for other co-monomers. For other co-monomers the activity of the catalyst

  8. Grafting copolymerization of natural rubber with 2-hydroxyethyl methacrylate for plywood adhesion improvement

    Directory of Open Access Journals (Sweden)

    Yoopadee Promdum

    2009-10-01

    Full Text Available The graft copolymer of natural rubber (NR and 2-hydroxyethyl methacrylate (HEMA was prepared by seeded emulsion polymerization using cumene hydroperoxide (CHP and tetraethylene pentamine TEPA as an initiator system. The structures of the copolymers were characterized by FT-IR and 1H-NMR spectroscopy techniques. The adhesion properties of NR-g-HEMA were examined. The effects of monomer concentration, initiator concentration, reaction temperature,reaction time and the agitation speed on grafting and grafting efficiency were investigated. It was found that the optimumconditions for preparing NR-g-HEMA when 5 phr of HEMA with 0.15mol% of initiator was used were 60oC for 90 min under agitation speed of 50 rpm. Furthermore, the adhesion properties to plywood of the graft copolymers are higher than those of original NR.

  9. Spallation reactions; Reactions de spallation

    Energy Technology Data Exchange (ETDEWEB)

    Cugon, J.

    1996-12-31

    Spallation reactions dominate the interactions of hadrons with nuclei in the GeV range (from {approx} 0.1 to {approx} 10 GeV). They correspond to a sometimes important ejection of light particles leaving most of the time a residue of mass commensurate with the target mass. The main features of the experimental data are briefly reviewed. The most successful theoretical model, namely the intranuclear cascade + evaporation model, is presented. Its physical content, results and possible improvements are critically discussed. Alternative approaches are shortly reviewed. (author). 84 refs.

  10. Template copolymerization to control site structure around metal ions: Applications towards sensing and gas storage and release

    Science.gov (United States)

    Mitchell-Koch, Jeremy T.

    The development of functional materials for sensing and gas storage and release is useful in a number of chemical and biological applications. Investigating function of molecularly imprinted polymers (MIP), often used for these purposes, has relied on circumstantial evidence because direct examination of immobilized sites is not possible. Described in this dissertation is the design, synthesis, characterization and function studies of materials synthesized by template copolymerization methods. Metal ions exhibit unique spectroscopic properties and their utilization makes site examination more feasible. Ligand binding modulates these properties such that the event can be measured by spectroscopy. The metal ion's secondary coordination environment can also be tuned to increase or decrease function of the material. In Chapter Two the utilization of template copolymerization to immobilize a europium-containing compound for the detection of volatile organic compounds is described. Luminescence of the immobilized complex is quenched in the presence of volatile organic compounds (VOC). The quenching effect is dependent on concentration of VOC and the nature of polymeric host. Chapters Three and Four describe the development of materials for the photolytic release of nitric oxide (NO). In Chapter Three, a novel manipulation of the immobilized complex is employed to produce binding sites that contain ligands covalently embedded into the host in a position to bind the metal ion upon NO release in order to block rebinding. Incompatible binding affinities of the iron-containing templates made it impossible to study NO photo-release from this material. Second-row transition metals are more compatible with NO binding, and Chapter Four describes a ruthenium salen-containing polymer that releases NO in response to light. Additionally, transfer of NO to a metalloporphyrin and myoglobin has been achieved. This is the first report of photolytic heterogeneous NO transfer by a material

  11. Preparation of Syndiotactic Poly(vinyl alcohol)/Poly(vinyl pivalate/vinyl acetate) Microspheres with Radiopacity Using Suspension Copolymerization and Saponification

    Science.gov (United States)

    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).

  12. Isoselective 3,4-(co)polymerization of bio-renewable myrcene using NSN-ligated rare-earth metal precursor: an approach to a new elastomer.

    Science.gov (United States)

    Liu, Bo; Li, Lei; Sun, Guangping; Liu, Dongtao; Li, Shihui; Cui, Dongmei

    2015-01-21

    The polymerization of bio-renewable myrcene (MY), using a cationic β-diimidosulfonate lutetium catalyst in high activity, afforded an unprecedented isotactic 3,4-polymyrcene (PMY) with a low Tg (-42 °C). Based on this result, the random and block copolymerization of myrcene and isoprene (IP) resulted in novel elastomers that comprise the amorphous iso-3,4-PMY and iso-3,4-PIP sequences.

  13. Thiol-functionalized copolymeric polyesters by lipase-catalyzed esterification and transesterification of 1,12-dodecanedioic acid and its diethyl ester, respectively, with 1-thioglycerol

    OpenAIRE

    Fehling, Eberhard; Bergander, Klaus; Klein, Erika; Weber, Nikolaus; Vosmann, Klaus

    2010-01-01

    Abstract Copolymeric polyoxoesters containing branched-chain methylenethiol functions, i.e., poly(1,12-dodecanedioic acid-co-1-thioglycerol) and poly(diethyl 1,12-dodecanedioate-co-1-thioglycerol), were formed by lipase-catalyzed polyesterification and polytransesterification of 1,12-dodecanedioic acid and diethyl 1,12-dodecanedioate, respectively, with 1-thioglycerol (3-mercaptopropane-1,2-diol) using immobilized lipase B from Candida antarctica (Novozym 435) in vacuo without dryi...

  14. PREPARATION OF TELECHELICS BY OXIDATIVE COUPLING COPOLYMERIZATION OF 2,6-DIMETHYLPHENOL WITH TETRAMETHYL BISPHENOL-A CATALYZED BY COPPER(II) COMPLEXES OF N-METHYLIMIDAZOLE

    NARCIS (Netherlands)

    WEI, C; CHALLA, G; REEDIJK, J

    1991-01-01

    A series of copolymerizations of 2,6-dimethylphenol (DMP) with 2,2-di(4-hydroxy-3,5-dimethylphenyl)-propane (tetramethyl bisphenol-A, TMBPA) catalysed by N-methylimidazole Cu(II) complexes in toluene/methanol (12/3 v/v) was performed with TMBPA/Cu = 1. The main product alpha-omega-bis(2,6-dimethylph

  15. 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

    Energy Technology Data Exchange (ETDEWEB)

    Rodríguez, W.; Torres, D. A.; Cristancho, F. [Universidad Nacional de Colombia, Bogotá (Colombia); Medina, N. H. [Departamento de Fisica Nuclear, Universidade de Saõ Paulo (Brazil); 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. [School of Engineering and Science, University of the West of Scotland, Paisley, PA1 2BE (United Kingdom); 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.

  16. 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

    Science.gov (United States)

    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.

  17. In vitro drug release behavior, mechanism and antimicrobial activity of rifampicin loaded low molecular weight PLGA-PEG-PLGA triblock copolymeric nanospheres.

    Science.gov (United States)

    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.

  18. Chemical kinetics of gas reactions

    CERN Document Server

    Kondrat'Ev, V N

    2013-01-01

    Chemical Kinetics of Gas Reactions explores the advances in gas kinetics and thermal, photochemical, electrical discharge, and radiation chemical reactions. This book is composed of 10 chapters, and begins with the presentation of general kinetic rules for simple and complex chemical reactions. The next chapters deal with the experimental methods for evaluating chemical reaction mechanisms and some theories of elementary chemical processes. These topics are followed by discussions on certain class of chemical reactions, including unimolecular, bimolecular, and termolecular reactions. The rema

  19. Experimental and theoretical analysis of polymerization reaction process on the polydopamine membranes and its corrosion protection properties for 304 Stainless Steel

    Science.gov (United States)

    Yu, Fei; Chen, Shougang; Chen, Yan; Li, Houmin; Yang, Lejiao; Chen, Yuanyuan; Yin, Yansheng

    2010-10-01

    Inspired by the bio-adhesion principle, polydopamine membrane was fabricated by dipping the 304 Stainless Steel (304 SS) substrate into an aqueous alkaline dopamine solution and its possible reaction mechanism and the temperature effect were studied. The membranes were characterized by scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDS), surface reflection Fourier transform infrared spectrum (SR-FTIR), UV-visible spectrum. The polymerization reactions of dopamine in solution were also analyzed by the LUMO energies, simulated infrared spectrum and HOMO-LUMO energy gaps of selected structure models calculation, and the possible interfacial reaction mechanism was also discussed by the molecular orbital analysis of melanin clusters. Moreover, the corrosion behaviors of the polydopamine films prepared at different temperatures and dipping days were evaluated by the electrochemical impedance spectroscopy (EIS), as well as that of bare 304 SS, especially long stability in 3.5% NaCl solution.

  20. Experimental study of the excitation functions of proton induced nuclear reactions on (167)Er for production of medically relevant (167)Tm.

    Science.gov (United States)

    Tárkányi, F; Hermanne, A; Takács, S; Király, B; Spahn, I; Ignatyuk, A V

    2010-02-01

    (167)Tm (T(1/2)=9.25d) is a candidate radioisotope for medical therapy and diagnostics due to its Auger-electron and low-energy X- and gamma-ray emission. Excitation functions of the (167)Er(p,n)(167)Tm reaction and (168)Er(p,n)(168)Tm, (167)Er(p,2n)(166)Tm, (166)Er(p,2n)(165)Tm disturbing reactions were measured up to 15MeV by using the stacked foil irradiation technique and gamma-ray spectroscopy. The measured excitation functions agree well with the results of ALICE-IPPE, EMPIRE-II and TALYS nuclear reaction model codes. The thick target yield of (167)Tm in the 15-8MeV energy range is 6.9MBq/microAh. A short comparison of charged particle production routes of (167)Tm is given. Copyright (c) 2009 Elsevier Ltd. All rights reserved.

  1. Experimental and theoretical studies of the reaction between CF3 and NO2 at 298 K

    DEFF Research Database (Denmark)

    Pagsberg, P.; Jodkowski, J.T.; Ratajczak, E.;

    1998-01-01

    The title reaction has been studied by pulse radiolysis combined with time-resolved infrared diode laser spectroscopy. The kinetics of CF3 were analysed taking into account the two competing reactions CF3 + CF3 M --> C2F6 + M (1) and CF3 + NO2 --> CF2O + FNO (2a). Based on studies of the yield...... and kinetics of CF3 we determined values of the absorption cross section, sigma(CF3) = (1.96 +/- 0.20) X 10(-17) cm(2) molecule(-1) at 1263.567 cm(-1) and the bimolecular rate constant, k(1) = (1.04 +/- 0.12) X 10(-11) cm(3) molecule(-1) s(-1) with a bath gas pressure of 20 mbar at 298 K. Reaction (2a...

  2. Conventional and atom transfer radical copolymerization of phenoxycarbonylmethyl methacrylate-styrene and thermal behavior of their copolymers

    Directory of Open Access Journals (Sweden)

    2007-08-01

    Full Text Available The atom transfer radical polymerization (ATRP of phenoxycarbonylmethyl methacrylate (PCMMA with styrene (St were performed in bulk at 110°C in the presence of ethyl 2-bromoacetate, cuprous(Ibromide (CuBr, and N,N,N’,N”,N”-pentamethyldiethyltriamine. Also, a series conventional free-radical polymerization (CFRP of PCMMA and styrene were carried out in the presence of 2,2’-azobisisobutyronitrile in 1,4-dioxane solvent at 60°C. The structure of homo and copolymers was characterized by IR, 1H and 13C-NMR techniques. The composition of the copolymers was calculated by 1H-NMR spectra. The average-molecular weight of the copolymers were investigated by Gel Permeation Chromatography (GPC. For copolymerization system, their monomer reactivity ratios were obtained by using both Kelen-Tüdõs and Fineman-Ross equations. Thermal analysis measurements of homo- and copolymers prepared CFRP and ATRP methods were measured by TGA-50 and DSC-50. Blends of poly(PCMMA and poly(St obtained via ATRP method have been prepared by casting films from dichlorormethane solution. The blends were characterized by differential scanning calorimetry. The initial decomposition temperatures of the resulting copolymers increased with increasing mole fraction of St.

  3. Characterization of polyethyleneterephthalate (PET) based proton exchange membranes prepared by UV-radiation-induced graft copolymerization of styrene

    Energy Technology Data Exchange (ETDEWEB)

    Ahmed, Mostak; Khan, Mohammad B.; Alam, S. Shamsul; Khan, M. Anwar H. [Department of Chemistry, Shahjalal University of Science and Technology, Sylhet 3114 (Bangladesh); Khan, Mubarak A. [Radiation and Polymer Chemistry Laboratory, Institute of Nuclear Science and Technology, Bangladesh Atomic Energy Commission, P.O. Box 3787, Dhaka (Bangladesh); Halim, Md. Abdul [Department of Chemistry, Jahangirnagar University, savar, Dhaka (Bangladesh)

    2011-01-15

    Polymer electrolyte membranes (PEMs) were successfully prepared by simultaneous ultraviolet (UV) radiation-induced graft copolymerization of styrene (35 vol.% concentration) onto poly(ethyleneterephthalate) (PET) film, followed by sulfonation on the styrene monomer units in the grafting chain using 0.05 M chlorosulfonic acid (ClSO{sub 3}H). The radiation grafting and the sulfonation have been confirmed by titrimetric and gravimetric analyses as well as Fourier Transform Infrared (FTIR) spectroscopy. The maximum ion-exchange capacity (IEC) of the PEM was measured to be 0.04385 mmol g{sup -1} at its highest level of grafting and sulfonation. They exhibited high thermal and mechanical properties as well as oxidative stability. They are highly stable in H{sub 2}SO{sub 4} solutions and can be used in the acidic fuel cells. The membranes showed low water uptake as well as low proton conductivity than Nafion. In this study, the preparation of PEMs from commodity-type polymers is found to be very inexpensive and is a suitable candidate for applications in fuel cells. (author)

  4. Furfuralcohol Co-Polymerized Urea Formaldehyde Resin-derived N-Doped Microporous Carbon for CO2 Capture

    Science.gov (United States)

    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.

  5. Study of Graft Copolymerization of Acrylic Acid Onto Nata De Coco and its Application as Microfiltration Membrane

    Directory of Open Access Journals (Sweden)

    T. Puspitasari

    2006-07-01

    Full Text Available Chemical and physical modifications of membrane can be carried out by radiation induced graft copolymerization. The aim of this research is to prepare graft copolymers of acrylic acid onto nata de coco (NDC-g-AAc by radiation and to study the performance of grafted copolymer as microfiltration membrane. Using a total dose of 30 kGy, the highest degree of grafting obtained were 209% and 142% for r (weight ratio of monomers to nata de coco equal to 61.3 and 35.7 respectively. The increasing degree of grafting resulted in decreasing flux due to high hydrogen bonding between grafted acrylic groups and water. It was found that the degree of swelling of NDC-g-AAc membrane with r = 35.7 was higher than that of r = 63.1. The changes of chemical structure of membrane were characterized by FTIR spectroscopy which showed a new band at 1720 cm-1 attributed to the carbonyl group of acrylic acid

  6. Sulfated Alkyl Glucopyranans with Potent Antiviral Activity Synthesized by Ring-Opening Copolymerization of Anhydroglucose and Alkyl Anhydroglucose Monomers

    Directory of Open Access Journals (Sweden)

    Shiming Bai

    2015-01-01

    Full Text Available Sulfated glucopyranans having long alkyl groups were prepared by the ring-opening copolymerization of benzylated 1,6-anhydroglucopyranose with 3-O-octadecyl 1,6-anhydro-β-d-glucopyranose monomers, and subsequent deprotection and sulfation. Water-soluble sulfated glucopyranans with 2.8 and 4.7 mol% of 3-O-octadecyl group and lower molecular weights of M-n = 2.5 × 103–5.1 × 103 have potent anti-HIV activity at 0.05–1.25 μg/mL, even though sulfated polysaccharides with molecular weights below M-n = 6 × 103 had low anti-HIV activity. The interaction with poly-l-lysine as a model compound of proteins was analyzed by SPR, DSL, and zeta potential, indicating that the sulfated 3-O-octadecyl glucopyranans had high association and low dissociation rate constants, and the particle size increased after addition of poly-l-lysine. The anti-HIV activity was induced by electrostatic interaction between sulfate groups and amino groups of poly-l-lysine and by the synergistic effect of the hydrophobic long alkyl chain and hydrophilic sulfated group.

  7. Application of fluid-rock reaction studies to in situ recovery from oil sand deposits, Alberta Canada. II. Mineral transformations during an experimental-statistical study of water-bitumen-shale reactions

    Energy Technology Data Exchange (ETDEWEB)

    Boon, J.A.; Hitchon, B.

    1983-01-01

    During the experiment, calculations were made of the mud-mineral equilibrium and studies were made of the x-ray diffractogram of the solid phases. Data on deviations from equilibriums and intensity of the normalized x-ray diffraction peaks were processed by the method of dispersion analysis. It was established that in addition to dissolving the quartz, formation of montmorillonite occurs, probably by forming transitional illite-montmorillonite interstratified layered structures. The reactions promote high pH values of the aqueous medium. The solubility of siderite to a considerable degree is determined by the reaction time and mineralization of the aqueous phase, and also the ratios of pH/mineralization, time/mineralization and pH/temperature/time. Despite the limitations associated with laboratory nature of the experiment, one can draw the conclusion that during development of the bituminous sands by the in situ method, processes of dissolving minerals are widespread.

  8. Correlating Reactivity and Selectivity to Cyclopentadienyl Ligand Properties in Rh(III)-Catalyzed C-H Activation Reactions: An Experimental and Computational Study.

    Science.gov (United States)

    Piou, Tiffany; Romanov-Michailidis, Fedor; Romanova-Michaelides, Maria; Jackson, Kelvin E; Semakul, Natthawat; Taggart, Trevor D; Newell, Brian S; Rithner, Christopher D; Paton, Robert S; Rovis, Tomislav

    2017-01-25

    Cp(X)Rh(III)-catalyzed C-H functionalization reactions are a proven method for the efficient assembly of small molecules. However, rationalization of the effects of cyclopentadienyl (Cp(X)) ligand structure on reaction rate and selectivity has been viewed as a black box, and a truly systematic study is lacking. Consequently, predicting the outcomes of these reactions is challenging because subtle variations in ligand structure can cause notable changes in reaction behavior. A predictive tool is, nonetheless, of considerable value to the community as it would greatly accelerate reaction development. Designing a data set in which the steric and electronic properties of the Cp(X)Rh(III) catalysts were systematically varied allowed us to apply multivariate linear regression algorithms to establish correlations between these catalyst-based descriptors and the regio-, diastereoselectivity, and rate of model reactions. This, in turn, led to the development of quantitative predictive models that describe catalyst performance. Our newly described cone angles and Sterimol parameters for Cp(X) ligands served as highly correlative steric descriptors in the regression models. Through rational design of training and validation sets, key diastereoselectivity outliers were identified. Computations reveal the origins of the outstanding stereoinduction displayed by these outliers. The results are consistent with partial η(5)-η(3) ligand slippage that occurs in the transition state of the selectivity-determining step. In addition to the instructive value of our study, we believe that the insights gained are transposable to other group 9 transition metals and pave the way toward rational design of C-H functionalization catalysts.

  9. 苯酚苯胺共聚物在304不锈钢电极表面的电化学合成及成膜微观结构分析%Electrochemical Synthesis of Phenol-aniline Copolymerization Coating on 304 Stainless Steel Anodes and Coating Microstructure Analysis

    Institute of Scientific and Technical Information of China (English)

    鲍立垠; 熊蓉春; 张雯; 魏刚

    2011-01-01

    Electrochemical copolymerization of phenol and aniline was achieved on 304 stainless steel anodes in neutral water solution with an electrolyte of Na2SO4O4. Compared with pit corrosion potential of different copolymer coatings, the best solution composition was 0.09 mol/L phenol and 0.01 mol/L aniline. Through infrared spectrum analysis, polyaniline structure was proved in phenol-aniline copolymer, as well as more side chains. Scanning electron microscope was used to analyze microstructure of copolymer coating, taking advantage of part solubility of phenol-aniline copolymer in tetrahydrofuran, the bifurcate network structure was observed. The copolymer coating microstructure was summarized, compared with the performance of polyphenol coatings, the reasons of corrosion resistance enhancement with the addition of aniline in electropolymerization reaction was assumed as well.

  10. Study on copolymerization of cyclohexene and 1-12 olefins by aluminium-chloride-isopropanol-complex%AlCl3-异丙醇络合催化1-十二碳烯烃与环己烯共聚反应的研究

    Institute of Scientific and Technical Information of China (English)

    卢富强; 丁洪生; 刘晓宇; 杨晓明

    2012-01-01

    Polyolefin lubricating oil is one of the important synthetic lubricants.The copolymerization of cyclohexene and 1-12 olefins had been studied with aluminium chloride-isopropanol complex as the catalyst.The infLuence of various kinds of technological conditions, such as consumption quantity of the catalyst,molar ratios of the isopropanol to A1C13, reaction temperatures and reaction time on the yields of the products were studied.The optimum process conditions had been established as A1C13 mole fractions of 4%,isopropanol/A1C13 molar ratio of 0.5,reaction temperature of 50~60 °C and reaction time for 6h.Under these conditions, the influence of proportions of olefin materials on the properties of the products had been studied.The experimental results showed that, 1 : 2 was the best molar ratio of raw materials,the viscosity at 100 °C was 6.10 mm2/s,the viscosity index was 157,the condensation point was -35 °C ,and the yield of synthetic oil was 86%.The products had some advantages, such as lower viscosity, lower solidifying point and higher viscosity index, which proved the product was a kind of high quality polyolefin synthetic lubricant.%聚烯烃润滑油是重要的合成润滑油之一.采用AlCl3作催化剂对环己烯与1-十二烯烃的共聚反应进行了研究.考察了催化剂AlCl3的用量、n(异丙醇)∶n(AlCl3)、反应温度和反应时间对产品收率的影响.确定了最佳工艺条件,即x(AlCl3)=4%,n(异丙醇)∶n(AlCl3)=0.5,反应温度50~60℃,反应时间6h.在最佳工艺条件下,调节环己烯与1-十二碳烯的混合比例进行了实验,研究了产品的物化性能.实验结果表明:采用n(1-十二烯烃)∶72(环已烯)=2∶1时,可以合成100℃粘度为6.10 mm2/s,粘度指数为157,凝点为-35℃的聚烯烃合成油,收率为86%.具有粘度低、凝点低、粘度指数高的显著特点,是高质量的聚烯烃合成油.

  11. Experimental Research and Numerical Simulation of Afterburning Reaction of TNT Explosive by Underwater Explosion%TNT 后燃反应的水下爆炸实验研究与数值模拟

    Institute of Scientific and Technical Information of China (English)

    曹威; 何中其; 陈网桦

    2014-01-01

    To explore the afterburning reaction of TNT explosive,the underwater explosion method and an experimental device designed to enhance the afterburning reaction of explosives were used to inves-tigate the energy output structure,and the afterburning reaction energy in different ambient atmos-phere was calculated.The experimental data of afterburning reaction was simulated by using Miller energy release model.The results show that the experimental device filled with oxygen or air can increase the afterburning reaction energy output of TNT explosive significantly.The measured after-burning reaction energy increases with the increase of the content of oxygen,and in the studied range, the afterburning reaction energy reaches the maximum value of 4.90 kJ/g,but does not reach the theo-retically maximum value.The computed shock wave pressure histories agree with the measured ones well,which indicates that the Miller energy release model is practicable.%为了研究 TNT 炸药的后燃反应,采用水下爆炸实验方法和一种增强炸药后燃反应的实验装置,对 TNT 炸药的能量输出结构进行了研究,计算得到了不同气体氛围下的后燃反应能量。采用 Miller 能量释放模型,对后燃反应实验结果进行了数值模拟。结果表明:在实验装置中充入空气或氧气,可明显增强 TNT 炸药的后燃反应能量输出,实测的后燃反应能量随着氧含量的增加而增大,在实验研究范围内后燃反应能量的最大值达到4.90 kJ/g,但并没有达到后燃反应能量的理论最大值;冲击波压力时程曲线的数值模拟结果与实验结果基本一致,证明了 Miller 能量释放模型的可行性。

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

    DEFF Research Database (Denmark)

    Johansen, Jacob S.; Bildstein, V.; Borge, M. J. G.

    2013-01-01

    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 arra...

  13. Experimental cross section of the {sup 71}Ga(n,γ){sup 72}Ga reaction at 0.0334 eV energy

    Energy Technology Data Exchange (ETDEWEB)

    Afroze, N. [Institute of Nuclear Science and Technology, Atomic Energy Research Establishment, GPO Box No. 3787, Savar, Dhaka 1000 (Bangladesh); Department of Physics, Jahangirnagar University, Savar, Dhaka (Bangladesh); Uddin, M.S., E-mail: md.shuzauddin@yahoo.com [Institute of Nuclear Science and Technology, Atomic Energy Research Establishment, GPO Box No. 3787, Savar, Dhaka 1000 (Bangladesh); Hossain, S.M.; Islam, M.A.; Shariff, M.A.; Zakaria, A.K.M.; Datta, T.K. [Institute of Nuclear Science and Technology, Atomic Energy Research Establishment, GPO Box No. 3787, Savar, Dhaka 1000 (Bangladesh); Azharul Islam, S.M. [Department of Physics, Jahangirnagar University, Savar, Dhaka (Bangladesh)

    2014-10-01

    Highlights: •Neutrons were monochromatized from powder diffractometer. •The cross section of the {sup 71}Ga(n,γ){sup 72}Ga reaction at 0.0334 eV was measured. •The {sup 197}Au(n,γ){sup 198}Au reaction was used to monitor the neutron beam intensity. •Only thermal neutrons of a single energy was used for irradiation. -- Abstract: The cross section of the {sup 71}Ga(n,γ){sup 72}Ga reaction at 0.0334 eV was measured for the first time using monochromatic neutrons from powder diffractometer at TRIGA Mark II nuclear reactor. The {sup 197}Au(n,γ){sup 198}Au 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.

  14. [Hymenolepis nana var. fraterna (Cestoda: Hymenolepididae) in Leucophaea maderae (Dictyoptera: Blattidae): the host-parasite conflict after experimental inhibition of haemocytic reaction (author's transl)].

    Science.gov (United States)

    Pesson, B; Leger, N

    1978-01-01

    Development of non-encapsulated cysticercoids of Hymenolepis nana var. fraterna, in the haemocoele of Leucophaea maderae occured after the inhibition of the haemocytic reaction by irradiation or injection of a soluble antigen of Hymenolepis nana. Fine structure of the tegument of free larvae is observed and the mechanism of a possible defence of the parasite by the microvillar coat, discussed.

  15. The antinociceptive effect and adverse drug reactions of oxycodone in human experimental pain in relation to genetic variations in the OPRM1 and ABCB1 genes

    DEFF Research Database (Denmark)

    Zwisler, Stine T; Enggaard, Thomas P; Noehr-Jensen, Lene

    2010-01-01

    The aim of this study was to search for a possible association between the variant allele of the single nucleotide polymorphisms A118G in the OPRM1 gene and C3435T and G2677T/A in the ABCB1 gene and altered antinociceptive effect and adverse drug reactions of oxycodone. Thirty-three healthy subje...

  16. 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

    Energy Technology Data Exchange (ETDEWEB)

    Alizadeh, Taher, E-mail: talizadeh@ut.ac.ir [Department of Analytical Chemistry, Faculty of Chemistry, University College of Science, University of Tehran, P.O. Box 14155-6455, Tehran (Iran, Islamic Republic of); Bagherzadeh, Azam; Shamkhali, Amir Nasser [Department of Applied Chemistry, Faculty of Science, University of Mohaghegh Ardabili, Ardabil (Iran, Islamic Republic of)

    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. - Highlights: • A new chiral functional monomer of (S)-2-(acrylamido) propanoic acid was synthesized. • (S)-propranolol-selective imprinted polymer was synthesized using the chiral monomer. • Racemic propranolol mixed with Cu(II) was used as template in the imprinting. • Density functional theory was employed to clarify the imprinting mechanism. • (S)-propranolol-Cu(II) complex was shown to conduct the imprinting process.

  17. pH-sensitive wax emulsion copolymerization with acrylamide hydrogel using gamma irradiation for dye removal

    Science.gov (United States)

    Ghobashy, Mohamed Mohamady; Elhady, Mohamed., A.

    2017-05-01

    Emulsion polymerization is an efficient method for the production of new wax-hydrogel matrices of cetyl alcohol: stearic acid wax and acrylamide hydrogel using triethylamine (TEA) as an emulsifier. A cross-linking reaction occurred when a mixture of wax-hydrogel solution was irradiated with gamma rays at a dose of 20 kGy. The gelation percentage of the matrices (CtOH-StA/PAAm) was 86%, which indicates that a sufficiently high conversion occurred in these new wax-hydrogel matrices. The ability of PAAm and CtOH-StA/PAAm as an adsorbent for dye removal was investigated. The removal of three reactive dyes, namely Remazol Red (RR), Amido Black (AB), and Toluidine Blue (TB), from aqueous solutions depends on the pH of the dye solution. Removal efficiency was investigated by UV spectrophotometry, and the results showed the affinity of the wax hydrogel to adsorb TB was 98% after 320 min. Fourier transform infrared-attenuated total reflectance spectra confirmed the cross-linking process involved between the chains of wax and hydrogel; furthermore, scanning electron microscopy images showed that the wax and hydrogel were completely miscible to form a single matrix. Swelling measurements showed the high affinity of adsorbed dyes from aqueous solutions at different pH values to the wax-hydrogel network; the highest swelling values of 13.05 and 8.24 (g/g) were observed at pH 10 and 6, respectively

  18. Swelling, ion uptake and biodegradation studies of PE film modified through radiation induced graft copolymerization

    Science.gov (United States)

    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.

  19. Experimental cross section for the {sup 152}Sm(n, γ){sup 153}Sm reaction at 0.0334 eV

    Energy Technology Data Exchange (ETDEWEB)

    Uddin, M. Shuza; Datta, Tapash Kumar; Hossain, Syed Mohammod; Zakaria, A.K.M.; Islam, Mohammad Amirul; Naher, Kamrun; Shariff, M. Asad; Yunus, S.M. [Atomic Energy Research Establishment, Dhaka (Bangladesh). Inst. of Nuclear Science and Technology; Afroze, Nasmin [Atomic Energy Research Establishment, Dhaka (Bangladesh). Inst. of Nuclear Science and Technology; Jahangirnagar Univ., Dhaka (Bangladesh). Dept. of Physics; Islam, S.M. Ajharul [Jahangirnagar Univ., Dhaka (Bangladesh). Dept. of Physics

    2014-10-01

    The neutron capture cross section for the {sup 152}Sm(n, γ){sup 153}Sm reaction at an energy of 0.0334 eV was measured for the first time using monochromatic neutrons of a powder diffractometer at the TRIGA Mark II nuclear reactor at Dhaka, Bangladesh. The {sup 197}Au(n, γ){sup 198}Au reaction was used to monitor the neutron beam intensity. The radioactivity of the products was determined via high resolution γ-ray spectrometry. The obtained cross section value is 184 ± 22b, which is consistent with both the ENDF/B-VII and TENDL-2012 data libraries. The measured value at 0.0334 eV and the previous data at 0.0536 eV confirm the reliability of the data in the above libraries. (orig.)

  20. Experimental Probe to the Isospin-Dependent Properties of Hot Nuclei in Reactions 40Ar+112,124 Sn at 30 MeV/u

    Institute of Scientific and Technical Information of China (English)

    肖志刚; 靳根明; 吴和宇; 魏志勇; 王宏伟; 段利敏; 柳永英; 李祖玉; 张保国; 诸永泰; 王素芳; 卢朝晖; 朱海东; 胡荣江

    2001-01-01

    Protons are emitted in a greater quantity in a neutron-deficient system 40Ar+112Sn while triton emissions are greater in a neutron-rich system 40Ar+124Sn at an incident energy of 30 MeV/u. Similar to neutrons, proton emission provides a dominant contribution to neutralize the system N/Z in the decay process of the hot nuclei.The emission of hydrogen isotopes with high energies is much enhanced in the 112Sn system. The original temperature of the hot nuclei in the 40Ar+112Sn reaction is 5.8+0.3 MeV, about 0.7 MeV higher than 5.1+0.3MeV as in the 40Ar+124Sn reaction.

  1. Experimental investigation of the confinement of d(3He,p)α and d(d,p)t fusion reaction products in JET

    DEFF Research Database (Denmark)

    Bonheure, Georges; Hult, M.; Gonzalez de Orduna, R.

    2012-01-01

    In ITER, magnetic fusion will explore the burning plasma regime. Because such burning plasma is sustained by its own fusion reactions, alpha particles need to be confined (Hazeltine 2010 Fusion Eng. Des. 7–9 85). New experiments using d(3He,p)α and d(d,p)t fusion reaction products were performed...... in JET. Fusion product loss was measured from MHD-quiescent plasmas with a charged particle activation probe installed at a position opposite to the magnetic field ion gradient drift (see figure 1)—1.77 m above mid-plane—in the ceiling of JET tokamak. This new kind of escaping ion detector (Bonheure et...... al 2008 Fusion Sci. Technol. 53 806) provides for absolutely calibrated measurements. Both the mechanism and the magnitude of the loss are dealt with by this research. Careful analysis shows measured loss is in quantitative agreement with predictions from the classical orbit loss model. However...

  2. 我国MBO事件市场反应实证分析%The Experimental Analysis of Reaction of MBO Incident in the Market

    Institute of Scientific and Technical Information of China (English)

    廖理; 罗洪涛; 赵锋

    2005-01-01

    This paper used event study methods to study the market responses to MBO (Management Buyout).The result illustrates that after MBO, CAR (cumulated abnormal return)is significantly larger than zero (2.52%). And moreover, the volatility changes little after MBO. From this result, we can say that the reaction of investors for MBO is positive. At the same time, government can gradually loosen the limit for it to improve the market development and for the benefit of investors.

  3. Theoretical Analyses and Experimental Investigations of Selective Carbothermal Reactions of Vanadium-Bearing Titanomagnetite Concentrates for Preparation of Iron-Based Wear-Resistant Material

    Science.gov (United States)

    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.

  4. Charge state distribution of {sup 16}O from the {sup 4}He({sup 12}C,{sup 16}O)γ reaction of astrophysical interest studied both experimentally and theoretically

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Shengjin, E-mail: liusj@ihep.ac.cn [Institute of High Energy Physics, China Academy of Science, 19B YuquanLu, Shijingshan, Beijing 100049 (China); Department of Physics, Kobe University, 1-1 Rokkodai, Nada, Kobe 657-8501 (Japan); Sakurai, Makoto [Department of Physics, Kobe University, 1-1 Rokkodai, Nada, Kobe 657-8501 (Japan); Sagara, Kenshi; Teranishi, Takashi; Fujita, Kunihiro; Yamaguchi, Hiroyuki; Matsuda, Sayaka; Mitsuzumi, Tatsuki; Iwazaki, Makoto; Rosary, Mariya T. [Department of Physics, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581 (Japan); Kato, Daiji [Fusion Systems Research Division, National Institute for Fusion Science, 322-6 Oroshi-cho, Toki, Gifu 509-5292 (Japan); Tolstikhina, I.Yu. [P.N. Lebedev Physical Institute, Leninskii pr. 53, Moscow 119991 (Russian Federation)

    2014-06-01

    In astrophysics, {sup 4}He({sup 12}C,{sup 16}O)γ reaction places an important role. At Kyushu University Tandem accelerator Laboratory (KUTL), the measurement of {sup 4}He({sup 12}C,{sup 16}O)γ cross section is in progress in the energy range of astrophysical nuclear reaction. Since the charge state of product {sup 16}O ions after passing through the gas target is spread and only one charge state can be measured at terminal detector, it is necessary to know the charge state distribution of {sup 16}O ions passing through the He gas target precisely. Here, we report the charge state distribution of the {sup 16}O recoils both experimentally and theoretically. Experimentally, we measured the equilibrium charge state distribution of {sup 16}O ions in the windowless helium gas target with the beam energy of primary {sup 16}O ions at 7.2, 4.5, and 3.45 MeV at KUTL. The measured results showed a Gaussian distribution for the charge state fraction. Theoretically, we proposed a framework for the charge state distribution study. Charge state distribution was computed by solving a set of differential equations including a series of charge exchange cross sections. For the ionization cross section, plane-wave Born approximation was applied and modified by taking target atomic screening as a function of momentum transfer into account. For the capture cross section, continuum distorted wave approximation was applied and the influence of the gas target density was taken into account in the process of electron capture. Using above charge exchange cross sections, the charge state evolution was simulated. According to the equilibrium distribution, we compared the theoretical calculation to the experimental data. After taking into account the density effects in the charge exchange process, the theoretical charge state distributions shows a good agreement with the experimental data. Both experimental and theoretical results are useful to understand the charge fraction of recoil oxygen

  5. 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.

    Science.gov (United States)

    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.

  6. Preparation polystyrene/multiwalled carbon nanotubes nanocomposites by copolymerization of styrene and styryl-functionalized multiwalled carbon nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Hua, Jing, E-mail: huajing72@qust.edu.cn [Key Laboratory of Rubber-Plastics Ministry of Education, Qingdao University of Science and Technology, Qingdao (China); Wang, Zhongguang; Xu, Ling; Wang, Xin; Zhao, Jian; Li, Feifei [Key Laboratory of Rubber-Plastics Ministry of Education, Qingdao University of Science and Technology, Qingdao (China)

    2013-01-15

    Styryl-functionalized multiwalled carbon nanotubes (p-MWNTs) were prepared by esterification based on the carboxylate salt of carbon nanotubes and p-chloromethylstyrene in toluene. Then in situ radical copolymerization of p-MWNTs and styrene initiated by 2,2 Prime -azobis(isobutyronitrile) (AIBN) was applied to synthesize composites of styryl-functionalized multiwalled carbon nanotubes and polystyrene (PS) (p-MWNTs/PS). Characterizations carried out by FT-IR, {sup 1}H NMR, UV-vis show that styryl group covalently bond to the surface of MWNTs. The results of UV showed that the solutions of p-MWNTs/PS in chloroform have the hyperchromic effect. Transmission electron microscopy (TEM) images of p-MWNTs/PS composites and scanning electron microscopy (SEM) images of fracture surface of p-MWNTs/PS composites showed the functionalized nanotubes had a better dispersion than that of the unfunctionalized MWNTs in the matrix. The results of thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) suggested that the thermal stability of p-MWNTs/PS composites improved in the presence of MWNTs. -- Highlights: Black-Right-Pointing-Pointer A facile and simple way to successfully prepare the polystyrene/MWNTs nanocomposites. Black-Right-Pointing-Pointer Characterizations show that styryl group covalently bond to the surface of MWNTs. Black-Right-Pointing-Pointer The solutions of p-MWNTs/PS in chloroform have the hyperchromic effect. Black-Right-Pointing-Pointer Thermal stability of p-tpas composites improved in the presence of MWNTs. Black-Right-Pointing-Pointer The performance of polymer prepared by this method have great potential for exploitation.

  7. Observation of Different Catalytic Activity of Various 1-Olefins during Ethylene/1-Olefin Copolymerization with Homogeneous Metallocene Catalysts

    Directory of Open Access Journals (Sweden)

    Mingkwan Wannaborworn

    2011-01-01

    Full Text Available This research aimed to investigate the copolymerization of ethylene and various 1-olefins. The comonomer lengths were varied from 1-hexene (1-C6 up to 1-octadecene (1-C18 in order to study the effect of comonomer chain length on the activity and properties of the polymer in the metallocene/MAO catalyst system. The results indicated that two distinct cases can be described for the effect of 1-olefin chain length on the activity. Considering the short chain length comonomers, such as 1-hexene, 1-octene and 1-decene, it is obvious that the polymerization activity decreased when the length of comonomer was higher, which is probably due to increased steric hindrance at the catalytic center hindering the insertion of ethylene monomer to the active sites, hence, the polymerization rate decreased. On the contrary, for the longer chain 1-olefins, namely 1-dodecene, 1-tetradecene and 1-octadecene, an increase in the comonomer chain length resulted in better activity due to the opening of the gap aperture between Cp(centroid-M-Cp-(centroid, which forced the coordination site to open more. This effect facilitated the polymerization of the ethylene monomer at the catalytic sites, and thus, the activity increased. The copolymers obtained were further characterized using thermal analysis, X-ray diffraction spectroscopy and 13C-NMR techniques. It could be seen that the melting temperature and comonomer distribution were not affected by the 1-olefin chain length. The polymer crystallinity decreased slightly with increasing comonomer chain length. Moreover, all the synthesized polymers were typical LLDPE having random comonomer distribution.

  8. Oxidation-Responsive and "Clickable" Poly(ethylene glycol) via Copolymerization of 2-(Methylthio)ethyl Glycidyl Ether.

    Science.gov (United States)

    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.

  9. Surface modification of silicone rubber membrane by plasma induced graft copolymerization as artificial cornea.

    Science.gov (United States)

    Hsiue, G H; Lee, S D; Chang, P C

    1996-11-01

    In this study a highly biocompatible polymer membrane was prepared by surface modification. An artificial cornea was also developed for clinical applications. Silicone rubber (SR) membrane was grafted with hydrophilic monomers such as 2-hydroxyethyl methacrylate (HEMA) and acrylic acid by plasma induced grafted polymerization. Surface properties of the SR were characterized using secondary ions mass spectra, Fourier transform infrared/attenuated total reflection, and element spectra for chemical analysis. The corneal epithelial (CE) cell was cultured in vitro, and penetrating keratoplasty of albino rabbit cornea (in vivo) was performed to evaluate biological properties of modified SR membranes. The ability of the CE cell to attach onto various SR membranes was observed by inverted microscopy. The proliferation of CE cell was conducted in approximately 96 h. Experimental results indicated that the attachment and growth of CE onto SR-g-pHEMA (75 micrograms/ cm2) is enhanced. The morphologies of an attached CE cell are similar to those of a primary CE cell. In the in vivo study, the depth of anterior chamber was maintained 2 weeks after penetrating keratoplasty was performed with a SR grafted with pHEMA (210 micrograms/cm2). This phenomenon displayed a high biocompatibility of modified SR membrane with the CE cell. Furthermore, results in this study provide a valuable reference for application of the modified SR for an artificial cornea.

  10. Exploring chain length selectivity in HIC-catalyzed polycondensation reactions.

    Science.gov (United States)

    Feder, David; Gross, Richard A

    2010-03-08

    Polyester synthesis activity of immobilized Humicola insolens (HiC) was systematically studied with three-series of substrates varying in (i) omega-hydroxyalkanoic acid (omegaHA), (ii) alpha,omega-n-alkane diol, and (iii) alpha,omega-n-alkane diacid chain length. Covalent immobilization of HiC on Amberzyme oxirane (AO) resin (i.e., AO-HiC) was prepared. HiC-AO's activity for omegaHA substrates with 6, 10, 12, and 16 carbons was C16 > C12, where C10-omegaHA and C6-omegaHA were not polymerized. In contrast, N435's activity for omegaHA substrates was C16 = C12 > C10, where C6-omegaHA was not polymerized. HiC-AO activity for copolymerization of sebacic acid (C10-diacid) with alpha,omega-n-alkane diols with 3-, 4-, 5-, 6-, and 8-carbon chain lengths was C8 > C6, where C3, C4, and C5 diols were not polymerized. N435's relative activity for diol substrates was C8 = C6 = C5 > C4 > C3. HiC-AO activity for copolymerizations of 1,8-octanediol with alpha,omega-n-alkane diacids with 6-, 8-, 9-, 10-, and 13-carbon chain lengths was C13 = C10, where HiC showed little activity for C6, C8, and C9 diacid copolymerization. N435 displayed similar activity for all these diacid chain lengths. Thus, N435 has a broader substrate promiscuity than HiC-AO. This is most apparent for shorter chain length omegaHA, diol, and diacid monomers. These trends were similarly observed for a series of small molecule esterification reactions. Comparison of HiC-AO- and N435-catalyzed C16-HA homopolymerization at 8 h gave polymers with M(n) 40.4 and 25.5 kg/mol, respectively. Furthermore, HiC-AO- and N435-catalyzed copolymerization of 1,8-octanediol/C13-diacid polymerizations at 8 h gave polymers with M(n) of 11.0 and 9.6 kg/mol, respectively.

  11. Triblock and pentablock terpolymers by sequential base-assisted living cationic copolymerization of functionalized vinyl ethers

    KAUST Repository

    Bouchekif, Hassen

    2015-01-01

    A series of novel, well-defined triblock (PnBVE-b-PCEVE-b-PSiDEGVE) and pentablock (PSiDEGVE-b-PCEVE-b-PnBVE-b-PCEVE-b-PSiDEGVE) terpolymers of n-butyl vinyl ether (nBVE), 2-chloroethyl vinyl ether (CEVE) and tert-butyldimethylsilyl ethylene glycol vinyl ether (SiEGVE) were synthesized by sequential base-assisted living cationic polymerization. The living character of the homopolymerization of the three VE monomers and the crossover reaction resulting in the formation of well-defined block copolymers were investigated in various solvents (toluene, dichloromethane and n-hexane) using either a monofunctional [nBVE-acetic acid adduct (nBEA), CEVE-acetic acid adduct (CEEA) and SiDEGVE-acetic acid adduct (SiDEGEA)] or a difunctional [1,4-cyclohexane-1,4-diyl bis(2-methoxyethyl acetate) (cHDMEA)] initiator. All initiators are structurally equivalent to the dormant species of the corresponding monomers in order to achieve fast initiation. The optimal conditions of polymerization were achieved in n-hexane at -20 °C, in the presence of 1 M AcOEt (base). Good control over the number average molecular weight (Mn) and the polydispersity index (PDI) was obtained only at [Et3Al2Cl3]0 = [Chain-end]0 ≤ 10 mM. 2,6-Di-tert-butylpyridine (DtBP) was used as a non-nucleophilic proton trap to suppress any protonic initiation from moisture (i.e., Et3Al2Cl3·H2O). Well-defined PnBVEn-b-PCEVEp-b-PSiDEGVEq and PSiDEGVEq-b-PCEVEp-b-PnBVEn-b-PCEVEp-b-PSiDEGVEq terpolymers with a high crossover efficiency, no PCEVE-induced physical gelation, and predictable Mn and PDI < 1.15 were synthesized successfully provided that the targeted DPCEVE/DPnBVE ratio (i.e., p/n) did not exceed 2 and 0.2, respectively. The quantitative desilylation of the PSiEGVE by n-Bu4N+F- in THF at 0 °C led to triblock and pentablock terpolymers in which the PCEVE is the central block and the polyalcohol is the outer block. The thermal properties of the synthesized materials were examined by differential scanning

  12. Swelling, ion uptake and biodegradation studies of PE film modified through radiation induced graft copolymerization

    Energy Technology Data Exchange (ETDEWEB)

    Kaur, Inderjeet, E-mail: ij_kaur@hotmail.com [Department Chemistry, HPU Shimla 171005 (India); Gupta, Nitika; Kumari, Vandna [Department Chemistry, HPU Shimla 171005 (India)

    2011-09-15

    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 {gamma}-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=204.6x10{sup -2} mol/L ([MAAc]=176.5x10{sup -2} mol/L, [AAm]=28.1x10{sup -2} mol/L), [BPO]=8.3x10{sup -2} mol/L at 100 deg. 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. - Highlights: > Binary mixture of methacrylic acid (MAAc) and acrylamide (AAm) onto PE film by preirradiation method was carried out. > Graft copolymers of MAAc+AAm and PE film were characterized by FTIR, TGA and SEM studies and was found to be thermally stable. > Grafting of MAAc+AAm improved swelling behavior giving maximum swelling (485.71%) in water as against PE with 0% swelling. > The grafted PE-g-poly (MAAc-co-AAm) behaves as an excellent material for ion separation. > Biodegradation studies by soil burial test showed 47.19% of

  13. Experimental Study on Reaction Energy Release Characteristics of Hydrocarbon and Chlorine Trifluoride%三氟化氯与碳氢燃料反应放能试验研究

    Institute of Scientific and Technical Information of China (English)

    高洪泉; 卢芳云; 王少龙; 罗永锋; 闫华; 刘志勇

    2011-01-01

    Using a designed experimental device,explosion experiments of hydrocarbon with chlorine trifluoride in confined space were carried out,based on the analysis of the hydrocarbon and chlorine trifluoride reaction mechanism. The energy released from the reaction of hydrocarbon and chlorine trifluoride without oxygen was calculated based on experimental results. Results show that (1) The reaction of hydrocarbon and chlorine trifluoride accompanies an intense release of great deal of energy,so that part of the hydrocarbon is vaporized and dispersed,a violent deflagrating would be ignited once the vaporized hydrocarbon be mixed with the air. (2) The TNT equivalence of the explosion reaction of hydrocarbon and chlorine trifluoride without oxygen is about 1.8.%在对三氟化氯与碳氢燃料反应机理进行分析的基础上,进行了密闭环境下三氟化氯与碳氢燃料的反应放能试验研究.结果表明:三氟化氯与碳氢燃料可以发生剧烈反应,释放大量的能量,将碳氢燃料部分雾化并喷出密闭空间,激活的碳氢燃料一旦接触空气,便诱发碳氢燃料的剧烈爆燃;在无氧条件下,三氟化氯与碳氢燃料爆炸反应所释放的能量相当于1.8倍TNT当量.

  14. Experimental and theoretical investigation of benzyl--pyrrolylketene, one- step procedure for preparing of new -lactams by [2+2] cycloaddition reaction

    Indian Academy of Sciences (India)

    Masoumeh Behzadi; Kazem Saidi; Mohammad Reza Islami; Hojatollah Khabazzadeh

    2016-01-01

    3-Phenyl-2-(1--pyrrol-1-yl) propanoic acid has been used as a ketene source in synthesizing of monocyclic-2-azetidinones. Hindrance in ketene and imines successfully controlled the diastereoselectivity of the reaction. For example, in some cases only one isomer was achieved. By using Mukaiyama reagent, the leaving group in acid was activated and the by-products were separated by simple aqueous work-up. DFT calculation indicated that the benzyl--pyrrolylketene has nonconjugated structure and the pyrrolyl ring is perpendicular to the ketene plane in both the twisted and planar structures.

  15. Using potassium catalytic gasification to improve the performance of solid oxide direct carbon fuel cells: Experimental characterization and elementary reaction modeling

    OpenAIRE

    Yu, Xiankai; Shi, Yixiang; Wang, Hongjian; Cai, Ningsheng; Li, Chen; Ghoniem, Ahmed F

    2013-01-01

    The performance of a solid oxide electrolyte direct carbon fuel cell (SO-DCFC) is limited by the slow carbon gasification kinetics at the typical operating temperatures of cell: 650–850 °C. To overcome such limitation, potassium salt is used as a catalyst to speed up the dry carbon gasification reactions, increasing the power density by five-fold at 700–850 °C. The cell performance is shown to be sensitive to the bed temperature, emphasizing the role of gasification rates and that of CO produ...

  16. THERMOKINETIC STUDY OF THE ZERO, FIRST AND SECOND ORDER REACTIONS IN A PSEUDO-ADIABATIC CALORIMETER: Numerical approach and experimental dat

    Directory of Open Access Journals (Sweden)

    Johanna Mendoza

    2012-11-01

    Full Text Available The signal produced by a pseudo-adiabaticcalorimeter is simulated by numericalsolution of the differential equations thatmodel the chemical kinetics [1], the thermalproperties of the calorimetric cell[2], and the response of the thermistorused as a thermometric sensor [3]. These equations show that the calorimetricsignal is related with concentrationin a complex way. Therefore, a comparisonbetween the signals of the threebasic kinetics reactions (zero, first andsecond order was made, as a first stepto obtain a standard procedure to followchemical kinetics using a calorimeter. Inorder to help understanding this relationship,the initial rate method was applied to the simulated data to assess the relationshipbetween the order and the kineticconstants calculated with those usedfor the simulations. As it was expected,the initial rate method for the calorimetricdata, do not give a slope directly relatedwith the order of the reaction, as itwould be produced, for example, in datafrom a spectrophotometer. However, alinear relationship was found betweenwhat we call the “calorimetric order”and the kinetic order. Finally, the developedprocedure was applied to the studyof the H2O2 decomposition catalyzedwith Fe3+ in homogeneous phase andwith activated carbon in heterogeneousphase, finding the order and the kineticsconstants of the global processes, whichwere in close agreement with those inthe literature.

  17. Experimental verification of proton beam monitoring in a human body by use of activity image of positron-emitting nuclei generated by nuclear fragmentation reaction.

    Science.gov (United States)

    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.

  18. Experimental and density functional theoretical study of the effects of Fenton’s reaction on the degradation of Bisphenol A in a high voltage plasma reactor

    Energy Technology Data Exchange (ETDEWEB)

    Dai, Fei, E-mail: daif@clarkson.edu [Department of Civil and Environmental Engineering, 8 Clarkson Avenue, Clarkson University, Potsdam, 13699 NY (United States); Fan, Xiangru, E-mail: fanx@clarkson.edu [Department of Chemical and Biomolecular Engineering, 8 Clarkson Avenue, Clarkson University, Potsdam, 13699 NY (United States); Stratton, Gunnar R., E-mail: strattgr@clarkson.edu [Department of Chemical and Biomolecular Engineering, 8 Clarkson Avenue, Clarkson University, Potsdam, 13699 NY (United States); Bellona, Christopher L., E-mail: cbellona@clarkson.edu [Department of Civil and Environmental Engineering, 8 Clarkson Avenue, Clarkson University, Potsdam, 13699 NY (United States); Department of Civil and Environmental Engineering, 1500 Illinois St., Colorado School of Mines, Golden, 80401 CO (United States); Holsen, Thomas M., E-mail: tholsen@clarkson.edu [Department of Civil and Environmental Engineering, 8 Clarkson Avenue, Clarkson University, Potsdam, 13699 NY (United States); Crimmins, Bernard S., E-mail: bcrimmin@clarkson.edu [Department of Civil and Environmental Engineering, 8 Clarkson Avenue, Clarkson University, Potsdam, 13699 NY (United States); Xia, Xiaoyan, E-mail: xiax@clarkson.edu [Department of Civil and Environmental Engineering, 8 Clarkson Avenue, Clarkson University, Potsdam, 13699 NY (United States); Mededovic Thagard, Selma, E-mail: smededov@clarkson.edu [Department of Chemical and Biomolecular Engineering, 8 Clarkson Avenue, Clarkson University, Potsdam, 13699 NY (United States)

    2016-05-05

    Highlights: • Combining the Fenton reaction with the plasma treatment reduces Bisphenol A concentration below the detection limit within 30 min. • Carbon steel electrode in the plasma reactor can be used as a source of iron ions. • OH radical attack on Bisphenol A is the primary pathway for byproduct formation. - Abstract: A novel electrical discharge plasma reactor configuration with and without iron ions was evaluated for the degradation of 0.02 mM Bisphenol A (BPA). The pseudo-first-order reaction rate constant calculated for the plasma treatment of BPA with a stainless steel electrode in the presence of dissolved ferrous ion (Fe{sup 2+}) salts (termed plasma/Fenton treatment) was higher than in the plasma treatment in the absence of iron salts. At the optimal ferrous ion concentration, longer plasma treatment times resulted in higher BPA degradation rates, likely due to increased hydroxyl (OH) radical concentration formed through the decomposition of H{sub 2}O{sub 2}. Replacing the stainless steel with a carbon steel grounded electrode resulted in the release of iron ions from the carbon steel thereby increasing the rate of BPA removal and eliminating the need for iron salts. After the plasma/Fenton treatment, >97% of the residual iron salts were removed by coagulation/flocculation/sedimentation. Byproduct identification coupled with density functional theory (DFT) calculations confirmed that OH radical attack on BPA’s hydroxyl group is the primary pathway for byproduct formation.

  19. Catalytic amine-borane dehydrogenation by a PCP-pincer palladium complex: a combined experimental and DFT analysis of the reaction mechanism.

    Science.gov (United States)

    Rossin, Andrea; Bottari, Giovanni; Lozano-Vila, Ana M; Paneque, Margarita; Peruzzini, Maurizio; Rossi, Andrea; Zanobini, Fabrizio

    2013-03-14

    Catalytic dehydrogenation of ammonia-borane (NH(3)·BH(3), AB) and dimethylamine borane (NHMe(2)·BH(3), DMAB) by the Pd(II) complex [((tBu)PCP)Pd(H(2)O)]PF(6) [(tBu)PCP = 2,6-C(6)H(3)(CH(2)P(t)Bu(2))(2)] leads to oligomerization and formation of spent fuels of general formula cyclo-[BH(2)-NR(2)](n) (n = 2,3; R = H, Me) as reaction byproducts, while one equivalent of H(2) is released per amine-borane equivalent. The processes were followed through multinuclear ((31)P, (1)H, (11)B) variable temperature NMR spectroscopy; kinetic measurements on the hydrogen production rate and the relative rate constants were also carried out. One non-hydridic intermediate could be detected at low temperature, whose chemical nature was explored through a DFT modeling of the reaction mechanism, at the M06//6-31+G(d,p) computational level. The computational output was of help to propose a reliable mechanistic picture of the process.

  20. First result of the experimental search for the 9.4 keV solar axion reactions with Kr-83 in the copper proportional counter

    CERN Document Server

    Gavrilyuk, Yu M; Derbin, A V; Kazalov, V V; Kim, H J; Kim, Y D; Kobychev, V V; Kuzminov, V V; Ali, Luqman; Muratova, V N; Panasenko, S I; Ratkevich, S S; Semenov, D A; Tekueva, D A; Yakimenko, S P; Unzhakov, E V

    2014-01-01

    The experimental search for solar hadronic axions is started at the Baksan Neutrino Observatory of the Institute for Nuclear Researches Russian Academy of Science. It is assumed that axions are created in the Sun during M1-transition between the first thermally excited level at 9.4 keV and the ground state in Kr-83. The experiment is based on axion detection via resonant absorption process by the same nucleus in the detector. The big copper proportional counter filled with krypton is used to detect signals from axions. The experimental setup is situated in the deep underground low background laboratory. No evidence of axion detection were found after the 26.5 days data collection. Resulting new upper limit on axion mass is m_{A} < 130 eV at 95% C.L.

  1. First result of the experimental search for the 9.4 keV solar axion reactions with 83Kr in the copper proportional counter

    Science.gov (United States)

    Gavrilyuk, Yu. M.; Gangapshev, A. M.; Derbin, A. V.; Kazalov, V. V.; Kim, H. J.; Kim, Y. D.; Kobychev, V. V.; Kuzminov, V. V.; Ali, Luqman; Muratova, V. N.; Panasenko, S. I.; Ratkevich, S. S.; Semenov, D. A.; Tekueva, D. A.; Yakimenko, S. P.; Unzhakov, E. V.

    2015-03-01

    The experimental search for solar hadronic axions is started at the Baksan Neutrino Observatory of the Institute for Nuclear Researches of Russian Academy of Science (BNO INR RAS). It is assumed that axions are created in the Sun during M1 transition between the first thermally excited level at 9.4 keV and the ground state in 83Kr. The experiment is based on axion detection via resonant absorption process by the same nucleus in the detector. The big copper proportional counter filled with krypton is used to detect signals from axions. The experimental setup is situated in the deep underground low background laboratory. No evidence of axion detection were found after the 26.5 days data collection. Resulting new upper limit on axion mass is m A ≤ 130 eV at 95% C.L.

  2. Mechanism of Reaction in NaAlCl4 Molten Salt Batteries with Nickel Felt Cathodes and Aluminum Anodes. Part II: Experimental Results and Comparison with Model Calculations

    DEFF Research Database (Denmark)

    Knutz, B.C.; Berg, Rolf W.; Hjuler, Hans Aage

    1993-01-01

    The battery systems: Al/NaCl-AlCl3-Al(2)X(3)/Ni-felt (X = S, Se, Te) and the corresponding system without chalcogen have been studied experimentally at 175 degrees C. Charge/discharge experimental performed on cells with NaCl saturated melts, show that advantages with regard to rate capability....../decomposition of essentially NiySz and NiySez in the sulfide and selenide system, respectively. Cells containing selenide revealed extra capacity below the NiySez-plateau, most probably associated with a AlvNiySez compound. On the second plateau of sulfide systems NiCl2 or a NiySzCl2y-2z compound with y > (4.4 +/- 0.2). z...

  3. Silica-supported (nBuCp)2ZrCl2: Effect of catalyst active center distribution on ethylene-1-hexene copolymerization

    KAUST Repository

    Atiqullah, Muhammad

    2013-08-12

    Metallocenes are a modern innovation in polyolefin catalysis research. Therefore, two supported metallocene catalysts-silica/MAO/(nBuCp)2ZrCl2 (Catalyst 1) and silica/nBuSnCl3/MAO/(nBuCp)2ZrCl2 (Catalyst 2), where MAO is methylaluminoxane-were synthesized, and subsequently used to prepare, without separate feeding of MAO, ethylene-1-hexene Copolymer 1 and Copolymer 2, respectively. Fouling-free copolymerization, catalyst kinetic stability and production of free-flowing polymer particles (replicating the catalyst particle size distribution) confirmed the occurrence of heterogeneous catalysis. The catalyst active center distribution was modeled by deconvoluting the measured molecular weight distribution and copolymer composition distribution. Five different active center types were predicted for each catalyst, which was corroborated by successive self-nucleation and annealing experiments, as well as by an extended X-ray absorption fine structure spectroscopy report published in the literature. Hence, metallocenes impregnated particularly on an MAO-pretreated support may be rightly envisioned to comprise an ensemble of isolated single sites that have varying coordination environments. This study shows how the active center distribution and the design of supported MAO anions affect copolymerization activity, polymerization mechanism and the resulting polymer microstructures. Catalyst 2 showed less copolymerization activity than Catalyst 1. Strong chain transfer and positive co-monomer effect-both by 1-hexene-were common. Each copolymer demonstrated vinyl, vinylidene and trans-vinylene end groups, and compositional heterogeneity. All these findings were explained, as appropriate, considering the modeled active center distribution, MAO cage structure repeat units, proposed catalyst surface chemistry, segregation effects and the literature that concerns and supports this study. While doing so, new insights were obtained. Additionally, future research, along the direction

  4. Sterically (un)encumbered mer-tridentate N-heterocyclic carbene complexes of titanium(iv) for the copolymerization of cyclohexene oxide with CO2.

    Science.gov (United States)

    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.

  5. PREPARATION OF POLYSTYRENE/SiO2 COMPOSITE NANOPARTICLES BEARING SULFONIC GROUPS ON THE SURFACE VIA EMULSION COPOLYMERIZATION USING A POLYMERIZABLE EMULSIFIER

    Institute of Scientific and Technical Information of China (English)

    Yi-zhang Chen; Zhao-xia Guo; Jian Yu; Mao-sheng Zhan

    2009-01-01

    Functionalized PS/SiO2 composite nanoparticles bearing sulfonic groups on the surface were successfully synthesized via emulsion copolymerization using a polymerizable emulsifier α olefin solfonate(AOS).As demonstrated by transmission electron microscopy and atomic force microscopy,well-defined core-shell PS/SiO2 composite nanoparticles with a diameter of 50 nm were obtained.Sulfonic groups introduced onto the surface of the composite nanoparticles were quantified by FTIR,and can be controlled to some extent via a two-stage procedure.

  6. Experimental study of the rate of OH + HO2 --> H2O + O2 at high temperatures using the reverse reaction.

    Science.gov (United States)

    Hong, Zekai; Vasu, Subith S; Davidson, David F; Hanson, Ronald K

    2010-05-06

    The rate constant of the reaction OH + HO(2) --> H(2)O + O(2) (1) can be inferred at high temperatures from measurements of the rate of its reverse reaction H(2)O + O(2) --> OH + HO(2) (-1). In this work, we used laser absorption of both H(2)O and OH to study the reverse reaction in shock-heated H(2)O/O(2)/Ar mixtures over the temperature range 1600-2200 K. Initial H(2)O concentrations were determined using tunable diode laser absorption near 2.5 microm, and OH concentration time-histories were measured using UV ring dye laser absorption near 306.7 nm. Detailed kinetic analysis of the OH time-history profiles yielded a value for the rate constant k(1) of (3.3 +/- 0.9) x 10(13) [cm(3) mol(-1) s(-1)] between 1600 and 2200 K. The results of this study agree well with those reported by Srinivasan et al. (Srinivasan, N.K.; Su, M.-C.; Sutherland, J.W.; Michael, J.V.; Ruscic, B. J. Phys. Chem. A 2006, 110, 6602-6607) in the temperature regime between 1200 and 1700 K. The combination of the two studies suggests only a weak temperature dependence of k(1) above 1200 K. Data from the current study and that of Keyser (Keyser, L.F. J. Phys. Chem. 1988, 92, 1193-1200) at lower temperatures can be described by the k(1) expression proposed by Baulch et al. (Baulch, D.L.; Cobos, C.J.; Cox, R.A.; Esser, C.; Frank, P.; Just, Th.; Kerr, J.A.; Pilling, M.J.; Troe, J.; Walker, R.W.; Warnatz, J. J. Phys. Chem. Ref. Data 1992, 21, 411), k(1) = 2.89 x 10(13) exp(252/T) [cm(3) mol(-1) s(-1)]. However, it should be noted that some previous studies suggest a k(1) minimum around 1250 K (Hippler, H.; Neunaber, H.; Troe, J. J. Chem. Phys. 1995, 103, 3510-3516) or 1000 K (Kappel, C.; Luther, K.; Troe, J. Phys. Chem. Chem. Phys. 2002, 4, 4392-4398).

  7. Experimental evaluation of in situ CO2-water-rock reactions during CO2 injection in basaltic rocks: Implications for geological CO2 sequestration

    Science.gov (United States)

    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

  8. Experimental study of sediment-CO2 reactions with application to changes in groundwater quality due to leakage of sequestered CO2

    Science.gov (United States)

    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

  9. Study of castor oil polyurethane - poly(methyl methacrylate semi-interpenetrating polymer network (SIPN reaction parameters using a 2³ factorial experimental design

    Directory of Open Access Journals (Sweden)

    Fernanda Oliveira Vieira da Cunha

    2004-12-01

    Full Text Available In this work was employed a 2³ factorial experiment design to evaluate the castor oil polyurethane-poly(methyl methacrylate semi-IPN synthesis. The reaction parameters used as independent variables were NCO/OH molar ratio, polyurethane polymerization time and methyl methacrylate (MMA content. The semi-IPNs were cured over 28 h using two thermal treatments. The polymers were characterized by infrared and Raman spectroscopy, thermal analysis and swelling profiles in n-hexane. The glass transition temperature (Tg and the swelling were more affect by the NCO/OH molar ratio variation. The semi-IPNs showed Tg from - 27 to - 6 °C and the swelling range was from 3 to 22%, according to the crosslink density. The IPN mechanical properties were dependent on the cure temperature and MMA content in it. Lower elastic modulus values were observed in IPNs cured at room temperature.

  10. A selected reaction monitoring-based analysis of acute phase proteins in interstitial fluids from experimental equine wounds healing by secondary intention

    DEFF Research Database (Denmark)

    Bundgaard, Louise; Bendixen, Emøke; Sørensen, Mette Aa

    2016-01-01

    In horses, pathological healing with formation of exuberant granulation tissue (EGT) is a particular problem in limb wounds, whereas body wounds tend to heal without complications. Chronic inflammation has been proposed to be central to the pathogenesis of EGT. This study aimed to investigate...... levels of inflammatory acute phase proteins (APPs) in interstitial fluid from wounds in horses. A novel approach for absolute quantification of proteins, selected reaction monitoring (SRM)-based mass spectrometry in combination with a quantification concatamer (QconCAT), was used for the quantification...... five horses at days 1, 2, 7, and 14 after wounding and healing without (body) and with (limb) the formation of EGT. The QconCAT included proteotypic peptides representing each of the protein targets and was used to direct the design of a gene, which was expressed in Escherichia coli in a media...

  11. Experimental cross section for the {sup 139}La(n, {gamma}){sup 140}La reaction at 0.0536 eV

    Energy Technology Data Exchange (ETDEWEB)

    Chowdhury, M.H. [Inst. of Nuclear Science and Tech., Atomic Energy Research Establishment, Dhaka (Bangladesh); Dept. of Physics, Jahangirnagar Univ., Savar, Dhaka (Bangladesh); Uddin, M.S.; Hossain, S.M.; Latif, S.A; Hafiz, M.A.; Islam, M.A.; Zakaria, A.K.M. [Inst. of Nuclear Science and Tech., Atomic Energy Research Establishment, Dhaka (Bangladesh); Azharul Islam, S.M [Dept. of Physics, Jahangirnagar Univ., Savar, Dhaka (Bangladesh)

    2010-07-01

    The neutron capture cross section for the {sup 139}La(n, {gamma}){sup 140}La reaction at 0.0536 eV was measured for the first time using monochromatic neutrons coming from a Triple Axis Spectrometer at the TRIGA Mark-II reactor. The neutron beam intensity was determined by irradiating Au-monitor foil together La{sub 2}O{sub 3} target. The radioactivity of the products was determined via high resolution {gamma}-ray spectrometry. The obtained cross section value is 6.13 {+-} 0.3 b, which is 1.34% and 0.21% lower than that in the ENDF/B-VII and JENDL-3.3 data library, respectively. (orig.)

  12. Experimental Design for Green Chemistry Directed Hantzsch Reaction%绿色化学导向的Hantzsch反应实验设计

    Institute of Scientific and Technical Information of China (English)

    查正根; 郑媛; 郑小琦; 汪志勇

    2011-01-01

    在水相中,70℃时,六亚甲基四胺、乙酰乙酸乙酯与碳酸铵发生Hantzsch反应,生成1,4-二氢-2,6-二甲基吡啶-3,5-二羧酸二乙酯,产率达90%;在55~60℃时,醛、乙酰乙酸乙酯和碳酸铵Hantzsch反应得到对称的Hantzsch酯,反应时间1~4 h,产率为88%~99%.以醋酸铵代替碳酸铵,在绿色有机溶剂(水、乙醇)中,催化剂(脯氨酸、胍盐酸盐)催化该反应得到中等至定量的产率;以5,5-二甲基-1,3-环己二酮代替另一分子乙酰乙酸乙酯,反应产生不对称的Hantzsch酯.该反应甚至在无溶剂、无催化剂、室温条件下,主要得到空气氧化的芳构化产物.以绿色化学为导向,将Hantzsch反应基础研究的成果设计成设计型、综合型实验,合成在化学、生物和医学上有广泛应用的Hantzsch酯,既开拓了学生的创新能力,培养了他们绿色环保意识,又理论联系实际、学以致用.%In aqueous media, Hantzsch reaction of hexamethylenetetramine and ethyl acetoacetate with ammonium carbonate occured to diethyl 1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylate,in yield of 90% at 70 ℃.In 55 - 60℃ aldehyde and ethyl allylacetoacetate reacted with ammonium carbonate to give symmetrical Hantzsch ester in yield of 88% - 99% in 1 - 4 h.Instead of ammonium carbonate with ammonium acetate, in green organic solvent (water or ethanol),catalyst (proline or guanidine hydrochloride) catalyzed Hantzsch reaction in medium to quantitative yield.Instead of another ethyl allylacetoacetate with 5,5-dimethyl-cyclohexane-1, 3-dione, asymmetric Hantzsch reactions occured.Even without solvent and catalyst at ambient temperature, Hantzsch esters of aromatization were produced.With the green chemistry oriented, the basic research results of Hantzsch reaction were designed into were designed and comprehensive synthesis experiments to achieve Hantzsch esters, and they are widely used in chemistry, biology and medicine.Not only do they develop the

  13. Designing artificial enzymes from scratch: Experimental study and mesoscale simulation

    Science.gov (United States)

    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.

  14. First result of the experimental search for the 9.4 keV solar axion reactions with Kr-83 in the copper proportional counter

    OpenAIRE

    Gavrilyuk, Yu. M.; Gangapshev, A. M.; Derbin, A. V.; Kazalov, V. V.; Kim, H. J.; Kim, Y.D.(Center for Underground Physics, Institute for Basic Science (IBS), Daejon, 305-811, Korea); Kobychev, V. V.; Kuzminov, V. V.; Ali, Luqman; Muratova, V. N.; Panasenko, S. I.; Ratkevich, S. S.; Semenov, D. A.; Tekueva, D. A.; Yakimenko, S. P.

    2014-01-01

    The experimental search for solar hadronic axions is started at the Baksan Neutrino Observatory of the Institute for Nuclear Researches Russian Academy of Science. It is assumed that axions are created in the Sun during M1-transition between the first thermally excited level at 9.4 keV and the ground state in Kr-83. The experiment is based on axion detection via resonant absorption process by the same nucleus in the detector. The big copper proportional counter filled with krypton is used to ...

  15. Reaction between H2, CO, and H2S over Fe,Ni metal in the solar nebula: Experimental evidence for the formation of sulfur-bearing organic molecules and sulfides

    Science.gov (United States)

    Llorca, Jordi; Casanova, Ignasi

    2000-07-01

    Detailed laboratory studies have been carried out in order to simulate the interaction between nanometer-sized kamacite metal particles and different gas mixtures consisting of H2:H2S (250:0.1), H2:CO (250:1) and H2:CO:H2S (250:1:0.1) under nebular-type conditions (5x10-4 atm and 473 K). Reaction of H2+H2S with kamacite particles for 1000 h leads to the formation of pyrrhotite. Incorporation of CO into the gaseous reactant mixture results in the formation of both sulfide and carbide phases. At the same time, amorphous carbon is deposited onto the metal particles and organic molecules are evolved, namely hydrocarbons and thiols in the C1-C5 and C1-C2 range, respectively. Carbon deposition and production of organics are enhanced with respect to experiments performed with H2+CO, where a carbide phase is formed. There is no evidence for the existence of sulfur poisoning effects on the metal-catalysed hydrogenation of CO through Fischer-Tropsch-type reactions in nebular environments. In fact, it is experimentally demonstrated that sulfur-containing organic species could be synthesized by such reactions from nebular gas.

  16. The role of Fe and redox conditions in olivine carbonation rates: An experimental study of the rate limiting reactions at 90 and 150 °C in open and closed systems

    Science.gov (United States)

    Saldi, Giuseppe D.; Daval, Damien; Morvan, Gilles; Knauss, Kevin G.

    2013-10-01

    The mechanisms and rates of olivine carbonation reactions have been the object of a number of studies, but the thermodynamic limitations and the kinetics of the elementary processes that control the overall reaction are still poorly understood and characterized. The main objective of this study is to probe the effect of Fe on the measured rates of olivine carbonation and its role in the formation of Si-rich surface layers, which can significantly inhibit olivine dissolution and limit the extent of the carbonation reaction. A series of batch and flow-through reactor experiments was conducted in pure water at 90 and 150 °C and under a CO2 partial pressure of 100 and 200 bar, using both a natural sample of Fe-bearing olivine (Fo88) and a synthetic sample of pure forsterite (Fo100). Experimental results show that Fe plays an ambivalent role in the carbonation rates of olivine. On one hand, the presence of Fe favors the formation of Fe-Si-rich protective layers at the interface between olivine and aqueous solution, slowing down the dissolution reaction and limiting the extent of carbonation, whereas pure silica coatings have little to no inhibiting effect on measured carbonation rates. On the other hand, Fe enhances olivine to carbonate conversion rates at low degrees of supersaturation, by promoting the formation of fast precipitating Mg-Fe carbonate solid solutions. The passivating properties of Fe-Si-rich layers originate from the strong Fe(III)-Si interaction and are linked to the permanence of oxidizing conditions in the aqueous fluid. As a consequence, under reducing conditions, olivine carbonation rates can be significantly increased by higher extents of dissolution and by the formation of ferroan magnesites (Mg,Fe)CO3, which nucleate faster than the pure Mg end-member. Forsterite and olivine carbonation reactions can be hindered by the formation of secondary Mg sheet-silicates but, at the conditions studied, the formation of such silicate phases was observed to

  17. Control of the structure and properties of water-soluble associating polymers synthesized by micellar copolymerization; Controle de la structure et des proprietes de polymeres hydrosolubles associatifs synthetises par copolymerisation micellaire

    Energy Technology Data Exchange (ETDEWEB)

    Caputo, M.R.; Selb, J. [Institut Charles Sadron, CNRS, 67 - Strasbourg (France)

    2001-07-01

    In the so-called micellar copolymerization process, hydrophilic and hydrophobic monomers are radically co-polymerized in aqueous solution in the presence of surfactant micelles. This process leads to water-soluble polymers in which hydrophobic units are distributed as short blocks whose length can be easily varied. Such copolymers exhibit associative thickening properties. The kinetics of the hydrophobia incorporation within the hydrophilic polyacrylamide backbone has been compared for various anionic and cationic surfactants. A fluorescence technique based on excimer formation between fluorescent hydrophobic groups has been used to characterize the copolymer structure and the chain conformation in solution. (author)

  18. Experimental and density functional theoretical study of the effects of Fenton's reaction on the degradation of Bisphenol A in a high voltage plasma reactor.

    Science.gov (United States)

    Dai, Fei; Fan, Xiangru; Stratton, Gunnar R; Bellona, Christopher L; Holsen, Thomas M; Crimmins, Bernard S; Xia, Xiaoyan; Mededovic Thagard, Selma

    2016-05-05

    A novel electrical discharge plasma reactor configuration with and without iron ions was evaluated for the degradation of 0.02 mM Bisphenol A (BPA). The pseudo-first-order reaction rate constant calculated for the plasma treatment of BPA with a stainless steel electrode in the presence of dissolved ferrous ion (Fe(2+)) salts (termed plasma/Fenton treatment) was higher than in the plasma treatment in the absence of iron salts. At the optimal ferrous ion concentration, longer plasma treatment times resulted in higher BPA degradation rates, likely due to increased hydroxyl (OH) radical concentration formed through the decomposition of H2O2. Replacing the stainless steel with a carbon steel grounded electrode resulted in the release of iron ions from the carbon steel thereby increasing the rate of BPA removal and eliminating the need for iron salts. After the plasma/Fenton treatment, >97% of the residual iron salts were removed by coagulation/flocculation/sedimentation. Byproduct identification coupled with density functional theory (DFT) calculations confirmed that OH radical attack on BPA's hydroxyl group is the primary pathway for byproduct formation. Copyright © 2016 Elsevier B.V. All rights reserved.

  19. Simulation of delayed γ-ray emission following photofission reactions induced by pulsed bremsstrahlung x-rays using MCNPX and experimental validation

    Science.gov (United States)

    Wen, Xianfei; Yang, Haori

    2016-12-01

    There is a great demand to develop non-destructive techniques to identify and quantify Special Nuclear Materials (SNM) in homeland security and nuclear safeguards applications. Passive assay could be extremely challenging in some scenarios. Active interrogation technique based on photofission has been identified as one of the promising approaches. In radiation detection system design based on such technique, it is highly desired to have abilities to accurately and efficiently simulate delayed γ-rays emitted from photofission reactions. In this work, simulation results were compared with measurement outcomes to demonstrate the capabilities and limitations of the code MCNPX 2.7.0 in the simulation of delayed γ-rays from photofission of uranium and plutonium samples. First, high-energy delayed γ-rays (Eγ 2.7-4.5 MeV) from photofission of 238U were simulated and validated against the energy spectra measured in between linac pulses. Second, low-energy delayed γ-ray spectra (Eγ 0.6-2.7 MeV) measured with a list-mode system after irradiation of 239Pu were used in the validation.

  20. Experimental and theoretical investigation of electronic structure of SrFeO3-xFx epitaxial thin films prepared via topotactic reaction

    Science.gov (United States)

    Katayama, Tsukasa; Chikamatsu, Akira; Kamisaka, Hideyuki; Kumigashira, Hiroshi; Hasegawa, Tetsuya

    2016-02-01

    We investigated the electronic structure of perovskite SrFeO3-xFx (0.6 ≤ x ≤ 1) films by optical absorption, photoemission, and X-ray absorption spectroscopies, as well as density functional theory (DFT)-based calculations. The optical bandgap expanded with x, yielding a wider direct bandgap for the SrFeO2F film than for the LaFeO3 film. The DFT calculations suggested that the majority of FeO4F2 octahedra in the SrFeO2F film had cis configurations and that the enlarged bandgap mainly originated from bond bending in the O-Fe-O chains. We experimentally observed the valence and conduction bands of the SrFeO2F film, and found them to be qualitatively consistent with the results of DFT-based calculations.