WorldWideScience

Sample records for organometallic reactions development

  1. Organometallic Reactions Development, Mechanistic Studies and Synthetic Applications

    DEFF Research Database (Denmark)

    Dam, Johan Hygum

    of the successful total synthesis of the cyclophane cavicularin, which contains a bent aromatic moiety. The pivotal step in the synthesis embodied a pyrone-alkyne Diels-Alder cycloaddition with CO2-extrusion to deliver the bent aromatic residue. The fourth project involved further development of the conditions...... previously discovered in the Madsen group for the direct coupling of alcohols and amines to amides under dihydrogen liberation. The goal was to synthesize isolatable ruthenium catalysts and two 18-electron complexes capable of performing the reaction in excellent yields were prepared and characterized...

  2. Modules for Introducing Organometallic Reactions: A Bridge between Organic and Inorganic Chemistry

    Science.gov (United States)

    Schaller, Chris P.; Graham, Kate J.; Johnson, Brian J.

    2015-01-01

    Transition metal organometallic reactions have become increasingly important in the synthesis of organic molecules. A new approach has been developed to introduce organometallic chemistry, along with organic and inorganic chemistry, at the foundational level. This change highlights applications of organometallic chemistry that have dramatically…

  3. Catalytic Organometallic Reactions of Ammonia

    Science.gov (United States)

    Klinkenberg, Jessica L.

    2012-01-01

    Until recently, ammonia had rarely succumbed to catalytic transformations with homogeneous catalysts, and the development of such reactions that are selective for the formation of single products under mild conditions has encountered numerous challenges. However, recently developed catalysts have allowed several classes of reactions to create products with nitrogen-containing functional groups from ammonia. These reactions include hydroaminomethylation, reductive amination, alkylation, allylic substitution, hydroamination, and cross-coupling. This Minireview describes examples of these processes and the factors that control catalyst activity and selectivity. PMID:20857466

  4. Mechanisms of inorganic and organometallic reactions

    CERN Document Server

    The purpose of this series is to provide a continuing critical review of the literature concerned with mechanistic aspects of inorganic and organo­ metallic reactions in solution, with coverage being complete in each volume. The papers discussed are selected on the basis of relevance to the elucidation of reaction mechanisms and many include results of a nonkinetic nature when useful mechanistic information can be deduced. The period of literature covered by this volume is July 1982 through December 1983, and in some instances papers not available for inclusion in the previous volume are also included. Numerical results are usually reported in the units used by the original authors, except where data from different papers are com­ pared and conversion to common units is necessary. As in previous volumes material included covers the major areas of redox processes, reactions of the nonmetallic elements, reaction of inert and labile metal complexes and the reactions of organometallic compounds. While m...

  5. A computational glance at organometallic cyclizations and coupling reactions

    OpenAIRE

    Fiser, Béla

    2016-01-01

    210 p. Organometallic chemistry is one of the main research topics in chemical science.Nowadays, organometallic reactions are the subject of intensive theoretical investigations.However, in many cases, only joint experimental and theoretical effortscould reveal the answers what we are looking for.The fruits of such experimental and theoretical co-operations will be presentedhere. In this work, we are going to deal with homogeneous organometallic catalysisusing computational chemical tools....

  6. Physical organic studies of organometallic reactions

    Energy Technology Data Exchange (ETDEWEB)

    Bergman, Robert G. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States). Dept. of Chemistry

    1981-01-01

    The mechanisms of reactions of organotransition metal complexes have only begun to be understood in detail during the last ten years. The complementary interaction of techniques and concepts developed earlier in studies of organic reaction mechanisms, with those commonly used in inorganic chetnistry, has played a crucial role in helping to elucidate organor.1etall.ic reaction mechanisms. A few systems in which this interaction has proved especially fruitful are discussed in this article.

  7. Homogeneous photocatalytic reactions with organometallic and coordination compounds--perspectives for sustainable chemistry.

    Science.gov (United States)

    Hoffmann, Norbert

    2012-02-13

    Since the time of Giacomo Ciamician at the beginning of the 20th century, photochemical transformations have been recognized as contributing to sustainable chemistry. Electronic excitation significantly changes the reactivity of chemical compounds. Thus, the application of activation reagents is frequently avoided and transformations can be performed under mild conditions. Catalysis plays a central role in sustainable chemistry. Stoichiometric amounts of activation reagents are often avoided. This fact and the milder catalytic reaction conditions diminish the formation of byproducts. In the case of homogeneous catalysis, organometallic compounds are often applied. The combination of both techniques develops synergistic effects in the sense of "Green Chemistry". Herein, metal carbonyl-mediated reactions are reported. These transformations are of considerable interest for the synthesis of complex polyfunctionalized compounds. Copper(I)-catalyzed [2+2] photocycloaddition gives access to a large variety of cyclobutane derivatives. Currently, a large number of publications deal with photochemical electron-transfer-induced reactions with organometallic and coordination compounds, particularly with ruthenium complexes. Several photochemically induced oxidations can easily be performed with air or molecular oxygen when they are catalyzed with organometallic complexes. Photochemical reaction conditions also play a certain role in C-H activation with organometallic catalysts, for instance, with alkanes, although such transformations are conveniently performed with a variety of other photochemical reactions. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. 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

  9. Investigation of organometallic reaction mechanisms with one and two dimensional vibrational spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Cahoon, James Francis [Univ. of California, Berkeley, CA (United States)

    2008-12-01

    One and two dimensional time-resolved vibrational spectroscopy has been used to investigate the elementary reactions of several prototypical organometallic complexes in room temperature solution. The electron transfer and ligand substitution reactions of photogenerated 17-electron organometallic radicals CpW(CO)3 and CpFe(CO)2 have been examined with one dimensional spectroscopy on the picosecond through microsecond time-scales, revealing the importance of caging effects and odd-electron intermediates in these reactions. Similarly, an investigation of the photophysics of the simple Fischer carbene complex Cr(CO)5[CMe(OMe)] showed that this class of molecule undergoes an unusual molecular rearrangement on the picosecond time-scale, briefly forming a metal-ketene complex. Although time-resolved spectroscopy has long been used for these types of photoinitiated reactions, the advent of two dimensional vibrational spectroscopy (2D-IR) opens the possibility to examine the ultrafast dynamics of molecules under thermal equilibrium conditions. Using this method, the picosecond fluxional rearrangements of the model metal carbonyl Fe(CO)5 have been examined, revealing the mechanism, time-scale, and transition state of the fluxional reaction. The success of this experiment demonstrates that 2D-IR is a powerful technique to examine the thermally-driven, ultrafast rearrangements of organometallic molecules in solution.

  10. Organometallic copper I, II or III species in an intramolecular dechlorination reaction

    KAUST Repository

    Poater, Albert

    2013-03-15

    The present paper gives insight into an intramolecular dechlorination reaction involving Copper (I) and an ArCH2Cl moiety. The discussion of the presence of a CuIII organometallic intermediate becomes a challenge, and because of the lack of clear experimental detection of this proposed intermediate, and due to the computational evidence that it is less stable than other isomeric species, it can be ruled out for the complex studied here. Our calculations are completely consistent with the key hypothesis of Karlin et al. that TMPA-CuI is the substrate of intramolecular dechlorination reactions as well as the source to generate organometallic species. However the organometallic character of some intermediates has been refused because computationally these species are less stable than other isomers. Thus this study constitutes an additional piece towards the full understanding of a class of reaction of biological relevance. Further, the lack of high energy barriers and deep energy wells along the reaction pathway explains the experimental difficulties to trap other intermediates. © Springer-Verlag Berlin Heidelberg 2013.

  11. A paradigm shift for radical SAM reactions: The organometallic intermediate Ω is central to catalysis.

    Science.gov (United States)

    Byer, Amanda S; Yang, Hao; McDaniel, Elizabeth C; Kathiresan, Venkatesan; Impano, Stella; Pagnier, Adrien; Watts, Hope; Denler, Carly; Vagstad, Anna; Piel, Jörn; Duschene, Kaitlin S; Shepard, Eric M; Shields, Thomas P; Scott, Lincoln G; Lilla, Edward A; Yokoyama, Kenichi; Broderick, William E; Hoffman, Brian M; Broderick, Joan B

    2018-06-28

    Radical S-adenosyl-L-methionine (SAM) en-zymes comprise a vast superfamily catalyzing diverse reactions essential to all life through ho-molytic SAM cleavage to liberate the highly-reactive 5-deoxyadenosyl radical (5-dAdo•). Our recent observation of a catalytically compe-tent organometallic intermediate Ω that forms dur-ing reaction of the radical SAM (RS) enzyme py-ruvate formate-lyase activating-enzyme (PFL-AE) was therefore quite surprising, and led to the question of its broad relevance in the superfamily. We now show that Ω in PFL-AE forms as an in-termediate under a variety of mixing order condi-tions, suggesting it is central to catalysis in this enzyme. We further demonstrate that Ω forms in a suite of RS enzymes chosen to span the totality of superfamily reaction types, implicating Ω as essential in catalysis across the RS superfamily. Finally, EPR and electron nuclear double reso-nance spectroscopy establish that Ω involves an Fe-C5 bond between 5-dAdo• and the [4Fe-4S] cluster. An analogous organometallic bond is found in the well-known adenosylcobalamin (co-enzyme B12) cofactor used to initiate radical reac-tions via a 5'-dAdo• intermediate. Generation of a 5'-dAdo• intermediate via homolytic metal-carbon bond cleavage thus appears to be similar for Ω and coenzyme B12. However coenzyme B12 is involved in enzymes catalyzing of only a small number (~12) of distinct reactions, while the RS superfamily has more than 100,000 distinct se-quences and over 80 reaction types character-ized to date. The appearance of Ω across the RS superfamily therefore dramatically enlarges the sphere of bio-organometallic chemistry in Nature.

  12. Peroxide organometallic compounds and their transformations

    International Nuclear Information System (INIS)

    Razuvaev, G.A.; Brilkina, T.G.

    1976-01-01

    A survey is given experimental works on synthesis and reactions of peroxide organometallic compounds. Reactions have been considered of organometallic compounds with oxygen and organic peroxides which result in formation of both peroxide and non-peroxide products. Possible routes and mechanisms of chemical transformations of peroxide organometallic compounds have been discussed. Reactions of organometallic compounds with oxygen and peroxides have been considered

  13. NATO Advanced Research Workshop on the Mechanisms of Reactions of Organometallic Compounds with Surfaces

    CERN Document Server

    Williams, J

    1989-01-01

    A NATO Advanced Research Workshop on the "Mechanisms of Reactions of Organometallic Compounds with Surfaces" was held in St. Andrews, Scotland in June 1988. Many of the leading international researchers in this area were present at the workshop and all made oral presentations of their results. In addition, significant amounts of time were set aside for Round Table discussions, in which smaller groups considered the current status of mechanistic knowledge, identified areas of dispute or disagreement, and proposed experiments that need to be carried out to resolve such disputes so as to advance our understanding of this important research area. All the papers presented at the workshop are collected in this volume, together with summaries of the conclusions reached at the Round Table discussions. The workshop could not have taken place without financial support from NATO, and donations were also received from Associated Octel, Ltd., STC Ltd., and Epichem Ltd., for which the organisers are very grateful. The orga...

  14. Selective Organic and Organometallic Reactions in Water-Soluble Host-Guest Supramolecular Systems

    Energy Technology Data Exchange (ETDEWEB)

    Pluth, Michael D.; Raymond, Kenneth N.; Bergman, Robert G.

    2008-02-16

    Inspired by the efficiency and selectivity of enzymes, synthetic chemists have designed and prepared a wide range of host molecules that can bind smaller molecules with their cavities; this area has become known as 'supramolecular' or 'host-guest' chemistry. Pioneered by Lehn, Cram, Pedersen, and Breslow, and followed up by a large number of more recent investigators, it has been found that the chemical environment in each assembly - defined by the size, shape, charge, and functional group availability - greatly influences the guest-binding characteristics of these compounds. In contrast to the large number of binding studies that have been carried out in this area, the exploration of chemistry - especially catalytic chemistry - that can take place inside supramolecular host cavities is still in its infancy. For example, until the work described here was carried out, very few examples of organometallic reactivity inside supramolecular hosts were known, especially in water solution. For that reason, our group and the group directed by Kenneth Raymond decided to take advantage of our complementary expertise and attempt to carry out metal-mediated C-H bond activation reactions in water-soluble supramolecular systems. This article begins by providing background from the Raymond group in supramolecular coordination chemistry and the Bergman group in C-H bond activation. It goes on to report the results of our combined efforts in supramolecular C-H activation reactions, followed by extensions of this work into a wider range of intracavity transformations.

  15. Incorporation of radiohalogens via versatile organometallic reactions: applications in radiopharmaceutical chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Srivastava, P.C.; Goodman, M.M.; Knapp, F.F. Jr.

    1985-01-01

    Factors that must be considered for the design of radiohalogenated radio-pharmaceuticals include the stability and availability of the substrate, the physical half-life of the radiohalogen and the in vivo stability of the radiolabel. Vinyl and phenyl radiohalogen bonds show more in vivo stability than the alkyl radiohalogen bonds. Consequently, a variety of methods suitable for the synthesis of tissue specific radiopharmaceuticals bearing a vinyl or phenyl radiohalogen have been developed involving the synthesis and halogenation of metallovinyl and phenyl intermediates. The halogens and metallation reactions include iodine and bromine and alanation, boronation, mercuration, stannylation, and thallation, respectively. 19 refs., 1 fig., 1 tab.

  16. Organometallic copper I, II or III species in an intramolecular dechlorination reaction

    KAUST Repository

    Poater, Albert; Cavallo, Luigi

    2013-01-01

    these species are less stable than other isomers. Thus this study constitutes an additional piece towards the full understanding of a class of reaction of biological relevance. Further, the lack of high energy barriers and deep energy wells along the reaction

  17. Recent Applications of Polymer Supported Organometallic Catalysts in Organic Synthesis

    Directory of Open Access Journals (Sweden)

    Nina Kann

    2010-09-01

    Full Text Available Recent developments concerning the application of polymer supported organometallic reagents in solid phase synthesis are reviewed, with a special focus on methodology for carbon-carbon formation. Examples of reactions that are covered include the classical Suzuki, Sonogashira and Heck coupings, but also aryl amination, epoxide opening, rearrangements, metathesis and cyclopropanation. Applications in the field of asymmetric synthesis are also discussed.

  18. Understanding the electron-stimulated surface reactions of organometallic complexes to enable design of precursors for electron beam-induced deposition

    Energy Technology Data Exchange (ETDEWEB)

    Spencer, Julie A.; Rosenberg, Samantha G.; Barclay, Michael; Fairbrother, D. Howard [Johns Hopkins University, Department of Chemistry, Baltimore, MD (United States); Wu, Yung-Chien; McElwee-White, Lisa [University of Florida, Department of Chemistry, Gainesville, FL (United States)

    2014-12-15

    Standard practice in electron beam-induced deposition (EBID) is to use precursors designed for thermal processes, such as chemical vapor deposition (CVD). However, organometallic precursors that yield pure metal deposits in CVD often create EBID deposits with high levels of organic contamination. This contamination negatively impacts the deposit's properties (e.g., by increasing resistivity or decreasing catalytic activity) and severely limits the range of potential applications for metal-containing EBID nanostructures. To provide the information needed for the rational design of precursors specifically for EBID, we have employed an ultra-high vacuum (UHV) surface science approach to identify the elementary reactions of organometallic precursors during EBID. These UHV studies have demonstrated that the initial electron-induced deposition of the surface-bound organometallic precursors proceeds through desorption of one or more of the ligands present in the parent compound. In specific cases, this deposition step has been shown to proceed via dissociative electron attachment, involving low-energy secondary electrons generated by the interaction of the primary beam with the substrate. Electron beam processing of the surface-bound species produced in the initial deposition event usually causes decomposition of the residual ligands, creating nonvolatile fragments. This process is believed to be responsible for a significant fraction of the organic contaminants typically observed in EBID nanostructures. A few ligands (e.g., halogens) can, however, desorb during electron beam processing while other ligands (e.g., PF{sub 3}, CO) can thermally desorb if elevated substrate temperatures are used during deposition. Using these general guidelines for reactivity, we propose some design strategies for EBID precursors. The ultimate goal is to minimize organic contamination and thus overcome the key bottleneck for fabrication of relatively pure EBID nanostructures. (orig.)

  19. Hydrotelluration of alkynes: a unique route to Z-vinyl organometallics

    Directory of Open Access Journals (Sweden)

    Vieira Maurício L.

    2001-01-01

    Full Text Available The hydrotelluration reaction of alkynes is reviewed. The transformation of vinylic tellurides into reactive vinyl organometallics and the coupling reactions of vinylic tellurides with alkynes and organometallics are presented.

  20. Development of new organometallic species for the labelling of radiotracers with short half-lives radioisotopes

    International Nuclear Information System (INIS)

    Huet-Dales, A.

    2003-11-01

    The reactivity of clean organotins have been studied in the Stille coupling reaction in fast conditions, witch can be used with short half-life radioisotope. In a first part, development of the reaction conditions have been studied for the transfer of a methyl group by the Stille coupling reaction, via the synthesis of the correspond mono-organotin. The reaction time was optimized onto model compounds in 12-carbon and 11-carbon chemistry. In a second part, this methodology was applied to the synthesis of NK3 receptors radioligands, in 12-carbon and 11-carbon chemistry. Biological studies showed that these ligands have a good affinity with NK3 receptors, and are potential positron emission tomography tracers. (author)

  1. Quantitative DFT modeling of product concentration in organometallic reactions: Cu-mediated pentafluoroethylation of benzoic acid chlorides as a case study.

    Science.gov (United States)

    Jover, Jesús

    2017-11-08

    DFT calculations are widely used for computing properties, reaction mechanisms and energy profiles in organometallic reactions. A qualitative agreement between the experimental and the calculated results seems to usually be enough to validate a computational methodology but recent advances in computation indicate that a nearly quantitative agreement should be possible if an appropriate DFT study is carried out. Final percent product concentrations, often reported as yields, are by far the most commonly reported properties in experimental metal-mediated synthesis studies but reported DFT studies have not focused on predicting absolute product amounts. The recently reported stoichiometric pentafluoroethylation of benzoic acid chlorides (R-C 6 H 4 COCl) with [(phen)Cu(PPh 3 )C 2 F 5 ] (phen = 1,10-phenanthroline, PPh 3 = triphenylphosphine) has been used as a case study to check whether the experimental product concentrations can be reproduced by any of the most popular DFT approaches with high enough accuracy. To this end, the Gibbs energy profile for the pentafluoroethylation of benzoic acid chloride has been computed using 14 different DFT methods. These computed Gibbs energy profiles have been employed to build kinetic models predicting the final product concentration in solution. The best results are obtained with the D3-dispersion corrected B3LYP functional, which has been successfully used afterwards to model the reaction outcomes of other simple (R = o-Me, p-Me, p-Cl, p-F, etc.) benzoic acid chlorides. The product concentrations of more complex reaction networks in which more than one position of the substrate may be activated by the copper catalyst (R = o-Br and p-I) are also predicted appropriately.

  2. Organometallic compounds in the environment

    National Research Council Canada - National Science Library

    Craig, P. J

    2003-01-01

    ... of Organometallic Species in the Environment 20 1.10 Stability of Organometallic Compounds in Biological Systems 1.11 G eneral Comments on the Toxicities of Organometallic Compounds 22 1.12 General Considerations on Environmental R eactivity of Organometallic Compounds 24 1.13 Microbial Biotransformation of Metals and M etalloids 25 1.13.1 Introduction 25 1...

  3. Reactions of 5-[1-(2-phenylmethylidene]-3-phenylimidazolidine-2,4-diones with some organometallic reagents

    Directory of Open Access Journals (Sweden)

    Teresa A. R. Akeng'a

    2005-06-01

    Full Text Available The reaction of Grignard reagents with 5-[1-(2-chlorophenylmethylidene]-3-phenylimidazolidine-2,4-dione, 4, and 5-[1-(2-bromophenylmethylidene]-3-phenylimidazolidine-2,4-dione, 5, gave exclusively 1,2-addition products, 6-8, in 70-80% yields. Lithium dibutylcuprate reacted with 4 to yield exclusively 1,2-addition product 9 (92%. No conjugate or 1,4-addition products were obtained. These results indicate that 5-[1-(2-phenylmethylidene]-3-phenylimidazolidine-2,4-diones do not react like normal unsaturated carbonyl compounds.

  4. Advanced polymer chemistry of organometallic anions

    International Nuclear Information System (INIS)

    Chamberlin, R.M.; Abney, K.D.; Balaich, G.J.; Fino, S.A.

    1997-01-01

    This is the final report of a one-year, Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). The objective of the project was to prepare and characterize new polymers incorporating cobalt dicarbollide. Specific goals were to prepare polymerizable cobalt dicarbollide monomers using the nucleophilic substitution route discovered in laboratories and to establish the reaction conditions required to form polymers from these complexes. This one-year project resulted in two publications (in press), and provided the foundation for further investigations into polymer synthesis and characterization using cobalt dicarbollide and other metallocarboranes. Interest in synthesizing organometallic polymers containing the cobalt bis(dicarbollide) anion is motivated by their possible application as cation exchange materials for the remediation of cesium-137 and strontium-90 from nuclear wastes

  5. Organometallic chemistry of the f-elements: toward new development: cyanide ligand of f-elements

    International Nuclear Information System (INIS)

    Herve, Alexandre

    2014-01-01

    The cyanide ligand is one of the most widely used ligands in coordination chemistry of d-transition metals. The low number of cyanide complexes of lanthanides and actinides incited us to develop this field for reactivity and theoretical aspects, and also for their potentially interesting physicochemical properties. In this Ph.D., we investigated the reactivity of [An(Cot) 2 ] (An = Th, U ; Cot = C 8 H 8 2- ) and [M f (N*) 3 ] q+ (q = 0, 1; M f = Ce, U ; N* = -N(SiMe 3 ) 2 ) precursors toward the cyanide ion. The first chapter is dedicated to the synthesis and characterization of trivalent f-elements cyanide complexes [M f (N*) 3 (CN)][M], [M f (N*) 3 (CN) 2 ][M] 2 et [M f (N*) 2 (CN) 3 ][M] 2 and the cyanido-bridged binuclear compounds [{M f (N*) 3 } 2 (μ-CN)][M] (M = NR 4 , K(18-C-6)). Crystals of the bis(cyanido) uranium and cerium complexes are not isostructural since the data revealed distinct coordination modes of the CN group, through the C or N atom to the U 3+ or Ce 3+ metal center, respectively. In chapter 2, the novel silyl-amide uranium(IV) precursor [U(N*) 3 ][BPh 4 ] has been isolated, and proved to be useful for the synthesis of the cationic species [{U(N*) 3 } 2 (μ-CN)][BPh 4 ] and the neutral monocyanide [M f (N*) 3 (CN)] and anionic bis(cyanide) [M f (N*) 3 (CN) 2 ][M] derivatives. Here again, the X-ray data reveal the uncommon N coordination mode of the CN group to the U(IV) center. This global differentiation has been analyzed using density functional theory calculations. The observed preferential coordination of the cyanide ion in Ce(III)-NC, U(III)-CN and U(IV)-NC is corroborated by energetic considerations and by the comparison of DFT optimized geometries with the true crystal structures. Finally, the recent discovery of the first bent 'uranocene' species, eg [U(Cot) 2 (CN)] - , led us to compare the reactivity of the actinocenes [An(Cot) 2 ] (Th, U) in order to understand the effect of the metal electron configuration

  6. Organometallic and Bioorganometallic Chemistry - Ferrocene and Metal Carbonyls

    Directory of Open Access Journals (Sweden)

    Čakić Semenčić, M.

    2011-02-01

    Full Text Available Organometallic chemistry deals with compounds containing metal-carbon bonds. Basic organometallics derived from the s- and p-block metals (containing solely σ-bonds were understood earlier, while organometallic chemistry of the d- and f-block has developed much more recently. These compounds are characterized by three types of M-C bonds (σ, π and δand their structures are impossible to deduce by chemical means alone; fundamental advances had to await the development of X-ray diffraction, as well as IR- and NMR-spectroscopy. On the other hand, elucidation of the structure of e. g. vitamin B12 and ferrocene (discovered in 1951 contributed to progress in these instrumental analytical methods, influencing further phenomenal success of transition-metal organometallic chemistry in the second half of the twentieth century. The most thoroughly explored fields of application of organometallics were in the area of catalysis, asymmetric synthesis, olefin metathesis, as well as organic synthesis and access to new materials and polymers.The most usual ligands bound to d- and f-metals are carbon monoxide, phosphines, alkyls, carbenes and arenes, and in this review the bonding patterns in the metal carbonyls and ferrocene are elaborated. The common characteristics of these two classes are two-component bonds. The CO-M bonds include (i donation from ligand HOMO to vacant M d-orbitals (σ-bond, and (ii back-donation from the filled M d-orbitals in the ligand LUMO (π-bond. Similar (but much more complicated ferrocene contains delocalized bonds consisting of electron donation from Cp to Fe (σ-bonds- and π-bonding and δ-back-bonding from metal to Cp. In such a way ferrocene, i. e. (η5-Cp2Fe contains 18 bonding electrons giving to this compound "superaromatic" properties in the sense of stability and electrophilic substitution. In contrast to benzenoid aromatic compounds reactions in two Cp-rings can occur giving homo- and heteroannularly mono-, two-… per

  7. Development of novel strategy for the synthesis of organometallic compounds usable as protein ligands: application to the human cyclophilin hCyp-18

    International Nuclear Information System (INIS)

    Clavaud, C.

    2006-02-01

    This thesis describes a new strategy for the development of bioactive organometallic compounds, basing on the combinatorial assembly of sub-chemical libraries (A and B) independent but complementary and able to coordinate a metallic heart M to form A-M-B complex potential ligands of biomolecules. The coordination of metals, well adapted to the production of molecular variety is usually used in medicinal chemistry, in diagnostic and therapeutic nuclear medicine. Among the useful elements, the rhenium and the technetium are metals of choice for the development of the assembly strategy because of their chemical and radiochemical properties and of the structure analogy of their complexes. This strategy was validated in vitro. The protein chosen for this purpose was the cyclophilin hCyp-18. (N.C.)

  8. Ligand Rearrangements of Organometallic Complexes inSolution

    Energy Technology Data Exchange (ETDEWEB)

    Shanoski, Jennifer E. [Univ. of California, Berkeley, CA (United States)

    2006-01-01

    Many chemical reactions utilize organometallic complexes as catalysts. These complexes find use in reactions as varied as bond activation, polymerization, and isomerization. This thesis outlines the construction of a new ultrafast laser system with an emphasis on the generation of tunable mid-infrared pulses, data collection, and data analysis.

  9. Organometallic chemistry of bimetallic compounds. Progress report, January 1992--July 1995

    International Nuclear Information System (INIS)

    Casey, C.P.

    1994-07-01

    Four main projects at the interface between organometallic chemistry and homogeneous catalysis were pursued. All were designed to give increased understanding of the mechanisms of organometallic reactions related to homogeneous and heterogeneous catalysis. In addition, a minor study involving η 5 -to η 1 -cyclopentadienyl ring slippage in catalysis was completed

  10. Organometallic chemistry of bimetallic compounds. Progress report, January 1992--July 1995

    Energy Technology Data Exchange (ETDEWEB)

    Casey, C.P.

    1994-07-01

    Four main projects at the interface between organometallic chemistry and homogeneous catalysis were pursued. All were designed to give increased understanding of the mechanisms of organometallic reactions related to homogeneous and heterogeneous catalysis. In addition, a minor study involving {eta}{sup 5}-to {eta}{sup 1}-cyclopentadienyl ring slippage in catalysis was completed.

  11. The Future of Polar Organometallic Chemistry Written in Bio-Based Solvents and Water.

    Science.gov (United States)

    García-Álvarez, Joaquín; Hevia, Eva; Capriati, Vito

    2018-06-19

    There is a strong imperative to reduce the release of volatile organic compounds (VOCs) into the environment, and many efforts are currently being made to replace conventional hazardous VOCs in favour of safe, green and bio-renewable reaction media that are not based on crude petroleum. Recent ground-breaking studies from a few laboratories worldwide have shown that both Grignard and (functionalised) organolithium reagents, traditionally handled under strict exclusion of air and humidity and in anhydrous VOCs, can smoothly promote both nucleophilic additions to unsaturated substrates and nucleophilic substitutions in water and other bio-based solvents (glycerol, deep eutectic solvents), competitively with protonolysis, at room temperature and under air. The chemistry of polar organometallics in the above protic media is a complex phenomenon influenced by several factors, and understanding its foundational character is surely stimulating in the perspective of the development of a sustainable organometallic chemistry. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Organometallics Roundtable 2011

    Energy Technology Data Exchange (ETDEWEB)

    Gladysz, John A.; Ball, Zachary T.; Bertrand, Guy; Blum, Suzanne A.; Dong, Vy M.; Dorta, Reto; Hahn, F. Ekkehardt; Humphrey, Mark; Jones, William D.; Klosin, Jerzy; Manners, Ian; Marks, Tobin J.; Mayer, James M.; Rieger, Bernhard; Ritter, Joachim C.; Sattelberger, Alfred P.; Schomaker, Jennifer M.; Wing-Wah Yam, Vivian

    2012-01-09

    We are living in an era of unprecedented change in academic, industrial, and government-based research worldwide, and navigating these rough waters requires "all hands on deck". Toward this end, Organometallics has assembled a panel of seventeen experts who share their thoughts on a variety of matters of importance to our field. In constituting this panel, an attempt was made to secure representation from a number of countries and career stages, as well as from industry. We were fortunate that so many busy experts could take the time to spend with us. The following pages constitute an edited transcript of the panel discussion held on August 29, 2011, which was structured around the 10 questions summarized in the side bar and repeated below.

  13. Organometallic Chemistry. Final Progress Report

    Energy Technology Data Exchange (ETDEWEB)

    Wolczanski, Peter [Cornell Univ., Ithaca, NY (United States)

    2003-07-14

    The Gordon Research Conference (GRC) on Organometallic Chemistry was held at Salve Regina, Newport, Rhode Island, 7/21-26/02. Emphasis was placed on current unpublished research and discussion of the future target areas in this field.

  14. Organometallic chemistry of metal surfaces

    International Nuclear Information System (INIS)

    Muetterties, E.L.

    1981-06-01

    The organometallic chemistry of metal surfaces is defined as a function of surface crystallography and of surface composition for a set of cyclic hydrocarbons that include benzene, toluene, cyclohexadienes, cyclohexene, cyclohexane, cyclooctatetraene, cyclooctadienes, cyclooctadiene, cycloheptatriene and cyclobutane. 12 figures

  15. The organometallic chemistry of neptunium

    International Nuclear Information System (INIS)

    Bohlander, R.

    1986-09-01

    Organometallic compounds of neptunium with carbocyclic ligands (C 5 H 5 - =cp, C 8 H 8 2- =cot) have been prepared and investigated. Starting from tetrakis(cyclopentadienyle)neptunium(IV) (cp 4 Np) and tris(cyclopentadienyle)neptunium(IV) chloride (cp 3 NpCl) a lot of other Np(IV)-compounds can be obtained by ligand-exchange reactions. These have the general formula cp 3 NpL with either inorganic ionic (L=Br - , I - , 1/2SO 4 2- , NCS - , AlCl 4 - ) or organic ligands (L=NC 4 H 4 - , N 2 C 3 H 3 - , C=CH - , 1/2C= 2- , CH 3 - , C 2 H 5 - , C 6 H 5 - ). Produced by reduction, tris(cyclopentadienyle)neptunium(III), cp 3 Np) gives similar structured 1:1-adduct complexes, cp 3 Np * B, with Lewis-bases like THF, diethylether, acetonitrile. Physico-chemical properties and changes in the molecular structure of the complexes have been studied using IR-, FTIR- and optical spectroscopy (in the NIR, VIS and UV region) as well as by magnetic and EPR measurements and Moessbauer spectrometry. The results are discussed as to their classification within the actinide complex chemistry and to the comparison with lanthanide complexes. (orig./RB) [de

  16. Understanding of the structure activity relationship of PtPd bimetallic catalysts prepared by surface organometallic chemistry and ion exchange during the reaction of iso-butane with hydrogen

    KAUST Repository

    Al-Shareef, Reem A.; Harb, Moussab; Saih, Youssef; Ould-Chikh, Samy; Roldan, Manuel A.; Anjum, Dalaver H.; Guyonnet, Elodie Bile; Candy, Jean-Pierre; Jan, Deng-Yang; Abdo, Suheil F.; Aguilar-Tapia, Antonio; Proux, Olivier; Hazemann, Jean-Louis; Basset, Jean-Marie

    2018-01-01

    Well-defined silica supported bimetallic catalysts Pt100-x Pdx were prepared by Surface Organometallic Chemistry (SOMC) and Ionic-Exchange (IE) methods. For all investigated catalysts, iso-butane reaction with hydrogen under differential conditions led to the formation of methane and propane, n-butane, and traces of iso-butylene. The total reaction rate decreased with increasing the Pd loading for both catalysts series as a result of decreasing turnover rate of both isomerization and hydrogenolysis. In the case of Pt100-x Pdx(SOMC) catalysts, the experimental results in combination with DFT calculations suggested a selective coverage of Pt (1 0 0) surface by agglomerated Pd atoms like “islands”, assuming that each metal roughly keeps its intrinsic catalytic properties with relatively small electron transfer from Pt to Pd in the case of Pt-rich sample and from Pd to Pt in the case of Pd-rich sample. For the PtPd catalysts prepared by IE, the catalytic behavior could be explained by the formation of a surface alloy between Pt and Pd in the case of Pd-rich sample and by the segregation of a small amount of Pd on the surface in the case of Pt-rich sample, as demonstrated by TEM, EXAFS and DFT. The catalytic results were explained by a structure activity relationship based on the proposed mechanism of CH bond and CC bond activation and cleavage for iso-butane hydrogenolysis, isomerization, cracking and dehydrogenation.

  17. Understanding of the structure activity relationship of PtPd bimetallic catalysts prepared by surface organometallic chemistry and ion exchange during the reaction of iso-butane with hydrogen

    KAUST Repository

    Alshareef, Reem Abdul aziz Hamed

    2018-04-25

    Well-defined silica supported bimetallic catalysts Pt100-x Pdx were prepared by Surface Organometallic Chemistry (SOMC) and Ionic-Exchange (IE) methods. For all investigated catalysts, iso-butane reaction with hydrogen under differential conditions led to the formation of methane and propane, n-butane, and traces of iso-butylene. The total reaction rate decreased with increasing the Pd loading for both catalysts series as a result of decreasing turnover rate of both isomerization and hydrogenolysis. In the case of Pt100-x Pdx(SOMC) catalysts, the experimental results in combination with DFT calculations suggested a selective coverage of Pt (1 0 0) surface by agglomerated Pd atoms like “islands”, assuming that each metal roughly keeps its intrinsic catalytic properties with relatively small electron transfer from Pt to Pd in the case of Pt-rich sample and from Pd to Pt in the case of Pd-rich sample. For the PtPd catalysts prepared by IE, the catalytic behavior could be explained by the formation of a surface alloy between Pt and Pd in the case of Pd-rich sample and by the segregation of a small amount of Pd on the surface in the case of Pt-rich sample, as demonstrated by TEM, EXAFS and DFT. The catalytic results were explained by a structure activity relationship based on the proposed mechanism of CH bond and CC bond activation and cleavage for iso-butane hydrogenolysis, isomerization, cracking and dehydrogenation.

  18. Half-metallicity in 2D organometallic honeycomb frameworks

    Science.gov (United States)

    Sun, Hao; Li, Bin; Zhao, Jin

    2016-10-01

    Half-metallic materials with a high Curie temperature (T C) have many potential applications in spintronics. Magnetic metal free two-dimensional (2D) half-metallic materials with a honeycomb structure contain graphene-like Dirac bands with π orbitals and show excellent aspects in transport properties. In this article, by investigating a series of 2D organometallic frameworks with a honeycomb structure using first principles calculations, we study the origin of forming half-metallicity in this kind of 2D organometallic framework. Our analysis shows that charge transfer and covalent bonding are two crucial factors in the formation of half-metallicity in organometallic frameworks. (i) Sufficient charge transfer from metal atoms to the molecules is essential to form the magnetic centers. (ii) These magnetic centers need to be connected through covalent bonding, which guarantee the strong ferromagnetic (FM) coupling. As examples, the organometallic frameworks composed by (1,3,5)-benzenetricarbonitrile (TCB) molecules with noble metals (Au, Ag, Cu) show half-metallic properties with T C as high as 325 K. In these organometallic frameworks, the strong electronegative cyano-groups (CN groups) drive the charge transfer from metal atoms to the TCB molecules, forming the local magnetic centers. These magnetic centers experience strong FM coupling through the d-p covalent bonding. We propose that most of the 2D organometallic frameworks composed by molecule—CN—noble metal honeycomb structures contain similar half metallicity. This is verified by replacing TCB molecules with other organic molecules. Although the TCB-noble metal organometallic framework has not yet been synthesized, we believe the development of synthesizing techniques and facility will enable the realization of them. Our study provides new insight into the 2D half-metallic material design for the potential applications in nanotechnology.

  19. Half-metallicity in 2D organometallic honeycomb frameworks

    International Nuclear Information System (INIS)

    Sun, Hao; Li, Bin; Zhao, Jin

    2016-01-01

    Half-metallic materials with a high Curie temperature (T C ) have many potential applications in spintronics. Magnetic metal free two-dimensional (2D) half-metallic materials with a honeycomb structure contain graphene-like Dirac bands with π orbitals and show excellent aspects in transport properties. In this article, by investigating a series of 2D organometallic frameworks with a honeycomb structure using first principles calculations, we study the origin of forming half-metallicity in this kind of 2D organometallic framework. Our analysis shows that charge transfer and covalent bonding are two crucial factors in the formation of half-metallicity in organometallic frameworks. (i) Sufficient charge transfer from metal atoms to the molecules is essential to form the magnetic centers. (ii) These magnetic centers need to be connected through covalent bonding, which guarantee the strong ferromagnetic (FM) coupling. As examples, the organometallic frameworks composed by (1,3,5)-benzenetricarbonitrile (TCB) molecules with noble metals (Au, Ag, Cu) show half-metallic properties with T C as high as 325 K. In these organometallic frameworks, the strong electronegative cyano-groups (CN groups) drive the charge transfer from metal atoms to the TCB molecules, forming the local magnetic centers. These magnetic centers experience strong FM coupling through the d – p covalent bonding. We propose that most of the 2D organometallic frameworks composed by molecule—CN—noble metal honeycomb structures contain similar half metallicity. This is verified by replacing TCB molecules with other organic molecules. Although the TCB-noble metal organometallic framework has not yet been synthesized, we believe the development of synthesizing techniques and facility will enable the realization of them. Our study provides new insight into the 2D half-metallic material design for the potential applications in nanotechnology. (paper)

  20. New Concept of C–H and C–C Bond Activation via Surface Organometallic Chemistry

    KAUST Repository

    Samantaray, Manoja

    2015-08-18

    In this chapter we describe the recent applications of well-defined oxidesupported metal alkyls/alkylidenes/alkylidynes and hydrides of group IV, V, and VI transition metals in the field of C–H and C–C bond activation. The activation of ubiquitous C–H and C–C bonds of paraffin is a long-standing challenge because of intrinsic low reactivity. There are many concepts derived from surface organometallic chemistry (SOMC): surface organometallic fragments are always intermediates in heterogeneous catalysis. The study of their synthesis and reactivity is a way to rationalize mechanism of heterogeneous catalysis and to achieve structure activity relationship. By surface organometallic chemistry one can enter any catalytic center by a reaction intermediate leading in fine to single site catalysts. With surface organometallic chemistry one can coordinate to the metal which can play a role in different elementary steps leading for example to C–H activation and Olefin metathesis. Because of the development of SOMC there is a lot of space for the improvement of homogeneous catalysis. After the 1997 discovery of alkane metathesis using silica-supported tantalum hydride by Basset et al. at low temperature (150ºC) the focus in this area was shifted to the discovery of more and more challenging surface complexes active in the application of C–H and C–C bond activation. Here we describe the evolution of well-defined metathesis catalyst with time as well as the effect of support on catalysis. We also describe here which metal–ligand combinations are responsible for a variety of C–H and C–C bond activation.

  1. Organometallic neptunium(III) complexes

    Science.gov (United States)

    Dutkiewicz, Michał S.; Farnaby, Joy H.; Apostolidis, Christos; Colineau, Eric; Walter, Olaf; Magnani, Nicola; Gardiner, Michael G.; Love, Jason B.; Kaltsoyannis, Nikolas; Caciuffo, Roberto; Arnold, Polly L.

    2016-08-01

    Studies of transuranic organometallic complexes provide a particularly valuable insight into covalent contributions to the metal-ligand bonding, in which the subtle differences between the transuranium actinide ions and their lighter lanthanide counterparts are of fundamental importance for the effective remediation of nuclear waste. Unlike the organometallic chemistry of uranium, which has focused strongly on UIII and has seen some spectacular advances, that of the transuranics is significantly technically more challenging and has remained dormant. In the case of neptunium, it is limited mainly to NpIV. Here we report the synthesis of three new NpIII organometallic compounds and the characterization of their molecular and electronic structures. These studies suggest that NpIII complexes could act as single-molecule magnets, and that the lower oxidation state of NpII is chemically accessible. In comparison with lanthanide analogues, significant d- and f-electron contributions to key NpIII orbitals are observed, which shows that fundamental neptunium organometallic chemistry can provide new insights into the behaviour of f-elements.

  2. Organometallic neptunium(III) complexes.

    Science.gov (United States)

    Dutkiewicz, Michał S; Farnaby, Joy H; Apostolidis, Christos; Colineau, Eric; Walter, Olaf; Magnani, Nicola; Gardiner, Michael G; Love, Jason B; Kaltsoyannis, Nikolas; Caciuffo, Roberto; Arnold, Polly L

    2016-08-01

    Studies of transuranic organometallic complexes provide a particularly valuable insight into covalent contributions to the metal-ligand bonding, in which the subtle differences between the transuranium actinide ions and their lighter lanthanide counterparts are of fundamental importance for the effective remediation of nuclear waste. Unlike the organometallic chemistry of uranium, which has focused strongly on U(III) and has seen some spectacular advances, that of the transuranics is significantly technically more challenging and has remained dormant. In the case of neptunium, it is limited mainly to Np(IV). Here we report the synthesis of three new Np(III) organometallic compounds and the characterization of their molecular and electronic structures. These studies suggest that Np(III) complexes could act as single-molecule magnets, and that the lower oxidation state of Np(II) is chemically accessible. In comparison with lanthanide analogues, significant d- and f-electron contributions to key Np(III) orbitals are observed, which shows that fundamental neptunium organometallic chemistry can provide new insights into the behaviour of f-elements.

  3. Organometallic B12-DNA conjugate

    DEFF Research Database (Denmark)

    Hunger, Miriam; Mutti, Elena; Rieder, Alexander

    2014-01-01

    Design, synthesis, and structural characterization of a B12-octadecanucleotide are presented herein, a new organometallic B12-DNA conjugate. In such covalent conjugates, the natural B12 moiety may be a versatile vector for controlled in vivo delivery of oligonucleotides to cellular targets in hum...

  4. Organometallic-inorganic hybrid electrodes for lithium-ion batteries

    Science.gov (United States)

    Huang, Qian; Lemmon, John P.; Choi, Daiwon; Cosimbescu, Lelia

    2016-09-13

    Disclosed are embodiments of active materials for organometallic and organometallic-inorganic hybrid electrodes and particularly active materials for organometallic and organometallic-inorganic hybrid cathodes for lithium-ion batteries. In certain embodiments the organometallic material comprises a ferrocene polymer.

  5. Organometallic compounds of the lanthanides, actinides and early transition metals

    Energy Technology Data Exchange (ETDEWEB)

    Cardin, D J [Trinity Coll., Dublin (Ireland); Cotton, S A [Stanground School, Peterborough (UK); Green, M [Bristol Univ. (UK); Labinger, J A [Atlantic Richfield Co., Los Angeles, CA (USA); eds.

    1985-01-01

    This book provides a reference compilation of physical and biographical data on over 1500 of the most important and useful organometallic compounds of the lanthanides, actinides and early transition metals representing 38 different elements. The compounds are listed in molecular formula order in a series of entries in dictionary format. Details of structure, physical and chemical properties, reactions and key references are clearly set out. All the data is fully indexed and a structural index is provided.

  6. Photochemical reaction dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Moore, B.C. [Lawrence Berkeley Laboratory, Livermore, CA (United States)

    1993-12-01

    The purpose of the program is to develop a fundamental understanding of unimolecular and bimolecular reaction dynamics with application in combustion and energy systems. The energy dependence in ketene isomerization, ketene dissociation dynamics, and carbonyl substitution on organometallic rhodium complexes in liquid xenon have been studied. Future studies concerning unimolecular processes in ketene as well as energy transfer and kinetic studies of methylene radicals are discussed.

  7. Uncatalyzed hydroamination of electrophilic organometallic alkynes: fundamental, theoretical, and applied aspects.

    Science.gov (United States)

    Wang, Yanlan; Latouche, Camille; Rapakousiou, Amalia; Lopez, Colin; Ledoux-Rak, Isabelle; Ruiz, Jaime; Saillard, Jean-Yves; Astruc, Didier

    2014-06-23

    Simple reactions of the most used functional groups allowing two molecular fragments to link under mild, sustainable conditions are among the crucial tools of molecular chemistry with multiple applications in materials science, nanomedicine, and organic synthesis as already exemplified by peptide synthesis and "click" chemistry. We are concerned with redox organometallic compounds that can potentially be used as biosensors and redox catalysts and report an uncatalyzed reaction between primary and secondary amines with organometallic electrophilic alkynes that is free of side products and fully "green". A strategy is first proposed to synthesize alkynyl organometallic precursors upon addition of electrophilic aromatic ligands of cationic complexes followed by endo hydride abstraction. Electrophilic alkynylated cyclopentadienyl or arene ligands of Fe, Ru, and Co complexes subsequently react with amines to yield trans-enamines that are conjugated with the organometallic group. The difference in reactivities of the various complexes is rationalized from the two-step reaction mechanism that was elucidated through DFT calculations. Applications are illustrated by the facile reaction of ethynylcobalticenium hexafluorophosphate with aminated silica nanoparticles. Spectroscopic, nonlinear-optical and electrochemical data, as well as DFT and TDDFT calculations, indicate a strong push-pull conjugation in these cobalticenium- and Fe- and Ru-arene-enamine complexes due to planarity or near-planarity between the organometallic and trans-enamine groups involving fulvalene iminium and cyclohexadienylidene iminium mesomeric forms. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Hydrodeoxygenation of coal using organometallic catalyst precursors

    Science.gov (United States)

    Kirby, Stephen R.

    2002-04-01

    The objective of this dissertation was to determine the desirability of organometallic compounds for the hydrodeoxygenation (HDO) of coal during liquefaction. The primary focus of this study was the removal of phenol-like compounds from coal liquids for the production of a thermally stable jet fuel. Investigation of the HDO ability of an organometallic compound containing both cobalt and molybdenum (CoMo-T2) was achieved using a combination of model compound and coal experiments. Model compounds were chosen representing four oxygen functional groups present in a range of coals. Electron density and bond order calculations were performed for anthrone, dinaphthyl ether, xanthene, di-t-butylmethylphenol, and some of their derivatives to ascertain a potential order of hydrogenolysis and hydrogenation reactivity for these compounds. The four model compounds were then reacted with CoMo-T2, as well as ammonium tetrathiomolybdate (ATTM). Products of reaction were grouped as compounds that had undergone deoxygenation, those that had aromatic rings reduced, those that were products of both reaction pathways, and those produced through other routes. ATTM had an affinity for both reaction types. Its reaction order for the four model compounds with respect to deoxygenated compounds was the same as that estimated from electron density calculations for hydrogenolysis reactivity. CoMo-T2 appeared to show a preference toward hydrogenation, although deoxygenated products were still achieved in similar, or greater, yields, for almost all the model compounds. The reactivity order achieved for the four compounds with CoMo-T2 was similar to that estimated from bond order calculations for hydrogenation reactivity. Three coals were selected representing a range of coal ranks and oxygen contents. DECS-26 (Wyodak), DECS-24 (Illinois #6), and DECS-23 (Pittsburgh #8) were analyzed by CPMAS 13C NMR and pyrolysis-GC-MS to determine the functional groups comprising the oxygen content of these

  9. Use of ionic liquids as coordination ligands for organometallic catalysts

    Science.gov (United States)

    Li, Zaiwei [Moreno Valley, CA; Tang, Yongchun [Walnut, CA; Cheng,; Jihong, [Arcadia, CA

    2009-11-10

    Aspects of the present invention relate to compositions and methods for the use of ionic liquids with dissolved metal compounds as catalysts for a variety of chemical reactions. Ionic liquids are salts that generally are liquids at room temperature, and are capable of dissolving a many types of compounds that are relatively insoluble in aqueous or organic solvent systems. Specifically, ionic liquids may dissolve metal compounds to produce homogeneous and heterogeneous organometallic catalysts. One industrially-important chemical reaction that may be catalyzed by metal-containing ionic liquid catalysts is the conversion of methane to methanol.

  10. CORROSION RESISTANCE OF ORGANOMETALLIC COATING APLICATED IN FUEL TANKS USING ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY IN BIOFUEL – PART I

    Directory of Open Access Journals (Sweden)

    Milene Adriane Luciano

    2014-10-01

    Full Text Available Nowadays, the industry has opted for more sustainable production processes, and the planet has also opted for new energy sources. From this perspective, automotive tanks with organometallic coatings as well as a partial substitution of fossil fuels by biofuels have been developed. These organometallic coated tanks have a zinc layer, deposited by a galvanizing process, formed between the steel and the organometallic coating. This work aims to characterize the organometallic coating used in metal automotive tanks and evaluate their corrosion resistance in contact with hydrated ethyl alcohol fuel (AEHC. For this purpose, the resistance of all layers formed between Zinc and EEP steel and also the tin coated steel, which has been used for over thirty years, were evaluated. The technique chosen was the Electrochemical Impedance Spectroscopy. The results indicated an increase on the corrosion resistance when organometallic coatings are used in AEHC medium. In addition to that, these coatings allow an estimated 25% reduction in tanks production costs.

  11. Volatile organometallic and semiconductor materials

    International Nuclear Information System (INIS)

    Dickson, R.S.

    1991-01-01

    This article reports on a project concerned with the metal organic chemical vapour deposition (MOCVD) of mercury-cadmium telluride (MCT) undertaken by a research consortium based in the Clayton area involving Monash University Chemistry Department, Telecom Research Laboratories, and CSIRO Division of Material Sciences and Technology. An M.R. Semicon 226 MOCVD reactor, operating near atmospheric presure with hydrogen carrier gas has been used. Most applications of MCT are direct consequence of its responsiveness to radiation in infrared region spectrum. The main aims of the project were to prepare and assess a range of volatile organometallics that might find use as a dopant sources for MCT, to prepare and study the properties of a range of different lanthanide complexes for MOCVD applications and to fully characterize the semiconductor wafers after growth. 19 refs., 3 figs

  12. Synthesis, characterization and reactivity of some lanthanide organometallics

    International Nuclear Information System (INIS)

    Marchal, N.

    1991-12-01

    Organo lanthanides with reactive metal-carbon bonds are obtained by direct synthesis of the metal (powder) and a hydrocarbon in ether medium, like with alkali metals. Two types of synthesis are envisaged: formation of covalent bonds by opening cycles, only biphenylene is reactive enough in regard to ytterbium and samarium, these organometallic compounds can also be prepared by the classical way, i.e. reaction of 2.2'-dilithio biphenyl on rare earth halogenides and coupling of 6.6-dimethylfulvene leading to dicyclopentadienyl compounds with Sm and Yb. The reactivity of these complexes is studied by catalysis of ethylene polymerization

  13. New Route to Synthesize Surface Organometallic Complexes (SOMC): An Approach by Alkylating Halogenated Surface Organometallic Fragments

    KAUST Repository

    Hamieh, Ali Imad

    2017-02-01

    The aim of this thesis is to explore new simpler and efficient routes for the preparation of surface organometallic complexes (SOMC) for the transformation of small organic molecules to valuable products. The key element in this new route relies on surface alkylation of various halogenated surface coordination complexes or organometallic fragments (SOMF).

  14. New Route to Synthesize Surface Organometallic Complexes (SOMC): An Approach by Alkylating Halogenated Surface Organometallic Fragments

    KAUST Repository

    Hamieh, Ali Imad Ali

    2017-01-01

    The aim of this thesis is to explore new simpler and efficient routes for the preparation of surface organometallic complexes (SOMC) for the transformation of small organic molecules to valuable products. The key element in this new route relies on surface alkylation of various halogenated surface coordination complexes or organometallic fragments (SOMF).

  15. Sodium-concrete reaction model development

    International Nuclear Information System (INIS)

    Nguyen, D.H.; Muhlestein, L.D.; Postma, A.K.

    1982-07-01

    Major observations have been formulated after reviewing test results for over 100 sodium-concrete reaction tests. The observations form the basis for developing a mechanistic model to predict the transient behavior of sodium-concrete reactions. The major observations are listed. Mechanisms associated with sodium and water transport to the reaction zone are identified, and represented by appropriate mathematical expressions. The model attempts to explain large-scale, long-term (100 h) test results were sodium-concrete reactions terminated even in the presence of unreacted sodium and concrete

  16. Beyond organometallic flow chemistry : the principles behind the use of continuous-flow reactors for synthesis

    NARCIS (Netherlands)

    Noel, T.; Su, Y.; Hessel, V.; Noël, T.

    2015-01-01

    Flow chemistry is typically used to enable challenging reactions which are difficult to carry out in conventional batch equipment. Consequently, the use of continuous-flow reactors for applications in organometallic and organic chemistry has witnessed a spectacular increase in interest from the

  17. Supramolecular Dendriphores: Anionic Organometallic Phosphors Embedded in Polycationic Dendritic Species

    NARCIS (Netherlands)

    McDonald, A.R.; Mores, D.; de Mello-Donega, C.; van Walree, C.A.; Klein Gebbink, R.J.M.; Lutz, M.; Spek, A.L.; Meijerink, A.; van Klink, G.P.M.; van Koten, G.

    2009-01-01

    Heteroleptic iridium(III) organometallic complexes have been functionalized with sulfate tethers. These systems have been thoroughly characterized spectroscopically. Subsequently these iridium(III) complexes were reacted with polyionic dendritic materials yielding iridium(III) organometallic

  18. Synthesis and studies of some organometallic compounds of uranium IV

    International Nuclear Information System (INIS)

    Marquet-Ellis, Hubert; Folcher, Gerard.

    1975-06-01

    The organometallic compounds of uranium IV have been well known for a long-time but some difficulties in the synthese subsist. The procedures and the apparatus allowing to obtain these compounds with good yields are described. The cyclopenta dienyl compounds U(C 5 H 5 ) 3 Cl, U(C 5 H 5 ) 4 are prepared by reaction of UCl 4 with Na(C 5 H 5 ) in tetrahydrofurane. The cyclooctatetraene compound U(C 8 H 8 ) 2 ''Uranocene'' is obtained by reaction of K 2 (C 8 H 8 ) on UCl 4 in tetrahydrofurane. The NMR spectrum of the solution during the reaction shows the appearance of the product. These compounds have been identified by chemical analysis and X rays. The visible spectra of U(C 5 H 5 ) 2 Cl and U(C 8 H 8 ) 2 in gaseous phase have been obtained [fr

  19. Reaction path analysis of sodium-water reaction phenomena in support of chemical reaction model development

    International Nuclear Information System (INIS)

    Kikuchi, Shin; Ohshima, Hiroyuki; Hashimoto, Kenro

    2011-01-01

    Computational study of the sodium-water reaction at the gas (water) - liquid (sodium) interface has been carried out using ab initio (first-principle) method. A possible reaction channel has been identified for the stepwise OH bond dissociations of a single water molecule. The energetics including the binding energy of a water molecule to the sodium surface, the activation energies of the bond cleavages, and the reaction energies, have been evaluated, and the rate constants of the first and second OH bond-breakings have been compared. The results are used as the basis for constructing the chemical reaction model used in a multi-dimensional sodium-water reaction code, SERAPHIM, being developed by JAEA toward the safety assessment of the steam generator (SG) in a sodium-cooled fast reactor (SFR). (author)

  20. Automated building of organometallic complexes from 3D fragments.

    Science.gov (United States)

    Foscato, Marco; Venkatraman, Vishwesh; Occhipinti, Giovanni; Alsberg, Bjørn K; Jensen, Vidar R

    2014-07-28

    A method for the automated construction of three-dimensional (3D) molecular models of organometallic species in design studies is described. Molecular structure fragments derived from crystallographic structures and accurate molecular-level calculations are used as 3D building blocks in the construction of multiple molecular models of analogous compounds. The method allows for precise control of stereochemistry and geometrical features that may otherwise be very challenging, or even impossible, to achieve with commonly available generators of 3D chemical structures. The new method was tested in the construction of three sets of active or metastable organometallic species of catalytic reactions in the homogeneous phase. The performance of the method was compared with those of commonly available methods for automated generation of 3D models, demonstrating higher accuracy of the prepared 3D models in general, and, in particular, a much wider range with respect to the kind of chemical structures that can be built automatically, with capabilities far beyond standard organic and main-group chemistry.

  1. Development of Green and Sustainable Chemical Reactions

    DEFF Research Database (Denmark)

    Taarning, Esben

    Abstract This thesis entitled Development of Green and Sustainable Chemical Reactions is divided into six chapters involving topics and projects related to green and sustainable chemistry. The chapters can be read independently, however a few concepts and some background information is introduced...... as well as the possibility for establishing a renewable chemical industry is discussed. The development of a procedure for using unsaturated aldehydes as olefin synthons in the Diels- Alder reaction is described in chapter three. This procedure affords good yields of the desired Diels- Alder adducts...... in chapter one and two which can be helpful to know when reading the subsequent chapters. The first chapter is an introduction into the fundamentals of green and sustainable chemistry. The second chapter gives an overview of some of the most promising methods to produce value added chemicals from biomass...

  2. Part I. An investigation into the mechanism of the samarium (II)-promoted Barbier reaction: Sequential radical cyclization/organometallic addition. Part II. Conjugate addition reactions of organosamarium reagents by in situ transmetalation to cuprates. Part III. Approximate absolute rate constants for the reaction of tributyltin radicals with aryl and vinyl halides. Part IV. An investigation into the synthetic utility of tri-n-butylgermanium hydride

    Energy Technology Data Exchange (ETDEWEB)

    Totleben, M.J.

    1992-01-01

    An investigation of the mechanism of the samarium diiodide mediated Barbier reaction was conducted. Through a series of alkyl halide-carbonyl coupling and deuterium labelling experiments, evidence supportive of an organometallic addition mechanism was collected. Further probing led to an expansion of the utility of SmI[sub 2] in synthesis. The author has shown that radical cyclization of aryl and alkyl radicals to olefins, followed by reduction to primary and secondary organosamarium species is feasible. Organosamarium (III) reagents, produced by the reduction of alkyl and select aryl halides with 2 equiv of SmI[sub 2] in THF/HMPA, were treated with copper (I) salts and complexes to effect in situ transmetalation to cuprates. This allowed the 1,4-addition to [alpha],[beta]-unsaturated ketones. This new methodology allows for the sequential formation of carbon-carbon bonds through a combination of free radical and cuprate chemistry. Absolute rate constants for the abstraction of bromine atoms (k[sub Br]) by tri-n-butyltin radicals from a series of vinyl and aryl bromides have been determined. Atom abstraction was modestly enhanced by proximity of the halogen to a substituent in the following order: para < meta < ortho. Tri-n-butyl germanium hydride is known to be a poorer hydrogen atom donor than its tin analog. This feature makes it attractive for use in slow radical cyclizations where tin hydride would provide mainly for reduction. A brief study was executed to improve on the utility of the reagent as current conditions do not yield desired products in high amounts. Initial investigations examined the effect of initiator on reduction by germanium hydride, and subsequent experiments probed solvent effects. t-Butyl alcohol was determined to be superior to benzene or acetonitrile, giving consistently higher yields of reduction products.

  3. PREPARATION OF TANTALUM CARBIDE FROM AN ORGANOMETALLIC PRECURSOR

    Directory of Open Access Journals (Sweden)

    C. P. SOUZA

    1999-03-01

    Full Text Available In this work we have synthesized an organometallic oxalic precursor from tantalum oxide. This oxide was solubilized by heating with potassium hydrogen sulfate. In order to precipitate Ta2O5.nH2O, the fused mass obtained was dissolved in a sulfuric acid solution and neutralized with ammonia. The hydrated tantalum oxide precipitated was dissolved in an equimolar solution of oxalic acid/ammonium oxalate. The synthesis and the characterization of the tantalum oxalic precursor are described. Pyrolysis of the complex in a mixture of hydrogen and methane at atmospheric pressure was studied. The gas-solid reaction made it possible to obtain tantalum carbide, TaC, in the powder form at 1000oC. The natural sintering of TaC powder in an inert atmosphere at 1400°C during 10 hours, under inert atmosphere made it possible to densify the carbide to 96% of the theoretical value.

  4. Basic organometallic chemistry: containing comprehensive bibliography

    National Research Council Canada - National Science Library

    Haiduc, Ionel; Zuckerman, Jerry J

    1985-01-01

    .... Organometallic chemistry is the discipline dealing with compounds containing at least one direct metal-carbon bond. This bond can be simple covalent [as in lead tetraethyl, Pb(C H )J or π-dative [as in ferrocene, Fe(i/ 5 2 5 -C 5 H 5 ) 2 ] or even predominantly ionic [as in ethylsodium, N a + C 2 Hs ]. On this basis, compounds like metal alkoxides, [for example, alu...

  5. Enthalpies of vaporization of organometallic compounds

    International Nuclear Information System (INIS)

    Kuznetsov, N.T.; Sevast'yanov, V.G.; Mitin, V.A.; Krasnodubskaya, S.V.; Zakharov, L.N.; Domrachev, G.A.; AN SSSR, Gor'kij. Inst. Khimii)

    1987-01-01

    A possibility to use the method of additive schemes for the calculation of vaporizaton enthalpies of uranium organometallic compounds is discussed while comparing the values obtained using the method with experimental data. The possibility of apriori evaluation of evaporation enthalpy values of different uranium compounds using the method of additive schemes and structural characteristics of molecules, such as the sum of ligand solid angles, is shown

  6. Historical Development of War Stress Reaction Syndromes

    Directory of Open Access Journals (Sweden)

    Kamil Nahit Ozmenler

    2010-02-01

    Full Text Available The battles that have come to this day had spectacular psychologic and psychiatric effects. Battle stres reactions in historical development phase has been mentioned with such different names as nostalgia, shell shock, soldier’s heart, Da Costra Syndrome, old sergeant syndrome, agent orange effect and post traumatic stress disorder (PTSD due to the symptoms coming into prominence. On the othere hand they do tend to show similarities (palpilation, stomach complaints, rhomatizmal aches, neurological and psychiatric symptoms, etc. in the context of symptoms and findigs. During the historical phase, the transition of methods have also infliuenced the prominent clinical characteristics of the war stress syndromes. The symptoms that arose during the gulf War have exhibited neither similarities nor explainable characteristics with previous war stress reactions of the past. Therefore, in the context of diagnostics systems, there is no clarity about where it should be incorporated. The inability to find any satisfactory organic pathology in war stress reactions have been the unchanging characteristic of the illness. In collaboration with the increasing mortality and morbidity that arise in wars it is not only an important factor but the resistance of patients, who had been effected, to amelioration is continuing to be an important concern which preoccupies governments, military authorities and doctors. [TAF Prev Med Bull 2010; 9(1.000: 63-70

  7. Fabrication of superconducting wire using organometallic precursors and infiltration

    International Nuclear Information System (INIS)

    Lee, Y.J.

    1991-01-01

    Organometallic precursors from naphthenic acid and metal nitrates were used for the synthesis of YBCO oxide superconducting compounds. The characteristics of metal naphthenates as organometallic precursors were investigated by IR spectra, viscosity measurements, and infiltration. 123 superconducting compound obtained from 123 naphthenate showed a Tc of 90 degree K and a rather dense and elongated microstructure. Also, the melting behavior of Ba-cuprates which were used for 123 making was studied. A low-temperature melting process was developed to fabricate silver-sheathed superconducting wire with the powder-in-tube method; flowing argon gas is introduced to the system at 930-945 degree C to reduce the melting temperature of the 123 compound without silver sheath melting. It resulted in a 90 degree K Tc superconducting core with dense and locally aligned microstructure. SEM-EDS and XRD analysis, 4-probe resistance and Jc measurements, and carbon-content determinations were carried out to characterize the microstructure, grain alignment, and superconducting properties of the samples

  8. 2012 Gordon Research Conference, Organometallic Chemistry, 8-13 2012

    Energy Technology Data Exchange (ETDEWEB)

    Hillhouse, Gregory [Univ. of Chicago, IL (United States)

    2012-07-13

    The 2012 Organometallic Chemistry Gordon Research Conference will highlight new basic science and fundamental applications of organometallic chemistry in industrial, academic, and national lab settings. Scientific themes of the conference will include chemical synthesis, reactivity, catalysis, polymer chemistry, bonding, and theory that involve transition-metal (and main-group) interactions with organic moieties.

  9. ORGANOMETALLIC IRON(II) COMPLEXES CONTAINING P-SUBSTITUTED ACETOPHENONE-ARYLHYDRAZONE LIGANDS

    OpenAIRE

    Manzur, Carolina; Millán, Lorena; Figueroa, Walter; Hamon, Jean-René; Mata, Jose A.; Carrillo, David

    2002-01-01

    A series of twelve new organometallic acetophenone-hydrazone complexes of general formula [(h 5-Cp)Fe(h 6-o-RC6H4)-NHN=CMe-C6H4-p-R’]+PF6- (Cp= C5H5; R,R’=H,Me, [5]+PF6-; H,MeO, [6]+PF6-; H,NMe2, [7]+PF6-; Me,Me, [8]+PF6-; Me,MeO, [9]+PF6-; Me,NMe2, [10]+PF6-; MeO,Me, [11]+PF6-; MeO,MeO, [12]+PF6-; MeO,NMe2, [13]+PF6-; Cl,Me, [14]+PF6-; Cl,MeO, [15]+PF6-; Cl,NMe2, [16]+PF6-) has been prepared by reaction between their corresponding organometallic hydrazine precursors [(h 5-Cp)Fe(h 6-o-RC6H4)-...

  10. Highvalent and organometallic technetium and rhenium compounds

    International Nuclear Information System (INIS)

    Oehlke, Elisabeth

    2010-01-01

    Diagnostic methods in nuclear medicine allow a detailed description of morphological organ structures and their function. The beta emitting isotope Tc-99 has optimal physical properties (140 keV gamma rays, half-life 6 h) and is therefore used for radiopharmaceuticals. The thesis is concerned with the search for new technetium complexes and their reproducible production. The (TcO3) core is of main interest. The second part of the thesis deals with organometallic technetium and rhenium complexes with carbonyl ligands and N-heterocyclic carbenes that show stability in aerobic aqueous solutions.

  11. Organometallics and related molecules for energy conversion

    CERN Document Server

    Wong, Wai-Yeung

    2015-01-01

    This book presents a critical perspective of the applications of organometallic compounds (including those with metal or metalloid elements) and other related metal complexes as versatile functional materials in the transformation of light into electricity (solar energy conversion) and electricity into light (light generation in light emitting diode), in the reduction of carbon dioxide to useful chemicals, as well as in the safe and efficient production and utilization of hydrogen, which serves as an energy storage medium (i.e. energy carrier). This book focuses on recent research developmen

  12. Hydrodeoxygenation of O-containing polycyclic model compounds using a novel organometallic catalyst-precursor

    Energy Technology Data Exchange (ETDEWEB)

    Kirby, S.R.; Song, C.S.; Schobert, H.H. [Pennsylvania State University, University Park, PA (United States). Dept. of Materials Science and Engineering

    1996-09-05

    Compounds containing oxygen functional groups, especially phenols, are undesirable components of coal-derived liquids. Removal of these compounds from the products of coal liquefaction is required. A beneficial alternative would be the removal of these compounds, or the prevention of their formation, during the liquefaction reaction itself, rather than as a separate processing step. A novel organometallic catalyst precursor containing Co and Mo has been studied as a potential hydrogenation catalyst for coal liquefaction. To ascertain the hydrodeoxygenation activity of this catalyst under liquefaction conditions, model compounds were investigated. Anthrone, 2,6-di-r-btuyl-4-methyl-phenol, dinaphthyl ether and xanthene were reacted in the presence of the Co-Mo catalyst precursor and a precursor containing only Mo over a range of temperatures, providing a comparison of conversions to deoxygenated products. These conversions give an indication of the hydrodeoxygenating abilities of organometallic catalyst precursors within a coal liquefaction system. For example, at 400{degree}C dinaphthyl ether was converted 100% (4.5% O-containing products) in the presence of the Co-Mo organometallic precursor, compared to 76.5% conversion (7.4% O-products) in the presence of the Mo catalyst.

  13. 2011 Organometallic Chemistry (July 10-15, 2011, Salve Regina University, Newport, RI)

    Energy Technology Data Exchange (ETDEWEB)

    Dr. Emilio Bunel

    2011-07-15

    Organometallic chemistry has played and will continue to play a significant role in helping us understand the way bonds are made or broken in the presence of a transition metal complex. Current challenges range from the efficient exploitation of energy resources to the creative use of natural and artificial enzymes. Most of the new advances in the area are due to our extended understanding of processes at a molecular level due to new mechanistic studies, techniques to detect reaction intermediates and theory. The conference will bring the most recent advances in the field including nanocatalysis, surface organometallic chemistry, characterization techniques, new chemical reactivity and theoretical approaches along with applications to organic synthesis and the discovery of new materials. The Conference will bring together a collection of investigators who are at the forefront of their field, and will provide opportunities for junior scientists and graduate students to present their work in poster format and exchange ideas with leaders in the field. Six outstanding posters will be selected for short talks. The collegial atmosphere of this Conference, with programmed discussion sessions as well as opportunities for informal gatherings in the afternoons and evenings, provides an avenue for scientists from different disciplines to brainstorm and promotes cross-disciplinary collaborations in the various research areas represented. Graduate students and postdoctoral fellows should also consider participating in the Gordon Research Seminar on Organometallic Chemistry (July 9-10, same location) which is specially designed to promote interaction and discussion between junior scientists.

  14. Mechanistic Studies at the Interface Between Organometallic Chemistry and Homogeneous Catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Casey, Charles P

    2012-11-14

    Mechanistic Studies at the Interface Between Organometallic Chemistry and Homogeneous Catalysis Charles P. Casey, Principal Investigator Department of Chemistry, University of Wisconsin - Madison, Madison, Wisconsin 53706 Phone 608-262-0584 FAX: 608-262-7144 Email: casey@chem.wisc.edu http://www.chem.wisc.edu/main/people/faculty/casey.html Executive Summary. Our goal was to learn the intimate mechanistic details of reactions involved in homogeneous catalysis and to use the insight we gain to develop new and improved catalysts. Our work centered on the hydrogenation of polar functional groups such as aldehydes and ketones and on hydroformylation. Specifically, we concentrated on catalysts capable of simultaneously transferring hydride from a metal center and a proton from an acidic oxygen or nitrogen center to an aldehyde or ketone. An economical iron based catalyst was developed and patented. Better understanding of fundamental organometallic reactions and catalytic processes enabled design of energy and material efficient chemical processes. Our work contributed to the development of catalysts for the selective and mild hydrogenation of ketones and aldehydes; this will provide a modern green alternative to reductions by LiAlH4 and NaBH4, which require extensive work-up procedures and produce waste streams. (C5R4OH)Ru(CO)2H Hydrogenation Catalysts. Youval Shvo described a remarkable catalytic system in which the key intermediate (C5R4OH)Ru(CO)2H (1) has an electronically coupled acidic OH unit and a hydridic RuH unit. Our efforts centered on understanding and improving upon this important catalyst for reduction of aldehydes and ketones. Our mechanistic studies established that the reduction of aldehydes by 1 to produce alcohols and a diruthenium bridging hydride species occurs much more rapidly than regeneration of the ruthenium hydride from the diruthenium bridging hydride species. Our mechanistic studies require simultaneous transfer of hydride from ruthenium to

  15. A review of the inorganic and organometallic chemistry of zirconium

    International Nuclear Information System (INIS)

    Kalvins, A.K.

    1985-01-01

    The results of a literature review of the inorganic and organometallic chemistry of zirconium are presented. Compounds with physical and chemical properties compatible with the requirements of an ir laser zirconium isotope separation process have been identified

  16. New labeling methods via organometallic species: new synthesis of a chiral methyl group

    International Nuclear Information System (INIS)

    Faucher, Nicolas

    2000-01-01

    Chapter 1: New labeling methods via organometallic species. In the first part of this work, we have developed a new labeling strategy based on the hydrogenolysis of organolithium compounds with tritium gas or deuterium gas. This reaction is catalyzed with palladium on charcoal and leads to the labelled compounds with direct replacement of the proton by its isotopes ("2H or "3H) without further chemical modification of the target molecule. Using this strategy, tritium or deuterium atoms can be introduced in a region but also in a stereoselective fashion with more than 90% ee. The former result was obtained using (-)-sparteine during the lithiation step. Chapter II: New synthesis of a chiral methyl group. In the second part of this work, we have developed a new synthetic method to prepare chiral ditosyl-methylamine using 4,5-disubstituted oxazolidines. Dia-stereoselective substitution of the methoxy group of a 2-alkoxy-oxazolidine by a deuteride in the presence of a Lewis acid leads to the 2-deutero-oxazolidine in a highly stereoselective fashion (de = 100%). Still using a lewis acid, a tritiated hydride open the former 2-deutero-oxazolidine to afford chiral methyl group borne by the nitrogen. Further de-protection and re-protection steps lead to the ditosyl-methylamine with an ee of 65% (RIS= 83/17). Nowadays, this is the best known synthetic method, not only in terms of enantioselectivity but also in terms of chemical yield and number of radioactive steps. As NTs_2 is a fairly good leaving group, the ditosyl-methylamine offers the possibility of introducing chiral methyl group in many substrates using a S_N2 reaction with various nucleophiles. This last point leads to many potential applications in the field of biochemistry or for mechanical studies. (author) [fr

  17. Structure of organometallic compounds obtained by plasma of titanium isopropoxide

    International Nuclear Information System (INIS)

    Arreola R, M. L.

    2012-01-01

    This work presents a study on the synthesis and characterization of organometallic compounds of titanium oxide obtained from glow discharges of titanium tetraisopropoxide (TTIP) and water on glass and polyethylene. The objective is the synthesis of titanium oxide particles which can be fixed on different supports for use in further studies of contaminants degradation in effluent streams. The synthesis was carried out by plasma in a glass tubular reactor of 750 cm 3 and 15 cm length at 10 -1 mbar with power between 100 and 150 W during 2, 3 and 4 h. The precursors were TTIP and water vapor. TTIP is an organometallic compound composed of a central atom of Ti surrounded by 4 O atoms, which in turn are connected with chains of 3 C (propane s). The objective is the use of plasma collisions to separate the organic and inorganic phases of TTIP, so that both structure independently in a single material. The result was the formation of white titanium oxide powder composed with agglomerates of spherical particles with average diameter between 160 and 452 nm adhered to small films. The agglomerates have a tendency to change from film to particles with the energy applied to the synthesis. The study of the chemical structure showed a great presence of O 2 -Ti-O 2 (Ti surrounded by O) which can be found in most titanium oxides. Other chemical groups belonging to the organic phase were C=C=C, C=C=O and C 2 -C-Ch appearing from the dehydrogenation of TTIP, which can be a possible precursor of this reactions kind. The structural superficial analyses showed that the atomic composition varies according to type of substrate used. The greatest content of Ti was obtained on glass substrates. However, the synthesis conditions had not evident effect in the participation of chemical states found in the inorganic phase. The crystalline studies indicated that the material is amorphous, although the de convoluted X-ray spectra showed that the synthesized titanium oxides on glass tend to

  18. Sweetening ruthenium and osmium: organometallic arene complexes containing aspartame.

    Science.gov (United States)

    Gray, Jennifer C; Habtemariam, Abraha; Winnig, Marcel; Meyerhof, Wolfgang; Sadler, Peter J

    2008-09-01

    The novel organometallic sandwich complexes [(eta(6)-p-cymene)Ru(eta(6)-aspartame)](OTf)(2) (1) (OTf = trifluoromethanesulfonate) and [(eta(6)-p-cymene)Os(eta(6)-aspartame)](OTf)(2) (2) incorporating the artificial sweetener aspartame have been synthesised and characterised. A number of properties of aspartame were found to be altered on binding to either metal. The pK(a) values of both the carboxyl and the amino groups of aspartame are lowered by between 0.35 and 0.57 pH units, causing partial deprotonation of the amino group at pH 7.4 (physiological pH). The rate of degradation of aspartame to 3,6-dioxo-5-phenylmethylpiperazine acetic acid (diketopiperazine) increased over threefold from 0.12 to 0.36 h(-1) for 1, and to 0.43 h(-1) for 2. Furthermore, the reduction potential of the ligand shifted from -1.133 to -0.619 V for 2. For the ruthenium complex 1 the process occurred in two steps, the first (at -0.38 V) within a biologically accessible range. This facilitates reactions with biological reductants such as ascorbate. Binding to and activation of the sweet taste receptor was not observed for these metal complexes up to concentrations of 1 mM. The factors which affect the ability of metal-bound aspartame to interact with the receptor site are discussed.

  19. Development of novel strategy for the synthesis of organometallic compounds usable as protein ligands: application to the human cyclophilin hCyp-18; Developpement de ligands de proteines par assemblage combinatoire autour d'un coeur de rhenium{sup V}: application a la cyclophiline hCyp-18

    Energy Technology Data Exchange (ETDEWEB)

    Clavaud, C

    2006-02-15

    This thesis describes a new strategy for the development of bioactive organometallic compounds, basing on the combinatorial assembly of sub-chemical libraries (A and B) independent but complementary and able to coordinate a metallic heart M to form A-M-B complex potential ligands of biomolecules. The coordination of metals, well adapted to the production of molecular variety is usually used in medicinal chemistry, in diagnostic and therapeutic nuclear medicine. Among the useful elements, the rhenium and the technetium are metals of choice for the development of the assembly strategy because of their chemical and radiochemical properties and of the structure analogy of their complexes. This strategy was validated in vitro. The protein chosen for this purpose was the cyclophilin hCyp-18. (N.C.)

  20. The synthesis and properties of some organometallic compounds containing group IV (Ge, Sn)-group II (Zn, Cd) metal---metal bonds

    NARCIS (Netherlands)

    Des Tombe, F.J.A.; Kerk, G.J.M. van der; Creemers, H.M.J.C.; Carey, N.A.D.; Noltes, J.G.

    1972-01-01

    The reactions of triphenylgermane and triphenyltin hydride with coordinatively saturated organozinc or organocadmium compounds give organometallic complexes containing Group IV (Ge, Sn)-Group II(Zn, Cd) metal---metal bonds. The 2,2′-bipyridine complexes show solvent-dependent charge-transfer

  1. Molecular metal catalysts on supports: organometallic chemistry meets surface science.

    Science.gov (United States)

    Serna, Pedro; Gates, Bruce C

    2014-08-19

    Recent advances in the synthesis and characterization of small, essentially molecular metal complexes and metal clusters on support surfaces have brought new insights to catalysis and point the way to systematic catalyst design. We summarize recent work unraveling effects of key design variables of site-isolated catalysts: the metal, metal nuclearity, support, and other ligands on the metals, also considering catalysts with separate, complementary functions on supports. The catalysts were synthesized with the goal of structural simplicity and uniformity to facilitate incisive characterization. Thus, they are essentially molecular species bonded to porous supports chosen for their high degree of uniformity; the supports are crystalline aluminosilicates (zeolites) and MgO. The catalytic species are synthesized in reactions of organometallic precursors with the support surfaces; the precursors include M(L)2(acetylacetonate)1-2, with M = Ru, Rh, Ir, or Au and the ligands L = C2H4, CO, or CH3. Os3(CO)12 and Ir4(CO)12 are used as precursors of supported metal clusters, and some such catalysts are made by ship-in-a-bottle syntheses to trap the clusters in zeolite cages. The simplicity and uniformity of the supported catalysts facilitate precise structure determinations, even in reactive atmospheres and during catalysis. The methods of characterizing catalysts in reactive atmospheres include infrared (IR), extended X-ray absorption fine structure (EXAFS), X-ray absorption near edge structure (XANES), and nuclear magnetic resonance (NMR) spectroscopies, and complementary methods include density functional theory and atomic-resolution aberration-corrected scanning transmission electron microscopy for imaging of individual metal atoms. IR, NMR, XANES, and microscopy data demonstrate the high degrees of uniformity of well-prepared supported species. The characterizations determine the compositions of surface metal complexes and clusters, including the ligands and the metal

  2. A study on the photocatalytic reaction of the metals and organics

    Energy Technology Data Exchange (ETDEWEB)

    Na, Jeong Won; Cho, Young Hyun; Seong, Ki Woong; Kim, Yong Ik; Kang, Hee [Korea Atomic Energy Research Institute, Taejon (Korea, Republic of)

    1995-12-01

    TiO{sub 2}-based photocatalytic reactions in organometallic solution the form of metal(iron and copper)-EDTA complexes in order to examine the metal removal behavior were performed. Photocatalysis technology that have the ability to remove both organics and metal can be applied to efficiently treat the radioactive organic waste in the basis of appropriate process development. 10 tabs., 21 figs. (Author).

  3. A study on the photocatalytic reaction of the metals and organics

    International Nuclear Information System (INIS)

    Na, Jeong Won; Cho, Young Hyun; Seong, Ki Woong; Kim, Yong Ik; Kang, Hee

    1995-12-01

    TiO 2 -based photocatalytic reactions in organometallic solution the form of metal(iron and copper)-EDTA complexes in order to examine the metal removal behavior were performed. Photocatalysis technology that have the ability to remove both organics and metal can be applied to efficiently treat the radioactive organic waste in the basis of appropriate process development. 10 tabs., 21 figs. (Author)

  4. Organic or organometallic template mediated clay synthesis

    Science.gov (United States)

    Gregar, Kathleen C.; Winans, Randall E.; Botto, Robert E.

    1994-01-01

    A method for incorporating diverse Varieties of intercalants or templates directly during hydrothermal synthesis of clays such as hectorite or montmorillonite-type layer-silicate clays. For a hectorite layer-silicate clay, refluxing a gel of silica sol, magnesium hydroxide sol and lithium fluoride for two days in the presence of an organic or organometallic intercalant or template results in crystalline products containing either (a) organic dye molecules such as ethyl violet and methyl green, (b) dye molecules such as alcian blue that are based on a Cu(II)-phthalocyannine complex, or (c) transition metal complexes such as Ru(II)phenanthroline and Co(III)sepulchrate or (d) water-soluble porphyrins and metalloporphyrins. Montmorillonite-type clays are made by the method taught by U.S. Pat. No. 3,887,454 issued to Hickson, Jun. 13, 1975; however, a variety of intercalants or templates may be introduced. The intercalants or templates should have (i) water-solubility, (ii) positive charge, and (iii) thermal stability under moderately basic (pH 9-10) aqueous reflux conditions or hydrothermal pressurized conditions for the montmorillonite-type clays.

  5. Solar cells, structures including organometallic halide perovskite monocrystalline films, and methods of preparation thereof

    KAUST Repository

    Bakr, Osman; Peng, Wei; Wang, Lingfei

    2017-01-01

    Embodiments of the present disclosure provide for solar cells including an organometallic halide perovskite monocrystalline film (see fig. 1.1B), other devices including the organometallic halide perovskite monocrystalline film, methods of making

  6. Theoretical study of the structure and reactivity of lanthanide and actinide based organometallic complexes

    International Nuclear Information System (INIS)

    Barros, N.

    2007-06-01

    In this PhD thesis, lanthanide and actinide based organometallic complexes are studied using quantum chemistry methods. In a first part, the catalytic properties of organo-lanthanide compounds are evaluated by studying two types of reactions: the catalytic hydro-functionalization of olefins and the polymerisation of polar monomers. The reaction mechanisms are theoretically determined and validated, and the influence of possible secondary non productive reactions is envisaged. A second part focuses on uranium-based complexes. Firstly, the electronic structure of uranium metallocenes is analysed. An analogy with the uranyl compounds is proposed. In a second chapter, two isoelectronic complexes of uranium IV are studied. After validating the use of DFT methods for describing the electronic structure and the reactivity of these compounds, it is shown that their reactivity difference can be related to a different nature of chemical bonding in these complexes. (author)

  7. Solar cells, structures including organometallic halide perovskite monocrystalline films, and methods of preparation thereof

    KAUST Repository

    Bakr, Osman M.

    2017-03-02

    Embodiments of the present disclosure provide for solar cells including an organometallic halide perovskite monocrystalline film (see fig. 1.1B), other devices including the organometallic halide perovskite monocrystalline film, methods of making organometallic halide perovskite monocrystalline film, and the like.

  8. Identification of isomers of organometallic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Mbue, Sona Peter; Cho, Kwang Hwi [Dept. of Bioinformatics and Life Science, School of Systems Biomedical Science, Soongsil University,Seoul (Korea, Republic of)

    2015-06-15

    The yaChI is a newly suggested chemical naming system. However, yaChI is a derivative of the IUPAC InChI with a modified algorithm that includes additional layers of chemical structure information. Consequently, yaChI string contains more structure details while preserving the original structure file information and can distinctively identify very closely related compounds reducing the chances of ambiguity in chemical compound databases as opposed to the general SMILES, InChI, and InChIKey. This study examines the relative performances of yaChI, SMILES, InChI, and InChIKey in duplication check for isomers. For simplicity, a small data set of 28 organometallic compounds (structural isomers of Rh-containing compounds) subdivided into three major groups (A, B, and C) based on the number and the type of ligands attached to the center atom was used to study the performances of each encoding scheme in describing chemical structures. SMILES, InChI, and InChIKey were generated using Openbabel and RDkit, whereas yaChI strings were generated with in-house program. Strings generated from SMILES, InChI, and InChIKey though different, resulted to only three unique chemical identifiers, with each belonging to one group indicating the presence of only three unique compounds in the study data. However, yaChI results depicted that all structures in each group are indeed unique and differ among themselves as well as those from other groups, mapping each structure with a unique identifier given a total number of 28 unique structures in the study data. This high perception of yaChI probe justifies its accuracy and reliability in duplication check among closely related compounds especially structures exhibiting stereo properties.

  9. Recent developments in nuclear reaction theories and calculations

    International Nuclear Information System (INIS)

    Gardner, D.G.

    1980-01-01

    A brief review is given of some recent developments in the fields of optical model potentials; level densities; and statistical model, precompound, and direct reaction codes and calculations. Significant developments have occurred in all of these fields since the 1977 Conference on Neutron Cross Sections, which will greatly enhance the ability to calculate high-energy neutron-induced reaction cross sections in the next few years. 11 figures, 3 tables

  10. Organometallic vapor-phase epitaxy theory and practice

    CERN Document Server

    Stringfellow, Gerald B

    1989-01-01

    Here is one of the first single-author treatments of organometallic vapor-phase epitaxy (OMVPE)--a leading technique for the fabrication of semiconductor materials and devices. Also included are metal-organic molecular-beam epitaxy (MOMBE) and chemical-beam epitaxy (CBE) ultra-high-vacuum deposition techniques using organometallic source molecules. Of interest to researchers, students, and people in the semiconductor industry, this book provides a basic foundation for understanding the technique and the application of OMVPE for the growth of both III-V and II-VI semiconductor materials and the

  11. DNA-based asymmetric organometallic catalysis in water

    NARCIS (Netherlands)

    Oelerich, Jens; Roelfes, Gerard

    2013-01-01

    Here, the first examples of DNA-based organometallic catalysis in water that give rise to high enantioselectivities are described. Copper complexes of strongly intercalating ligands were found to enable the asymmetric intramolecular cyclopropanation of alpha-diazo-beta-keto sulfones in water. Up to

  12. Platinum-195 nuclear magnetic resonance of organometallic compounds

    OpenAIRE

    Ursini, Cleber Vinicius

    1997-01-01

    A brief review of 195Pt NMR is presented, focusing organometallic compounds. This article gives initially basic information of NMR processes involving 195Pt nucleus. It is followed by a discussion of the factors which affect the chemical shifts and coupling constants. Finally, some aspects of 195Pt NMR of solids are commented.

  13. Molecular orbital studies of the bonding in heavy element organometallics

    International Nuclear Information System (INIS)

    Bursten, B.E.

    1990-01-01

    This progress report contains highlights of research projects in actinide chemistry. Projects covered are bonding in Np, Pu, and transplutonium organometallic compounds, applications of the discrete variational Xα method to actinide chemistry, ab initio calculations on actinide molecules, and experimental comparisons of organoactinide and organotransition metal chemistry. Also included is brief discussions on budgets, funding, invited papers and invited presentations. (JL)

  14. Local structure of Iridium organometallic catalysts covalently bonded to carbon nanotubes.

    Science.gov (United States)

    Blasco, J.; Cuartero, V.; Subías, G.; Jiménez, M. V.; Pérez-Torrente, J. J.; Oro, L. A.; Blanco, M.; Álvarez, P.; Blanco, C.; Menéndez, R.

    2016-05-01

    Hybrid catalysts based on Iridium N-heterocyclic carbenes anchored to carbon nanotubes (CNT) have been studied by XAFS spectroscopy. Oxidation of CNT yields a large amount of functional groups, mainly hydroxyl groups at the walls and carboxylic groups at the tips, defects and edges. Different kinds of esterification reactions were performed to functionalize oxidized CNT with imidazolium salts. Then, the resulting products were reacted with an Ir organometallic compound to form hybrid catalysts efficient in hydrogen transfer processes. XANES spectroscopy agree with the presence of Ir(I) in these catalysts and the EXAFS spectra detected differences in the local structure of Ir atoms between the initial Ir organometallic compound and the Ir complexes anchored to the CNT. Our results confirm that the halide atom, present in the Ir precursor, was replaced by oxygen from -OH groups at the CNT wall in the first coordination shell of Ir. The lability of this group accounts for the good recyclability and the good efficiency shown by these hybrid catalysts.

  15. Development of nuclear reaction data retrieval system on Meme media

    International Nuclear Information System (INIS)

    Ohbayasi, Yosihide; Masui, Hiroshi; Aoyama, Shigeyoshi; Kato, Kiyoshi; Chiba, Masaki

    2000-01-01

    A newly designed retrieval system of charged particle nuclear reaction data is developed on Meme media architecture. We designed the network-based (client-server) retrieval system. The server system is constructed on a UNIX workstation with a relational database, and the client system is constructed on Microsoft Windows PC using an IntelligentPad software package. The IntelligentPad is currently available as developing Meme media. We will develop the system to realize effective utilization of nuclear reaction data: I. 'Re-production, Re-edit, Re-use', II. 'Circulation, Coordination and Evolution', III. 'Knowledge discovery'. (author)

  16. Development of Bioorthogonal Reactions and Their Applications in Bioconjugation

    Directory of Open Access Journals (Sweden)

    Mengmeng Zheng

    2015-02-01

    Full Text Available Biomolecule labeling using chemical probes with specific biological activities has played important roles for the elucidation of complicated biological processes. Selective bioconjugation strategies are highly-demanded in the construction of various small-molecule probes to explore complex biological systems. Bioorthogonal reactions that undergo fast and selective ligation under bio-compatible conditions have found diverse applications in the development of new bioconjugation strategies. The development of new bioorthogonal reactions in the past decade has been summarized with comments on their potentials as bioconjugation method in the construction of various biological probes for investigating their target biomolecules. For the applications of bioorthogonal reactions in the site-selective biomolecule conjugation, examples have been presented on the bioconjugation of protein, glycan, nucleic acids and lipids.

  17. The reductive decyanation reaction: an overview and recent developments

    Directory of Open Access Journals (Sweden)

    Jean-Marc R. Mattalia

    2017-02-01

    Full Text Available This review presents an overview of the reductive decyanation reaction with a special interest for recent developments. This transformation allows synthetic chemists to take advantages of the nitrile functional group before its removal. Mechanistic details and applications to organic synthesis are provided.

  18. Organometallic compounds of the 2-6 group elements of periodic system as perspective substances for microelectrnics

    International Nuclear Information System (INIS)

    Fedorov, V.A.

    1986-01-01

    Results of investigating methods of preparation and analysis of organometallic compounds (OMC) of the 2B-6B group elements, behaviour of microimpurities in the process of their complete purification, physical-chemical properties for developing rational flowsheets of OMC purification are presented. Results of microimpurities quantitative transition from OMC to gallium arsenide epitaxial layers are presented. Prospects for OMC application in microelectronics are discussed

  19. Surface and Interface Engineering of Organometallic and Two Dimensional Semiconductor

    Science.gov (United States)

    Park, Jun Hong

    For over half a century, inorganic Si and III-V materials have led the modern semiconductor industry, expanding to logic transistor and optoelectronic applications. However, these inorganic materials have faced two different fundamental limitations, flexibility for wearable applications and scaling limitation as logic transistors. As a result, the organic and two dimensional have been studied intentionally for various fields. In the present dissertation, three different studies will be presented with followed order; (1) the chemical response of organic semiconductor in NO2 exposure. (2) The surface and stability of WSe2 in ambient air. (3) Deposition of dielectric on two dimensional materials using organometallic seeding layer. The organic molecules rely on the van der Waals interaction during growth of thin films, contrast to covalent bond inorganic semiconductors. Therefore, the morphology and electronic property at surface of organic semiconductor in micro scale is more sensitive to change in gaseous conditions. In addition, metal phthalocyanine, which is one of organic semiconductor materials, change their electronic property as reaction with gaseous analytes, suggesting as potential chemical sensing platforms. In the present part, the growth behavior of metal phthalocyanine and surface response to gaseous condition will be elucidated using scanning tunneling microscopy (STM). In second part, the surface of layered transition metal dichalcogenides and their chemical response to exposure ambient air will be investigated, using STM. Layered transition metal dichalcogenides (TMDs) have attracted widespread attention in the scientific community for electronic device applications because improved electrostatic gate control and suppression of short channel leakage resulted from their atomic thin body. To fabricate the transistor based on TMDs, TMDs should be exposed to ambient conditions, while the effect of air exposure has not been understood fully. In this part

  20. Organometallic complexes of thiocarbanilides and substituted thiocarbanilides using manganese (II) chloride

    International Nuclear Information System (INIS)

    Babiker, Musa Elaballa Mohamed

    2000-01-01

    Organo-metallic complexes of substituted thiocarbanilide using manganese (II) chloride were prepared, these are: (VIII) 3:3'-Dichloro thiocarbanilide. Manganese (II) chloride. (IX) 3:3'-Dimethyl thiocarbanilide. Manganese (II) chloride. (X) 2:2'-dimethyl thiocarbanilide. Manganese (II) chloride. These compounds are coloured, soluble in most organic solvents, insoluble in water, decomposed by hot solvents. The physical properties of compounds (IX) and (X) were studied by UV and IR spectra, and the physical properties of compound (VIII) were studied by UV, IR, mass spectra and NMR. The molecular weight of the compound (VIII) was determined by three different methods; Rast's camphor method, mass spectra and the nitrogen contents. The stoichiometry of the reaction was found to be 2:1, and the coordination is from sulphur atom more than nitrogen.(Author)

  1. Homologation chemistry with nucleophilic α-substituted organometallic reagents: chemocontrol, new concepts and (solved) challenges.

    Science.gov (United States)

    Castoldi, Laura; Monticelli, Serena; Senatore, Raffaele; Ielo, Laura; Pace, Vittorio

    2018-05-31

    The transfer of a reactive nucleophilic CH2X unit into a preformed bond enables the introduction of a fragment featuring the exact and desired degree of functionalization through a single synthetic operation. The instability of metallated α-organometallic species often poses serious questions regarding the practicability of using this conceptually intuitive and simple approach for forming C-C or C-heteroatom bonds. A deep understanding of processes regulating the formation of these nucleophiles is a precious source of inspiration not only for successfully applying theoretically feasible transformations (i.e. determining how to employ a given reagent), but also for designing new reactions which ultimately lead to the introduction of molecular complexity via short experimental sequences.

  2. Micro-sized organometallic compound of ferrocene as high-performance anode material for advanced lithium-ion batteries

    Science.gov (United States)

    Liu, Zhen; Feng, Li; Su, Xiaoru; Qin, Chenyang; Zhao, Kun; Hu, Fang; Zhou, Mingjiong; Xia, Yongyao

    2018-01-01

    An organometallic compound of ferrocene is first investigated as a promising anode for lithium-ion batteries. The electrochemical properties of ferrocene are conducted by galvanostatic charge and discharge. The ferrocene anode exhibits a high reversible capacity and great cycling stability, as well as superior rate capability. The electrochemical reaction of ferrocene is semi-reversible and some metallic Fe remains in the electrode even after delithiation. The metallic Fe formed in electrode and the stable solid electrolyte interphase should be responsible for its excellent electrochemical performance.

  3. An Organometallic Future in Green and Energy Chemistry?

    Energy Technology Data Exchange (ETDEWEB)

    Crabtree, Robert H

    2011-01-10

    The title topic is reviewed with selected examples taken from recent work, such as: the 'hydrogen borrowing' amine alkylation by alcohols; the dehydrogenative coupling of amine and alcohol to give amide; Ru complexes as solar cell photosensitizers; Ir organometallics as water oxidation catalyst precursors and as OLED emitters; as well as recent hydrogen storage strategies involving catalytic dehydrogenation of ammonia-borane and of organic heterocycles.

  4. Mew organometallic complexes of technetium in different oxidation states

    International Nuclear Information System (INIS)

    Joachim, J.E.

    1993-09-01

    New organometallic compounds of Tc(I), Tc(III) and Tc(VII) were synthesized and their properties examined. These compounds were correlated with their homologous compounds of manganese and rhenium, which were also synthesized by the same route. The molecular and crystal structures of most technetium complexes and of the homologous complexes of manganese and rhenium were determined by single crystal X-ray diffraction. (orig.) [de

  5. Synthesis and X-ray crystal structure of a novel organometallic (µ(3)-oxido)(µ(3)-imido) trinuclear iridium complex

    DEFF Research Database (Denmark)

    Schau-Magnussen, Magnus; Malcho, Phillip; Herbst, Konrad

    2011-01-01

    Reaction of the organometallic aqua ion [Cp*Ir(H(2)O)(3)](2+) with tert-butyl(trimethylsilyl)amine in acetone yielded a novel trinuclear (µ(3)-oxido)(µ(3)-imido)pentamethylcyclopentadienyliridium(iii) complex, [(Cp*Ir)(3)(O)(N(t)Bu)](2+). Single crystal structure analyses show the complex can be ...... that a trinuclear (µ(3)-oxido)(µ(3)-imido) transition metal complex has been structurally characterized....

  6. Binding CO2 from Air by a Bulky Organometallic Cation Containing Primary Amines.

    Science.gov (United States)

    Luo, Yang-Hui; Chen, Chen; Hong, Dan-Li; He, Xiao-Tong; Wang, Jing-Wen; Ding, Ting; Wang, Bo-Jun; Sun, Bai-Wang

    2018-03-21

    The organometallic cation 1 (Fe(bipy-NH 2 ) 3 2+ , bipy-NH 2 = 4,4'-diamino-2,2'-bipyridine), which was constructed in situ in solution, can bind CO 2 from air effectively with a stoichiometric ratio of 1:4 (1/CO 2 ), through the formation of "H-bonded CO 2 " species: [CO 2 -OH-CO 2 ] - and [CO 2 -CO 2 -OH] - . These two species, along with the captured individual CO 2 molecules, connected 1 into a novel 3D (three-dimensional) architecture, that was crystal 1·2(OH - )·4(CO 2 ). The adsorption isotherms, recycling investigations, and the heat capacity of 1 have been investigated; the results revealed that the organometallic cation 1 can be recycled at least 10 times for the real-world CO 2 capture applications. The strategies presented here may provide new hints for the development of new alkanolamine-related absorbents or technologies for CO 2 capture and sequestration.

  7. Development of IAEA nuclear reaction databases and services

    Energy Technology Data Exchange (ETDEWEB)

    Zerkin, V.; Trkov, A. [International Atomic Energy Agency, Dept. of Nuclear Sciences and Applications, Vienna (Austria)

    2008-07-01

    From mid-2004 onwards, the major nuclear reaction databases (EXFOR, CINDA and Endf) and services (Web and CD-Roms retrieval systems and specialized applications) have been functioning within a modern computing environment as multi-platform software, working under several operating systems with relational databases. Subsequent work at the IAEA has focused on three areas of development: revision and extension of the contents of the databases; extension and improvement of the functionality and integrity of the retrieval systems; development of software for database maintenance and system deployment. (authors)

  8. Stereochemistry of organometallic and inorganic compounds

    CERN Document Server

    2012-01-01

    The authors of this fourth volume in the series have reviewed the making and breaking of chemical bonds in a sophisticated manner. In particular, new pressures brought about by environmental concerns, larger demands for the medical and pharmaceutical sectors and economics of the market place are forcing us into demanding greater stereochemical control and better product yields for chemical reactions capable of producing useful products. The chapters are written by leading experts in this area and give excellent overviews of the strengths and weaknesses of the various methodologies.In C

  9. RFQ Reaction Cells for AMS: Developments and Applications

    Directory of Open Access Journals (Sweden)

    Kieser William E.

    2013-12-01

    Full Text Available The use of anion-gas interactions in Radiofrequency Quadrupole (RFQ ion guide reaction cells has been shown to be very effective in the elimination of a number of atomic and molecular isobars which have caused difficulties for Accelerator Mass Spectrometry (AMS measurements [1,2]. This presentation begins with a review of the early work leading to the use of ion-gas reactions and continues with a discussion the recent measurements of the efficacy of this technique, some of which involve fluoride molecular anions. However, the transformation of the equipment used for these proof-of-principle measurements into a system suitable for routine analysis has required attention to aspects of the ion beam transport and gas handling subsystems. For example, the cross sections of the ion-gas reactions, involving both the analyte ion as well as the isobar, are critically dependent on the ion energy which has to be reduced from the ion source energy, usually between 20 and 80 keV, to energies typically in the range of several eV, a task complicated by the energy spread and divergence of beams from AMS sputter sources. With simulations using SIMION 8.1 [3] and tests of promising configurations in a laboratory system, principles for the design of the retarder optics have been developed. These are discussed, along with their planned implementation in a next generation analytical system.

  10. Reaction

    African Journals Online (AJOL)

    abp

    19 oct. 2017 ... Reaction to Mohamed Said Nakhli et al. concerning the article: "When the axillary block remains the only alternative in a 5 year old child". .... Bertini L1, Savoia G, De Nicola A, Ivani G, Gravino E, Albani A et al ... 2010;7(2):101-.

  11. Semiclassical Calculation of Reaction Rate Constants for Homolytical Dissociations

    Science.gov (United States)

    Cardelino, Beatriz H.

    2002-01-01

    There is growing interest in extending organometallic chemical vapor deposition (OMCVD) to III-V materials that exhibit large thermal decomposition at their optimum growth temperature, such as indium nitride. The group III nitrides are candidate materials for light-emitting diodes and semiconductor lasers operating into the blue and ultraviolet regions. To overcome decomposition of the deposited compound, the reaction must be conducted at high pressures, which causes problems of uniformity. Microgravity may provide the venue for maintaining conditions of laminar flow under high pressure. Since the selection of optimized parameters becomes crucial when performing experiments in microgravity, efforts are presently geared to the development of computational OMCVD models that will couple the reactor fluid dynamics with its chemical kinetics. In the present study, we developed a method to calculate reaction rate constants for the homolytic dissociation of III-V compounds for modeling OMCVD. The method is validated by comparing calculations with experimental reaction rate constants.

  12. New twists and turns for actinide chemistry. Organometallic infinite coordination polymers of thorium diazide

    Energy Technology Data Exchange (ETDEWEB)

    Monreal, Marisa J.; Seaman, Lani A.; Goff, George S.; Michalczyk, Ryszard; Morris, David E.; Scott, Brian L.; Kiplinger, Jaqueline L. [Los Alamos National Laboratory, Los Alamos, NM (United States)

    2016-03-07

    Two organometallic 1D infinite coordination polymers and two organometallic monometallic complexes of thorium diazide have been synthesized and characterized. Steric control of these self-assembled arrays, which are dense in thorium and nitrogen, has also been demonstrated: infinite chains can be circumvented by using steric bulk either at the metallocene or with a donor ligand in the wedge.

  13. Recent development of active nanoparticle catalysts for fuel cell reactions

    Energy Technology Data Exchange (ETDEWEB)

    Mazumder, Vismadeb; Lee, Youngmin; Sun, Shouheng [Department of Chemistry Brown University Providence, RI (United States)

    2010-04-23

    This review focuses on the recent advances in the synthesis of nanoparticle (NP) catalysts of Pt-, Pd- and Au-based NPs as well as composite NPs. First, new developments in the synthesis of single-component Pt, Pd and Au NPs are summarized. Then the chemistry used to make alloy and composite NP catalysts aiming to enhance their activity and durability for fuel cell reactions is outlined. The review next introduces the exciting new research push in developing CoN/C and FeN/C as non-Pt catalysts. Examples of size-, shape- and composition-dependent catalyses for oxygen reduction at cathode and formic acid oxidation at anode are highlighted to illustrate the potentials of the newly developed NP catalysts for fuel cell applications. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

  14. Theory of Hydrogen Storage: A New Strategy within Organometallic Chemistry

    Science.gov (United States)

    Zhao, Yufeng

    2006-03-01

    As one of the most vigorous fields in modern chemistry, organometallic chemistry has made vast contributions to a broad variety of technological fields including catalysis, light emitters, molecular devices, liquid crystals, and even superconductivity. Here we show that organometallic chemistry in nanoscale could be the frontier in hydrogen storage. Our study is based on the notion that the 3d transition metal (TM) atoms are superb absorbers for H storage, as their empty d orbital can bind dihydrogen ligands (elongated but non-dissociated H2) with high capacity at nearly ideal binding energy for reversible hydrogen storage. By embedding the TM atoms into a carbon-based nanostructures, high H capacity can be maintained. This presentation contains four parts. First, by comparing the conventional hydrogen storage media, e.g., metal hydrides and carbon-based materials, the general principles for designing hydrogen storage materials are outlined. Second, organometallic buckyballs are studied to demonstrate the novel strategy. The amount of H2 adsorbed on a Sc-coated fullerene, C48B12 [ScH]12, could approach 9 wt%, with binding energies of 30-40 kJ/mol. Third, the method is applied to the transition-metal carbide nanoparticles that have been synthesized experimentally. The similar non-dissociative H2 binding is revealed in our calculation, thereby demonstrating the resilience of the overall mechanism. Moreover, a novel self-catalysis process is identified. In the fourth part, transition-metal functionalization of highly porous carbon-based materials is discussed heuristically to foresee macroscopic media for hydrogen storage. Finally follows the summary and discussion of the remaining challenges to practical hydrogen storage. Work in collaboration with A. C. Dillon, Y.-H. Kim, M. Heben & S. B. Zhang and supported by the U.S. DOE/EERE under contract No. DE-AC36-99GO10337.

  15. Developed Hybrid Model for Propylene Polymerisation at Optimum Reaction Conditions

    Directory of Open Access Journals (Sweden)

    Mohammad Jakir Hossain Khan

    2016-02-01

    Full Text Available A statistical model combined with CFD (computational fluid dynamic method was used to explain the detailed phenomena of the process parameters, and a series of experiments were carried out for propylene polymerisation by varying the feed gas composition, reaction initiation temperature, and system pressure, in a fluidised bed catalytic reactor. The propylene polymerisation rate per pass was considered the response to the analysis. Response surface methodology (RSM, with a full factorial central composite experimental design, was applied to develop the model. In this study, analysis of variance (ANOVA indicated an acceptable value for the coefficient of determination and a suitable estimation of a second-order regression model. For better justification, results were also described through a three-dimensional (3D response surface and a related two-dimensional (2D contour plot. These 3D and 2D response analyses provided significant and easy to understand findings on the effect of all the considered process variables on expected findings. To diagnose the model adequacy, the mathematical relationship between the process variables and the extent of polymer conversion was established through the combination of CFD with statistical tools. All the tests showed that the model is an excellent fit with the experimental validation. The maximum extent of polymer conversion per pass was 5.98% at the set time period and with consistent catalyst and co-catalyst feed rates. The optimum conditions for maximum polymerisation was found at reaction temperature (RT 75 °C, system pressure (SP 25 bar, and 75% monomer concentration (MC. The hydrogen percentage was kept fixed at all times. The coefficient of correlation for reaction temperature, system pressure, and monomer concentration ratio, was found to be 0.932. Thus, the experimental results and model predicted values were a reliable fit at optimum process conditions. Detailed and adaptable CFD results were capable

  16. Highly Potent Antibacterial Organometallic Peptide Conjugates

    NARCIS (Netherlands)

    Albada, Bauke; Metzler-Nolte, Nils

    2017-01-01

    ConspectusResistance of pathogenic bacteria against currently marketed antibiotics is again increasing. To meet the societal need for effective cures, scientists are faced with the challenge of developing more potent but equally bacteria-specific drugs. Currently, most efforts are directed toward

  17. [Development the Japanese of the Self-Compassionate Reactions Inventory].

    Science.gov (United States)

    Miyagawa, Yuki; Taniguchi, Junichi

    2016-04-01

    Self-compassion is defined as being compassionate towards the self in times of suffering, and is composed of the following three components: self-kindness, common humanity, and mindfulness. This article reports the development of the Japanese version of the Self-Compassionate Reactions Inventory (SCRI-J). The SCRI-J measures self-compassion based on the degree to which people choose self-compassionate reactions to 8 hypothetical hardships. Study 1: (N = 179) showed that the SCRI-J had sufficient internal consistency. In terms of its validity, results showed a positive correlation between the SCRI-J and the Japanese version of the Self-Compassion Scale, supporting its concurrent validity. In addition, the SCRI-J was positively correlated with self-esteem and negatively correlated with psychological stress responses. Moreover, the association between the SCRI-J and stress responses remained significant when the effect of self-esteem was removed. In Study 2 (N = 90), the SCRI-J demonstrated high test-retest reliability over 3 weeks. Overall, the present study indicates that the SCRI-J has sufficient reliability and validity as a new scale for self-compassion.

  18. [3+2] Cycloaddition of propargylic alcohols and α-oxo ketene dithioacetals: synthesis of functionalized cyclopentadienes and further application in a Diels-Alder reaction.

    Science.gov (United States)

    Fang, Zhongxue; Liu, Jianquan; Liu, Qun; Bi, Xihe

    2014-07-07

    Cyclopentadienes are valuable intermediates in organic synthesis and also ubiquitous as the Cp ligands in organometallic chemistry. As part of ongoing efforts to develop novel organic reactions that employ functionalized alkynes, a [3+2] cycloaddition of propargylic alcohols and ketene dithioacetals has been developed, which leads to fully substituted 2,5-dialkylthio cyclopentadienes in good to excellent yields. In an unusual dethiolating Diels-Alder reaction, the cyclopentadienes were further reacted with maleimides to afford a family of novel fluorescent polycyclic compounds. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Two-Photon Absorption in Organometallic Bromide Perovskites

    KAUST Repository

    Walters, Grant

    2015-07-21

    Organometallic trihalide perovskites are solution processed semiconductors that have made great strides in third generation thin film light harvesting and light emitting optoelectronic devices. Recently it has been demonstrated that large, high purity single crystals of these perovskites can be synthesized from the solution phase. These crystals’ large dimensions, clean bandgap, and solid-state order, have provided us with a suitable medium to observe and quantify two-photon absorption in perovskites. When CH3NH3PbBr3 single crystals are pumped with intense 800 nm light, we observe band-to-band photoluminescence at 572 nm, indicative of two-photon absorption. We report the nonlinear absorption coefficient of CH3NH3PbBr3 perovskites to be 8.6 cm GW-1 at 800 nm, comparable to epitaxial single crystal semiconductors of similar bandgap. We have leveraged this nonlinear process to electrically autocorrelate a 100 fs pulsed laser using a two-photon perovskite photodetector. This work demonstrates the viability of organometallic trihalide perovskites as a convenient and low-cost nonlinear absorber for applications in ultrafast photonics.

  20. Two-Photon Absorption in Organometallic Bromide Perovskites

    KAUST Repository

    Walters, Grant; Sutherland, Brandon R; Hoogland, Sjoerd; Shi, Dong; Comin, Riccardo; Sellan, Daniel P.; Bakr, Osman; Sargent, Edward H.

    2015-01-01

    Organometallic trihalide perovskites are solution processed semiconductors that have made great strides in third generation thin film light harvesting and light emitting optoelectronic devices. Recently it has been demonstrated that large, high purity single crystals of these perovskites can be synthesized from the solution phase. These crystals’ large dimensions, clean bandgap, and solid-state order, have provided us with a suitable medium to observe and quantify two-photon absorption in perovskites. When CH3NH3PbBr3 single crystals are pumped with intense 800 nm light, we observe band-to-band photoluminescence at 572 nm, indicative of two-photon absorption. We report the nonlinear absorption coefficient of CH3NH3PbBr3 perovskites to be 8.6 cm GW-1 at 800 nm, comparable to epitaxial single crystal semiconductors of similar bandgap. We have leveraged this nonlinear process to electrically autocorrelate a 100 fs pulsed laser using a two-photon perovskite photodetector. This work demonstrates the viability of organometallic trihalide perovskites as a convenient and low-cost nonlinear absorber for applications in ultrafast photonics.

  1. p-type Mesoscopic nickel oxide/organometallic perovskite heterojunction solar cells.

    Science.gov (United States)

    Wang, Kuo-Chin; Jeng, Jun-Yuan; Shen, Po-Shen; Chang, Yu-Cheng; Diau, Eric Wei-Guang; Tsai, Cheng-Hung; Chao, Tzu-Yang; Hsu, Hsu-Cheng; Lin, Pei-Ying; Chen, Peter; Guo, Tzung-Fang; Wen, Ten-Chin

    2014-04-23

    In this article, we present a new paradigm for organometallic hybrid perovskite solar cell using NiO inorganic metal oxide nanocrystalline as p-type electrode material and realized the first mesoscopic NiO/perovskite/[6,6]-phenyl C61-butyric acid methyl ester (PC61BM) heterojunction photovoltaic device. The photo-induced transient absorption spectroscopy results verified that the architecture is an effective p-type sensitized junction, which is the first inorganic p-type, metal oxide contact material for perovskite-based solar cell. Power conversion efficiency of 9.51% was achieved under AM 1.5 G illumination, which significantly surpassed the reported conventional p-type dye-sensitized solar cells. The replacement of the organic hole transport materials by a p-type metal oxide has the advantages to provide robust device architecture for further development of all-inorganic perovskite-based thin-film solar cells and tandem photovoltaics.

  2. Development of the polymerase chain reaction for diagnosis of chancroid.

    Science.gov (United States)

    Chui, L; Albritton, W; Paster, B; Maclean, I; Marusyk, R

    1993-01-01

    The published nucleotide sequences of the 16S rRNA gene of Haemophilus ducreyi were used to develop primer sets and probes for the diagnosis of chancroid by polymerase chain reaction (PCR) DNA amplification. One set of broad specificity primers yielded a 303-bp PCR product from all bacteria tested. Two 16-base probes internal to this sequence were species specific for H. ducreyi when tested with 12 species of the families Pasteurellaceae and Enterobacteriaceae. The two probes in combination with the broad specificity primers were 100% sensitive with 51 strains of H. ducreyi isolated from six continents over a 15-year period. The direct detection of H. ducreyi from 100 clinical specimens by PCR showed a sensitivity of 83 to 98% and a specificity of 51 to 67%, depending on the number of amplification cycles. Images PMID:8458959

  3. Organometallic Routes into the Nanorealms of Binary Fe-Si Phases

    Directory of Open Access Journals (Sweden)

    Teddy M. Keller

    2010-02-01

    Full Text Available The Fe-Si binary system provides several iron silicides that have varied and exceptional material properties with applications in the electronic industry. The well known Fe-Si binary silicides are Fe3Si, Fe5Si3, FeSi, a-FeSi2 and b-FeSi2. While the iron-rich silicides Fe3Si and Fe5Si3 are known to be room temperature ferromagnets, the stoichiometric FeSi is the only known transition metal Kondo insulator. Furthermore, Fe5Si3 has also been demonstrated to exhibit giant magnetoresistance (GMR. The silicon-rich b-FeSi2 is a direct band gap material usable in light emitting diode (LED applications. Typically, these silicides are synthesized by traditional solid-state reactions or by ion beam-induced mixing (IBM of alternating metal and silicon layers. Alternatively, the utilization of organometallic compounds with reactive transition metal (Fe-carbon bonds has opened various routes for the preparation of these silicides and the silicon-stabilized bcc- and fcc-Fe phases contained in the Fe-Si binary phase diagram. The unique interfacial interactions of carbon with the Fe and Si components have resulted in the preferential formation of nanoscale versions of these materials. This review will discuss such reactions.

  4. Single-Site Palladium(II) Catalyst for Oxidative Heck Reaction: Catalytic Performance and Kinetic Investigations

    Energy Technology Data Exchange (ETDEWEB)

    Duan, Hui; Li, Mengyang; Zhang, Guanghui; Gallagher, James R.; Huang, Zhiliang; Sun, Yu; Luo, Zhong; Chen, Hongzhong; Miller, Jeffrey T.; Zou, Ruqiang; Lei, Aiwen; Zhao, Yanli

    2015-01-01

    ABSTRACT: The development of organometallic single-site catalysts (SSCs) has inspired the designs of new heterogeneous catalysts with high efficiency. Nevertheless, the application of SSCs in certain modern organic reactions, such as C-C bond formation reactions, has still been less investigated. In this study, a single-site Pd(II) catalyst was developed, where 2,2'-bipyridine-grafted periodic mesoporous organosilica (PMO) was employed as the support of a Pd(II) complex. The overall performance of the single-site Pd(II) catalyst in the oxidative Heck reaction was then investigated. The investigation results show that the catalyst displays over 99% selectivity for the product formation with high reaction yield. Kinetic profiles further confirm its high catalytic efficiency, showing that the rate constant is nearly 40 times higher than that for the free Pd(II) salt. X-ray absorption spectroscopy reveals that the catalyst has remarkable lifetime and recyclability.

  5. The Suzuki-Miyaura Cross-Coupling Reaction of Halogenated Aminopyrazoles: Method Development, Scope, and Mechanism of Dehalogenation Side Reaction.

    Science.gov (United States)

    Jedinák, Lukáš; Zátopková, Renáta; Zemánková, Hana; Šustková, Alena; Cankař, Petr

    2017-01-06

    The efficient Suzuki-Miyaura cross-coupling reaction of halogenated aminopyrazoles and their amides or ureas with a range of aryl, heteroaryl, and styryl boronic acids or esters has been developed. The method allowed incorporation of problematic substrates: aminopyrazoles bearing protected or unprotected pyrazole NH, as well as the free amino or N-amide group. Direct comparison of the chloro, bromo, and iodopyrazoles in the Suzuki-Miyaura reaction revealed that Br and Cl derivatives were superior to iodopyrazoles, as a result of reduced propensity to dehalogenation. Moreover, the mechanism and factors affecting the undesired dehalogenation side reaction were revealed.

  6. Development and Application of Ligand-Exchange Reaction Method ...

    African Journals Online (AJOL)

    Purpose: This paper presents an improved kinetic-spectrophotometric procedure for determining clonazepam (CZP) in pharmaceutical formulations and human serum. Methods: The method is based on ligand-exchange reaction. The reaction was followed spectrophotometrically by measuring the rate of change of ...

  7. Naturally Efficient Emitters: Luminescent Organometallic Complexes Derived from Natural Products

    Science.gov (United States)

    Zhang, Wen-Hua; Young, David J.

    2013-08-01

    Naturally occurring molecules offer intricate structures and functionality that are the basis of modern medicinal chemistry, but are under-represented in materials science. Herein, we review recent literature describing the use of abundant and relatively inexpensive, natural products for the synthesis of ligands for luminescent organometallic complexes used for organic light emitting diodes (OLEDs) and related technologies. These ligands are prepared from the renewable starting materials caffeine, camphor, pinene and cinchonine and, with the exception of caffeine, impart performance improvements to the emissive metal complexes and resulting OLED devices, with emission wavelengths that span the visible spectrum from blue to red. The advantages of these biologically-derived molecules include improved solution processibility and phase homogeneity, brighter luminescence, higher quantum efficiencies and lower turn-on voltages. While nature has evolved these carbon-skeletons for specific purposes, they also offer some intriguing benefits in materials science and technology.

  8. Development of Fluorous Lewis Acid-Catalyzed Reactions

    Directory of Open Access Journals (Sweden)

    Joji Nishikido

    2006-08-01

    Full Text Available Organic synthetic methodology in the 21st century aims to conform to the principles of green sustainable chemistry (GSC and we may expect that in the future, the realization of GSC will be an important objective for chemical industries. An important aim of synthetic organic chemistry is to implement waste-free and environmentally-benign industrial processes using Lewis acids as versatile as aluminum choride. A key technological objective of our work in this area has been to achieve a “catalyst recycling system that utilizes the high activity and structural features of fluorous Lewis acid catalysts”. Thus, we have developed a series of novel fluorous Lewis acid catalysts, namely the ytterbium(III, scandium(III, tin(IV or hafnium(IV bis(perfluoroalkanesulfonylamides or tris(perfluoro- alkanesulfonylmethides. Our catalysts are recyclable and effective for acylations of alcohols and aromatics, Baeyer-Villiger reactions, direct esterifications and transesterifications in a fluorous biphasic system (FBS, in supercritical carbon dioxide and on fluorous silica gel supports.

  9. Labeling of thymidine analog with an organometallic complex of technetium-99m for diagnostic of cancer: radiochemical and biological evaluation

    International Nuclear Information System (INIS)

    Santos, Rodrigo Luis Silva Ribeiro

    2007-01-01

    Thymidine analogs have been labeled with different radioisotopes due to their potential in monitoring the uncontrollable cell proliferation. Considering that the radioisotopes technetium-99m still keep a privileged position as a marker due to its chemical and nuclear properties, this dissertation was constituted by the developed of a new technique of labeling of thymidine analog with 99m Tc, by means of the organometallic complex. The aims of this research were: synthesis of the organometallic complex technetium-99m-carbonyl, thymidine labeling with this precursor, evaluation of stability, and radiochemical e biological evaluation with healthy and tumor-bearing animals. The preparation of the organometallic precursor, using the CO gas, was easily achieved, as well as the labeling of thymidine with this precursor, resulting itself a radiochemical pureness of ≥ 97% and ≥ 94%, respectively. Chromatography systems with good levels of trustworthiness were used, ensuring the qualification and quantification of the radiochemical samples. The result of in vitro testing of lipophilicity disclosed that the radiolabeled complex is hydrophilic, with a partition coefficient (log P) of -1.48. The precursor complex and the radiolabeled have good radiochemical stability up to 6 h in room temperature. The cysteine and histidine challenge indicated losses between 8 and 1 1 % for concentrations until 300 mM. The biodistribution assay in healthy mice revealed rapid blood clearance and low uptake by general organs with renal and hepatobiliary excretion. The tumor concentration was low with values of 0.28 and 0.18 %ID/g for lung and breast cancer, respectively. The results imply more studies in other tumor models or the modification of the structure of the organic molecule that act like ligand. (author)

  10. DFT and time-resolved IR investigation of electron transfer between photogenerated 17- and 19-electron organometallic radicals

    Energy Technology Data Exchange (ETDEWEB)

    Cahoon, James B.; Kling, Matthias F.; Sawyer, Karma R.; Andersen, Lars K.; Harris, Charles B.

    2008-04-30

    The photochemical disproportionation mechanism of [CpW(CO){sub 3}]{sub 2} in the presence of Lewis bases PR{sub 3} was investigated on the nano- and microsecond time-scales with Step-Scan FTIR time-resolved infrared spectroscopy. 532 nm laser excitation was used to homolytically cleave the W-W bond, forming the 17-electron radicals CpW(CO){sub 3} and initiating the reaction. With the Lewis base PPh{sub 3}, disproportionation to form the ionic products CpW(CO){sub 3}PPh{sub 3}{sup +} and CpW(CO){sub 3}{sup -} was directly monitored on the microsecond time-scale. Detailed examination of the kinetics and concentration dependence of this reaction indicates that disproportionation proceeds by electron transfer from the 19-electron species CpW(CO){sub 3}PPh{sub 3} to the 17-electron species CpW(CO){sub 3}. This result is contrary to the currently accepted disproportionation mechanism which predicts electron transfer from the 19-electron species to the dimer [CpW(CO){sub 3}]{sub 2}. With the Lewis base P(OMe){sub 3} on the other hand, ligand substitution to form the product [CpW(CO){sub 2}P(OMe){sub 3}]{sub 2} is the primary reaction on the microsecond time-scale. Density Functional Theory (DFT) calculations support the experimental results and suggest that the differences in the reactivity between P(OMe){sub 3} and PPh{sub 3} are due to steric effects. The results indicate that radical-to-radical electron transfer is a previously unknown but important process for the formation of ionic products with the organometallic dimer [CpW(CO){sub 3}]{sub 2} and may also be applicable to the entire class of organometallic dimers containing a single metal-metal bond.

  11. Development of a novel fingerprint for chemical reactions and its application to large-scale reaction classification and similarity.

    Science.gov (United States)

    Schneider, Nadine; Lowe, Daniel M; Sayle, Roger A; Landrum, Gregory A

    2015-01-26

    Fingerprint methods applied to molecules have proven to be useful for similarity determination and as inputs to machine-learning models. Here, we present the development of a new fingerprint for chemical reactions and validate its usefulness in building machine-learning models and in similarity assessment. Our final fingerprint is constructed as the difference of the atom-pair fingerprints of products and reactants and includes agents via calculated physicochemical properties. We validated the fingerprints on a large data set of reactions text-mined from granted United States patents from the last 40 years that have been classified using a substructure-based expert system. We applied machine learning to build a 50-class predictive model for reaction-type classification that correctly predicts 97% of the reactions in an external test set. Impressive accuracies were also observed when applying the classifier to reactions from an in-house electronic laboratory notebook. The performance of the novel fingerprint for assessing reaction similarity was evaluated by a cluster analysis that recovered 48 out of 50 of the reaction classes with a median F-score of 0.63 for the clusters. The data sets used for training and primary validation as well as all python scripts required to reproduce the analysis are provided in the Supporting Information.

  12. Recent developments in biocatalysis in multiphasic ionic liquid reaction systems.

    Science.gov (United States)

    Meyer, Lars-Erik; von Langermann, Jan; Kragl, Udo

    2018-06-01

    Ionic liquids are well known and frequently used 'designer solvents' for biocatalytic reactions. This review highlights recent achievements in the field of multiphasic ionic liquid-based reaction concepts. It covers classical biphasic systems including supported ionic liquid phases, thermo-regulated multi-component solvent systems (TMS) and polymerized ionic liquids. These powerful concepts combine unique reaction conditions with a high potential for future applications on a laboratory and industrial scale. The presence of a multiphasic system simplifies downstream processing due to the distribution of the catalyst and reactants in different phases.

  13. Writing nanopatterns with electrochemical oxidation on redox responsive organometallic multilayers by AFM

    NARCIS (Netherlands)

    Song, Jing; Hempenius, Mark A.; Chung, H.J.; Vancso, Gyula J.

    2015-01-01

    Nanoelectrochemical patterning of redox responsive organometallic poly(ferrocenylsilane) (PFS) multilayers is demonstrated by electrochemical dip pen lithography (EDPN). Local electrochemical oxidation and Joule heating of PFS multilayers from the tip are considered as relevant mechanisms related to

  14. Mechanistic interpretation of glass reaction: Input to kinetic model development

    International Nuclear Information System (INIS)

    Bates, J.K.; Ebert, W.L.; Bradley, J.P.; Bourcier, W.L.

    1991-05-01

    Actinide-doped SRL 165 type glass was reacted in J-13 groundwater at 90 degree C for times up to 278 days. The reaction was characterized by both solution and solid analyses. The glass was seen to react nonstoichiometrically with preferred leaching of alkali metals and boron. High resolution electron microscopy revealed the formation of a complex layer structure which became separated from the underlying glass as the reaction progressed. The formation of the layer and its effect on continued glass reaction are discussed with respect to the current model for glass reaction used in the EQ3/6 computer simulation. It is concluded that the layer formed after 278 days is not protective and may eventually become fractured and generate particulates that may be transported by liquid water. 5 refs., 5 figs. , 3 tabs

  15. New twists and turns for actinide chemistry: organometallic infinite coordination polymers of thorium diazide

    Energy Technology Data Exchange (ETDEWEB)

    Monreal, Marisa J.; Seaman, Lani A.; Goff, George S.; Michalczyk, Ryszard; Morris, David E.; Scott, Brian L.; Kiplinger, Jaqueline L. [Los Alamos National Laboratory, Los Alamos, NM (United States)

    2016-03-07

    Two organometallic 1D infinite coordination polymers and two organometallic monometallic complexes of thorium diazide have been synthesized and characterized. Steric control of these self-assembled arrays, which are dense in thorium and nitrogen, has also been demonstrated: infinite chains can be circumvented by using steric bulk either at the metallocene or with a donor ligand in the wedge. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  16. Phosphane-Based Cyclodextrins as Mass Transfer Agents and Ligands for Aqueous Organometallic Catalysis

    Directory of Open Access Journals (Sweden)

    Eric Monflier

    2012-11-01

    Full Text Available The replacement of hazardous solvents and the utilization of catalytic processes are two key points of the green chemistry movement, so aqueous organometallic catalytic processes are of great interest in this context. Nevertheless, these processes require not only the use of water-soluble ligands such as phosphanes to solubilise the transition metals in water, but also the use of mass transfer agents to increase the solubility of organic substrates in water. In this context, phosphanes based on a cyclodextrin skeleton are an interesting alternative since these compounds can simultaneously act as mass transfer agents and as coordinating species towards transition metals. For twenty years, various cyclodextrin-functionalized phosphanes have been described in the literature. Nevertheless, while their coordinating properties towards transition metals and their catalytic properties were fully detailed, their mass transfer agent properties were much less discussed. As these mass transfer agent properties are directly linked to the availability of the cyclodextrin cavity, the aim of this review is to demonstrate that the nature of the reaction solvent and the nature of the linker between cyclodextrin and phosphorous moieties can deeply influence the recognition properties. In addition, the impact on the catalytic activity will be also discussed.

  17. Chromocene in porous polystyrene: an example of organometallic chemistry in confined spaces.

    Science.gov (United States)

    Estephane, Jane; Groppo, Elena; Vitillo, Jenny G; Damin, Alessandro; Lamberti, Carlo; Bordiga, Silvia; Zecchina, Adriano

    2009-04-07

    In this work, we present an innovative approach to investigate the structure and the reactivity of a molecularly dispersed organometallic compound. The poly(4-ethylstyrene-co-divinylbenzene) microporous system (PS) is used as "solid solvent" able to molecularly disperse CrCp2, allowing: (i) its full characterization by means of spectroscopic techniques; (ii) the pressure and temperature dependent study of its interaction towards simple molecules like CO freely diffusing through the pores; (iii) the accurate determination of the reaction enthalpies by both direct microcalorimetric measurements and by an indirect spectroscopic approach. The experimental results are compared with quantum-mechanical calculations adopting the DFT approximation with two different functionals (namely BP86 and B3-LYP), showing the limitations and the potentialities of DFT methods in predicting the properties of open shell systems. It is concluded that modern DFT methods are able to give a coherent view of the vibrational properties of the CrCp2 molecule (and of the complex formed upon CO adsorption) that well match the experimental results, while the energetic predictions should be taken with care as they are significantly dependent on the functionals used.

  18. New organometallic salts as precursors for the functionalization of carbon nanotubes with metallic nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Alonso-Nunez, G., E-mail: galonso@cnyn.unam.mx; Garza, L. Morales de la; Rogel-Hernandez, E.; Reynoso, E. [Universidad Nacional Autonoma de Mexico, Centro de Nanociencias y Nanotecnologia (Mexico); Licea-Claverie, A.; Felix-Navarro, R. M. [Instituto Tecnologico de Tijuana, Centro de Graduados e Investigacion (Mexico); Berhault, G. [UMR 5256 CNRS-Universite de Lyon, Institut de Recherches sur la Catalyse et l' Environnement de Lyon (France); Paraguay-Delgado, F. [Centro de Investigacion en Materiales Avanzados S. C. (Mexico)

    2011-09-15

    New organometallic salts were synthesized in aqueous solution and were used as precursors for the functionalization of carbon nanotubes (CNT) by metallic nanoparticles. The precursors were obtained by reaction between HAuCl{sub 4}, (NH{sub 4}){sub 2}PtCl{sub 6}, (NH{sub 4}){sub 2}PdCl{sub 6}, or (NH{sub 4}){sub 3}RhCl{sub 6} with cetyltrimethylammonium bromide (CTAB). The as-obtained (CTA){sub n}Me{sub x}Cl{sub y} salts (with Me = Au, Pt, Pd, Rh) were characterized by Fourier-transform infra-red (FTIR) spectroscopy, {sup 1}H nuclear magnetic resonance (NMR) spectroscopy, and thermogravimetric analysis. These precursors were then used to synthesize metallic nanoparticles of Au, Pt, Pd, and Rh over multiwalled carbon nanotubes (MWCNT). Characterization by scanning transmission electron microscopy (STEM) and thermogravimetric analysis under air reveals that the CNT-supported catalysts exhibit high loading and good dispersion of the metallic nanoparticles with small average particle sizes. The present preparation procedure therefore allows obtaining high densities of small metallic nanoparticles at the surface of MWCNT.

  19. Recent developments in semiclassical mechanics: eigenvalues and reaction rate constants

    International Nuclear Information System (INIS)

    Miller, W.H.

    1976-04-01

    A semiclassical treatment of eigenvalues for a multidimensional non-separable potential function and of the rate constant for a chemical reaction with an activation barrier is presented. Both phenomena are seen to be described by essentially the same semiclassical formalism, which is based on a construction of the total Hamiltonian in terms of the complete set of ''good'' action variables (or adiabatic invariants) associated with the minimum in the potential energy surface for the eigenvalue case, or the saddle point in the potential energy surface for the case of chemical reaction

  20. Group IB organometallic Chemistry XXIII. Reaction of Ar4Cu2Li2 with RhI complexes; Synthesis of 2-[(dimethylamino)methyl] phenylrhodium dicarbon monoxide and electron-transfer induced selective formation of diarylketones ArC(O)Ar

    NARCIS (Netherlands)

    Koten, G. van; Jastrzebski, J.T.B.H.; Noltes, J.G.

    1978-01-01

    The 1/1 reaction of (2-Me{2}NCH{2}C{6}H{4}){4}M{2}Li{2} (M = Cu or Au) with (CO){2}ClRh-dimer affords (2-Me{2}NCH{2}C{6}H{4}M){n} and the novel 2-Me{2}NCH{2}C{6}H{4}Rh(CO){2}. In contrast, the reaction of (x-tolyl){4}M{2}Li{2} (x = 2, M = Cu or Au) under a CO atmosphere results in the formation of

  1. Organometallic Gold(III) Complexes Similar to Tetrahydroisoquinoline Induce ER-Stress-Mediated Apoptosis and Pro-Death Autophagy in A549 Cancer Cells.

    Science.gov (United States)

    Huang, Ke-Bin; Wang, Feng-Yang; Tang, Xiao-Ming; Feng, Hai-Wen; Chen, Zhen-Feng; Liu, Yan-Cheng; Liu, You-Nian; Liang, Hong

    2018-04-26

    Agents inducing both apoptosis and autophagic death can be effective chemotherapeutic drugs. In our present work, we synthesized two organometallic gold(III) complexes harboring C^N ligands that structurally resemble tetrahydroisoquinoline (THIQ): Cyc-Au-1 (AuL 1 Cl 2 , L 1 = 3,4-dimethoxyphenethylamine) and Cyc-Au-2 (AuL 2 Cl 2 , L 2 = methylenedioxyphenethylamine). In screening their in vitro activity, we found both gold complexes exhibited lower toxicity, lower resistance factors, and better anticancer activity than those of cisplatin. The organometallic gold(III) complexes accumulate in mitochondria and induce elevated ROS and an ER stress response through mitochondrial dysfunction. These effects ultimately result in simultaneous apoptosis and autophagy. Importantly, compared to cisplatin, Cyc-Au-2 exhibits lower toxicity and better anticancer activity in a murine tumor model. To the best of our knowledge, Cyc-Au-2 is the first organometallic Au(III) compound that induces apoptosis and autophagic death. On the basis of our results, we believe Cyc-Au-2 to be a promising anticancer agent or lead compound for further anticancer drug development.

  2. Synthesis and structure determination of a stable organometallic uranium(V) imine complex and its isolobal anionic U(IV)-ate complex

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, M.; Botoshanskii, M.; Eisen, M.S. [Schulich Faculty of Chemistry, and Institute of Catalysis Science and Technology, Technion Israel Institute of Technology, Haifa (Israel); Bannenberg, Th.; Tamm, M. [Institut fur Anorganische und Analytische Chemie, Technische Universitat Braunschweig (Germany)

    2010-06-15

    The reaction of one equivalent of Cp*{sub 2}UCl{sub 2} with 2-(trimethylsilyl-imino)-1,3-di-tert-butyl-imidazoline in boiling toluene afforded a one electron oxidation of the uranium metal and the opening of the N-heterocyclic ring, resulting in the formation of an organometallic uranium(V) imine complex. This complex crystallized with one molecule of toluene in the unit cell, and its solid-state structure was determined by X-ray diffraction analysis. When the same reaction was performed in perdeuterated toluene, a myriad of organometallic complexes were obtained, however, when equimolar amounts of water were used in toluene, the same complex was obtained, and its solid state characterization shows two independent molecules in the unit cell with an additional water molecule. For comparison of the geometric parameters, the corresponding isolobal anionic uranium(IV) complex [Cp*{sub 2}UCl{sub 3}]{sup -} was synthesized by the reaction of Cp*{sub 2}UCl{sub 2} with 1,3-di-tert-butyl-imidazolium chloride, and the resulting U(IV)-ate complex was characterized by X-ray diffraction analysis. (authors)

  3. Development of various reaction abilities and their relationships with favorite play activities in preschool children.

    Science.gov (United States)

    Miyaguchi, Kazuyoshi; Demura, Shinich; Sugiura, Hiroki; Uchiyama, Masanobu; Noda, Masahiro

    2013-10-01

    This study examines the development of various reaction movements in preschool children and the relationship between reaction times and favorite play activities. The subjects were 167 healthy preschool children aged 4-6 (96 boys and 71 girls). This study focused on the reaction times of the upper limbs (reaction 1: release; reaction 2: press) and the whole body (reaction 3: forward jump). The activities frequently played in preschools are largely divided into dynamic play activities (tag, soccer, gymnastics set, dodge ball, and jump rope) and static play activities (drawing, playing house, reading, playing with sand, and building blocks). The subjects chose 3 of 10 cards picturing their favorite play activities, depicting 10 different activities. All intraclass correlation coefficients of measured reaction times were high (0.73-0.79). In addition, each reaction time shortened with age. Reaction 1 showed a significant and low correlation with reaction 3 (r = 0.37). The effect size of the whole body reaction time was the largest. Whole body reaction movement, which is largely affected by the exercise output function, develops remarkably in childhood. Children who liked "tag" were faster in all reaction times. The children who chose "soccer" were faster in reactions 2 and 3. In contrast, children who liked "playing house" tended to have slower reaction times. Dynamic activities, such as tag and soccer, promote development of reaction speed and agility in movements involving the whole body. Preschool teachers and physical educators should re-examine the effect of tag and use it periodically as one of the exercise programs to avoid unexpected falls and injuries in everyday life.

  4. Recent developments in research on catalytic reaction networks

    Directory of Open Access Journals (Sweden)

    Roberto Serra

    2013-09-01

    Full Text Available Over the last years, analyses performed on a stochastic model of catalytic reaction networks have provided some indications about the reasons why wet-lab experiments hardly ever comply with the phase transition typically predicted by theoretical models with regard to the emergence of collectively self-replicating sets of molecule (also defined as autocatalytic sets, ACSs, a phenomenon that is often observed in nature and that is supposed to have played a major role in the emergence of the primitive forms of life. The model at issue has allowed to reveal that the emerging ACSs are characterized by a general dynamical fragility, which might explain the difficulty to observe them in lab experiments. In this work, the main results of the various analyses are reviewed, with particular regard to the factors able to affect the generic properties of catalytic reactions network, for what concerns, not only the probability of ACSs to be observed, but also the overall activity of the system, in terms of production of new species, reactions and matter.

  5. [Development of boomerang-type intramolecular cascade reactions and application to natural product synthesis].

    Science.gov (United States)

    Takasu, K

    2001-12-01

    Intramolecular cascade reaction has received much attention as a powerful methodology to construct a polycyclic framework in organic synthesis. We have been developing "boomerang-type cascade reaction" to construct a variety of polycyclic skeletons efficiently. In the above reactions, a nucleophilic function of substrates changes the character into an electrophile after the initial reaction, and the electrophilic group acts as a nucleophile in the second reaction. That is, the reaction center stepwise moves from one functional group back to the same one via other functional groups. The stream of the electron concerning the cascade reaction is like a locus of boomerang. We show here three different boomerang-type reactions via ionic species or free radicals. 1) Diastereoselective Michael-aldol reaction based on the chiral auxiliary method and enantioselective Michael-aldol reaction by the use of external chiral sources. 2) Short and efficient total syntheses of longifolane sesquiterpenes utilizing intramolecular double Michael addition as a key step. 3) Development of boomerang-type radical cascade reaction of halopolyenes to construct terpenoid skeletons and its regioselectivity.

  6. Generation of Well-Defined Pairs of Silylamine on Highly Dehydroxylated SBA-15: Application to the Surface Organometallic Chemistry of Zirconium

    KAUST Repository

    Azzi, Joachim

    2012-11-01

    Design of a new well-defined surface organometallic species [O-(=Si–NH)2Zr(IV)Np2] has been obtained by reaction of tetraneopentyl zirconium (ZrNp4) on SBA-15 surface displaying mainly silylamine pairs [O-(=Si–NH2)2]. These surface species have been achieved by an ammonia treatment of a highly dehydroxylated SBA-15 at 1000°C (SBA-151000). This support is known to contain mainly strained reactive siloxane bridges (≡Si-O-Si≡)[1] along with a small amount of isolated plus germinal silanols =Si(OH)2. Chemisorption of ammonia occurs primarily by opening these siloxane bridges[2] to generate silanol/silylamine pairs [O-(=Si–NH2)(=SiOH)] followed by substitution of the remaining silanol. Further treatment using hexamethyldisilazane (HMDS) results in the protection of the isolated remaining silanol groups by formation of ≡Si-O-SiMe3 and =Si(OSiMe3)2 but leaves ≡SiNH2 untouched. After reaction of this functionalized surface with ZrNp4, this latter displays mainly a bi-podal zirconium neopentyl organometallic complex [O-(=Si–NH)2Zr(IV)Np2] which has been fully characterized by diverse methods such as infrared transmission spectroscopy, magic angle spinning solid state nuclear magnetic resonance, surface elemental analysis, small angle X-ray powder diffraction (XRD), nitrogen adsorption and energy filtered transmission electron microscopy (EFTEM). These different characterization tools unambiguously prove that the zirconium organometallic complex reacts mostly with silylamine pairs to give a bi-podal zirconium bis-neopentyl complex, uniformly distributed into the channels of SBA-151000. Therefore this new material opens a new promising research area in Surface Organometallic Chemistry which, so far, was dealing mainly with O containing surface. It is expected that vicinal amine functions may play a very different role as compared with classical inorganic supports. Given the importance in the last decades of N containing ligands in catalysis, one may expect

  7. Horizons of organic and organoelemental chemistry. 7. All-Russian conference on organometallic chemistry. Summaries of reports. V. 2

    International Nuclear Information System (INIS)

    1999-01-01

    Abstracts of the seventh All-Russian conference on organometallic chemistry are presented. The main part of reports are devoted to the synthesis of organometallic compounds with assigned properties of rare earths, transition elements and other metals. Data on molecular structure, chemical and electrochemical properties of these compounds are presented

  8. Natural History of Food-Triggered Atopic Dermatitis and Development of Immediate Reactions in Children.

    Science.gov (United States)

    Chang, Angela; Robison, Rachel; Cai, Miao; Singh, Anne Marie

    2016-01-01

    Case reports suggest that children with food-triggered atopic dermatitis (AD) on elimination diets may develop immediate reactions on accidental ingestion or reintroduction of an avoided food. The objective of this study was to systematically study the incidence and risk factors associated with these immediate reactions. A retrospective chart review of 298 patients presenting to a tertiary-care allergy-immunology clinic based on concern for food-triggered AD was performed. Data regarding triggering foods, laboratory testing, and clinical reactions were collected prospectively from the initial visit. Food-triggered AD was diagnosed by an allergist-immunologist with clinical evaluation and laboratory testing. We identified immediate reactions as any reaction to a food for which there was evidence of sIgE and for which patients developed timely allergic signs and symptoms. Differences between children with and without new immediate reactions were determined by a Mann-Whitney, χ(2), or Fisher's exact test as appropriate. A total of 19% of patients with food-triggered AD and no previous history of immediate reactions developed new immediate food reactions after initiation of an elimination diet. Seventy percent of reactions were cutaneous but 30% were anaphylaxis. Cow's milk and egg were the most common foods causing immediate-type reactions. Avoidance of a food was associated with increased risk of developing immediate reactions to that food (P food. A significant number of patients with food-triggered AD may develop immediate-type reactions. Strict elimination diets need to be thoughtfully prescribed as they may lead to decreased oral tolerance. Copyright © 2015 American Academy of Allergy, Asthma & Immunology. Published by Elsevier Inc. All rights reserved.

  9. Development of a utility system for charged particle nuclear reaction data by using intelligentPad

    International Nuclear Information System (INIS)

    Aoyama, Shigeyoshi; Ohbayashi, Yoshihide; Masui, Hiroshi; Kato, Kiyoshi; Chiba, Masaki

    2000-01-01

    We have developed a utility system, WinNRDF2, for a nuclear charged particle reaction data of NRDF (Nuclear Reaction Data File) on the IntelligentPad architecture. By using the system, we can search the experimental data of a charged particle reaction of NRDF. Furthermore, we also see the experimental data by using graphic pads which was made through the CONTIP project. (author)

  10. Theoretical Study of Indium Compounds of Interest for Organometallic Chemical Vapor Deposition

    Science.gov (United States)

    Cardelino, B. H.; Moore, C. E.; Cardelino, C. A.; Frazier, D. O.; Backmann, K. J.

    2000-01-01

    The structural. electronic and therinochemical properties of indium compounds which are of interest in halide transport and organometallic chemical vapor deposition processes have been studied by ab initio and statistical mechanics methods. The compounds reported include: indium halides and hydrides (InF, InCl, InCl3, InH, InH2, InH3); indium clusters (In2, In3); methylindium, dimethylindium, and their hydrogen derivatives [In(CH3), In(CH3)H, In(CH3)H2, In(CH3)2, In(CH3)2H]; dimethyl-indium dimer [In2(CH3)4], trimethyl-indium [In(CH3)3]; dehydrogenated methyl, dimethyl and trimethylindium [In(CH3)2CH2, In(CH3)CH2, In(CH2)], trimethylindium adducts with ammonia, trimethylamine and hydrazine [(CH3)3In:NH3, (CH3)3In:N(CH3)3, (CH3)3In:N(H2)N(H2)]; dimethylamino-indium and methylimino-indium [In(CH3)2(NH2), In(CH3)(NH)]; indium nitride and indium nitride dimer (InN, In2N2), indium phosphide, arsenide and antimonide ([InP, InAs, InSb). The predicted electronic properties are based on density functional theory calculations; the calculated thermodynamic properties are reported following the format of the JANAF (Joint Army, Navy, NASA, Air Force) Tables. Equilibrium compositions at two temperatures (298 and 1000 K) have been analyzed for groups of competing simultaneous reactions.

  11. Recent developments in heavy ion deep inelastic reactions

    International Nuclear Information System (INIS)

    Lefort, M.; Ngo, C.

    1979-01-01

    In the first attempts to understand deep inelastic reactions (DIR), the attention was focussed on the dissipation mechanism and simple classical models have been elaborated to describe the dynamical evolution of the mean values of the macroscopic variables. Very early, it has also been realized that the distributions around the mean values were rather broad and that this might reveal the importance of fluctuations which are mainly expected to be statistical fluctuations. In section II, we shall only say a few words about the two classes of models: dynamical evolution and diffusion model, which have been described many time. Each of them accounts for a particular aspect of the DI phenomena. It appeared worthwhile to unify these approaches and to treat on the same footing both dissipation and statistical fluctuations. Microscopic attempts have succeeded in understanding the evolution of the macroscopic degrees which are slow as compared to the intrinsic degrees. In section III we shall briefly discuss them and in section IV we will more extensively see how they can be applied to the computation of multidifferential cross section for DIR. (autho.)

  12. Sodium-concrete reactions experiments and code development

    International Nuclear Information System (INIS)

    Casselman, C.; Malet, J.C.; Dufresne, J.; Bolvin, M.

    1988-01-01

    Hypothesis of hot sodium leak in a fast breeder reactor implies, for the safety organism to consider spillage of sodium on concrete. This safety analysis involves the understanding of sodium-concrete reactions, the knowledge of their consequences and to test the choiced preventive solutions. In association with EDF, the nuclear safety department had carried out an extensive experimental program, the different parts of which are connected with each aspect of this problem: - firstly, interaction between sodium and bare surface of usual concrete; - secondly, the case of a sodium spillage on a concrete surface covered with a defected liner; - thirdly, special concrete tests for a comparison with usual concrete behavior, in direct contact with hot sodium; - at last, a test which concerns a new design with a layer of the selected concrete protected with a defected liner. On the same time, theoretical work leads to elaborate a physical model to describe temporal evolution of thermal and chemical decomposition of a concrete slab under hot sodium action. SORBET-REBUS system will use quoted above test results to its validation

  13. Development of a redox-free Mitsunobu reaction exploiting phosphine oxides as precursors to dioxyphosphoranes.

    Science.gov (United States)

    Tang, Xiaoping; Chapman, Charlotte; Whiting, Matthew; Denton, Ross

    2014-07-14

    The development of the first redox-free protocol for the Mitsunobu reaction is described. This has been achieved by exploiting triphenylphosphine oxide--the unwanted by-product in the conventional Mitsunobu reaction--as the precursor to the active P(V) coupling reagent. Multinuclear NMR studies are consistent with hydroxyl activation via an alkoxyphosphonium salt.

  14. Development of utility system of charged particle Nuclear Reaction Data on Unified Interface

    International Nuclear Information System (INIS)

    Aoyama, Shigeyoshi; Ohbayashi, Yosihide; Kato, Kiyoshi; Masui, Hiroshi; Ohnishi, Akira; Chiba, Masaki

    1999-01-01

    We have developed a utility system, WinNRDF, for a nuclear charged particle reaction data of NRDF (Nuclear Reaction Data File) on a unified interface of Windows95, 98/NT. By using the system, we can easily search the experimental data of a charged particle reaction in NRDF and also see the graphic data on GUI (Graphical User Interface). Furthermore, we develop a mechanism of making a new index of keywords in order to include the time developing character of the NRDF database. (author)

  15. Recent developments in gold-catalyzed cycloaddition reactions

    Directory of Open Access Journals (Sweden)

    Fernando López

    2011-08-01

    Full Text Available In the last years there have been extraordinary advances in the development of gold-catalyzed cycloaddition processes. In this review we will summarize some of the most remarkable examples, and present the mechanistic rational underlying the transformations.

  16. Chemical Reactions: What Understanding Do Students with Blindness Develop?

    Science.gov (United States)

    Lewis, Amy L. Micklos; Bodner, George M.

    2013-01-01

    This study examined the understanding of chemical equations developed by three students with blindness who were enrolled in the same secondary-school chemistry class. The students were interviewed while interpreting and balancing chemical equations. During the course of these interviews, the students produced diagrams using Braille symbols that…

  17. Metathesis of alkanes and related reactions

    KAUST Repository

    Basset, Jean-Marie

    2010-02-16

    (Figure Presented) The transformation of alkanes remains a difficult challenge because of the relative inertness of the C-H and C-C bonds. The rewards for asserting synthetic control over unfunctionalized, saturated hydrocarbons are considerable, however, because converting short alkanes into longer chain analogues is usually a value-adding process. Alkane metathesis is a novel catalytic and direct transformation of two molecules of a given alkane into its lower and higher homologues; moreover, the process proceeds at relatively low temperature (ambient conditions or higher). It was discovered through the use of a silica-supported tantalum hydride, (=SiO)2TaH, a multifunctional catalyst with a single site of action. This reaction completes the story of the metathesis reactions discovered over the past 40 years: olefin metathesis, alkyne metathesis, and ene-yne cyclizations. In this Account, we examine the fundamental mechanistic aspects of alkane metathesis as well as the novel reactions that have been derived from its study. The silica-supported tantalum hydride catalyst was developed as the result of systematic and meticulous studies of the interaction between oxide supports and organometallic complexes, a field of study denoted surface organometallic chemistry (SOMC). A careful examination of this surface-supported tantalum hydride led to the later discovery of aluminasupported tungsten hydride, W(H)3/Al 2O3, which proved to be an even better catalyst for alkane metathesis. Supported tantalum and tungsten hydrides are highly unsaturated, electron-deficient species that are very reactive toward the C-H and C-C bonds of alkanes. They show a great versatility in various other reactions, such as cross-metathesis between methane and alkanes, cross-metathesis between toluene and ethane, or even methane nonoxidative coupling. Moreover, tungsten hydride exhibits a specific ability in the transformation of isobutane into 2,3-dimethylbutane as well as in the metathesis of

  18. Metathesis of alkanes and related reactions.

    Science.gov (United States)

    Basset, Jean-Marie; Copéret, Christophe; Soulivong, Daravong; Taoufik, Mostafa; Cazat, Jean Thivolle

    2010-02-16

    The transformation of alkanes remains a difficult challenge because of the relative inertness of the C-H and C-C bonds. The rewards for asserting synthetic control over unfunctionalized, saturated hydrocarbons are considerable, however, because converting short alkanes into longer chain analogues is usually a value-adding process. Alkane metathesis is a novel catalytic and direct transformation of two molecules of a given alkane into its lower and higher homologues; moreover, the process proceeds at relatively low temperature (ambient conditions or higher). It was discovered through the use of a silica-supported tantalum hydride, ([triple bond]SiO)(2)TaH, a multifunctional catalyst with a single site of action. This reaction completes the story of the metathesis reactions discovered over the past 40 years: olefin metathesis, alkyne metathesis, and ene-yne cyclizations. In this Account, we examine the fundamental mechanistic aspects of alkane metathesis as well as the novel reactions that have been derived from its study. The silica-supported tantalum hydride catalyst was developed as the result of systematic and meticulous studies of the interaction between oxide supports and organometallic complexes, a field of study denoted surface organometallic chemistry (SOMC). A careful examination of this surface-supported tantalum hydride led to the later discovery of alumina-supported tungsten hydride, W(H)(3)/Al(2)O(3), which proved to be an even better catalyst for alkane metathesis. Supported tantalum and tungsten hydrides are highly unsaturated, electron-deficient species that are very reactive toward the C-H and C-C bonds of alkanes. They show a great versatility in various other reactions, such as cross-metathesis between methane and alkanes, cross-metathesis between toluene and ethane, or even methane nonoxidative coupling. Moreover, tungsten hydride exhibits a specific ability in the transformation of isobutane into 2,3-dimethylbutane as well as in the metathesis

  19. Integrated rotating-compensator polarimeter for real-time measurements and analysis of organometallic chemical vapor deposition

    Energy Technology Data Exchange (ETDEWEB)

    Flock, K.; Kim, S.-J.; Asar, M.; Kim, I.K.; Aspnes, D.E

    2004-05-01

    We describe a single-beam rotating-compensator rotating-sample spectroscopic polarimeter (RCSSP) integrated with an organometallic chemical vapor deposition (OMCVD) reactor for in-situ diagnostics and control of epitaxial growth, and report representative results. The rotating compensator generates Fourier coefficients that provide information about layer thicknesses and compositions, while sample rotation provides information about optical anisotropy and therefore surface chemistry. We illustrate capabilities with various examples, including the simultaneous determination of <{epsilon}> and {alpha}{sub 10} during exposure of (001)GaAs to TMG, the heteroepitaxial growth of GaP on GaAs, and the growth of (001)GaSb with TMG and TMSb. Using a recently developed approach for quantitatively determining thickness and dielectric function of depositing layers, we find the presence of metallic Ga on TMG-exposed (001)GaAs. The (001)GaSb data show that Sb deposition is self-limiting, in contrast to expectations.

  20. A [4Fe-4S]-Fe(CO)(CN)-l-cysteine intermediate is the first organometallic precursor in [FeFe] hydrogenase H-cluster bioassembly

    Science.gov (United States)

    Rao, Guodong; Tao, Lizhi; Suess, Daniel L. M.; Britt, R. David

    2018-05-01

    Biosynthesis of the [FeFe] hydrogenase active site (the 'H-cluster') requires the interplay of multiple proteins and small molecules. Among them, the radical S-adenosylmethionine enzyme HydG, a tyrosine lyase, has been proposed to generate a complex that contains an Fe(CO)2(CN) moiety that is eventually incorporated into the H-cluster. Here we describe the characterization of an intermediate in the HydG reaction: a [4Fe-4S][(Cys)Fe(CO)(CN)] species, 'Complex A', in which a CO, a CN- and a cysteine (Cys) molecule bind to the unique 'dangler' Fe site of the auxiliary [5Fe-4S] cluster of HydG. The identification of this intermediate—the first organometallic precursor to the H-cluster—validates the previously hypothesized HydG reaction cycle and provides a basis for elucidating the biosynthetic origin of other moieties of the H-cluster.

  1. Development of linear free energy relationships for aqueous phase radical-involved chemical reactions.

    Science.gov (United States)

    Minakata, Daisuke; Mezyk, Stephen P; Jones, Jace W; Daws, Brittany R; Crittenden, John C

    2014-12-02

    Aqueous phase advanced oxidation processes (AOPs) produce hydroxyl radicals (HO•) which can completely oxidize electron rich organic compounds. The proper design and operation of AOPs require that we predict the formation and fate of the byproducts and their associated toxicity. Accordingly, there is a need to develop a first-principles kinetic model that can predict the dominant reaction pathways that potentially produce toxic byproducts. We have published some of our efforts on predicting the elementary reaction pathways and the HO• rate constants. Here we develop linear free energy relationships (LFERs) that predict the rate constants for aqueous phase radical reactions. The LFERs relate experimentally obtained kinetic rate constants to quantum mechanically calculated aqueous phase free energies of activation. The LFERs have been applied to 101 reactions, including (1) HO• addition to 15 aromatic compounds; (2) addition of molecular oxygen to 65 carbon-centered aliphatic and cyclohexadienyl radicals; (3) disproportionation of 10 peroxyl radicals, and (4) unimolecular decay of nine peroxyl radicals. The LFERs correlations predict the rate constants within a factor of 2 from the experimental values for HO• reactions and molecular oxygen addition, and a factor of 5 for peroxyl radical reactions. The LFERs and the elementary reaction pathways will enable us to predict the formation and initial fate of the byproducts in AOPs. Furthermore, our methodology can be applied to other environmental processes in which aqueous phase radical-involved reactions occur.

  2. Organometallic halide perovskite single crystals having low deffect density and methods of preparation thereof

    KAUST Repository

    Bakr, Osman; Shi, Dong

    2016-01-01

    The present disclosure presents a method of making a single crystal organometallic halide perovskites, with the formula: AMX3, wherein A is an organic cation, M is selected from the group consisting of: Pb, Sn, Cu, Ni, Co, Fe, Mn, Pd, Cd, Ge, and Eu

  3. Redox responsive nanotubes from organometallic polymers by template assisted layer by layer fabrication

    NARCIS (Netherlands)

    Song, Jing; Janczewski, D.J.; Guo, Y.Y.; Guo, Yuanyuan; Xu, Jianwei; Vancso, Gyula J.

    2013-01-01

    Redox responsive nanotubes were fabricated by the template assisted layer-by-layer (LbL) assembly method and employed as platforms for molecular payload release. Positively and negatively charged organometallic poly(ferrocenylsilane)s (PFS) were used to construct the nanotubes, in combination with

  4. A golden future in medicinal inorganic chemistry : The promise of anticancer gold organometallic compounds

    NARCIS (Netherlands)

    Bertrand, B.; Casini, A.

    2014-01-01

    From wedding rings on fingers to stained glass windows, by way of Olympic medals, gold has been highly prized for millennia. Nowadays, organometallic gold compounds occupy an important place in the field of medicinal inorganic chemistry due to their unique chemical properties with respect to gold

  5. Using Molecular Modeling in Teaching Group Theory Analysis of the Infrared Spectra of Organometallic Compounds

    Science.gov (United States)

    Wang, Lihua

    2012-01-01

    A new method is introduced for teaching group theory analysis of the infrared spectra of organometallic compounds using molecular modeling. The main focus of this method is to enhance student understanding of the symmetry properties of vibrational modes and of the group theory analysis of infrared (IR) spectra by using visual aids provided by…

  6. Efficient organometallic spin filter between single-wall carbon nanotube or graphene electrodes

    DEFF Research Database (Denmark)

    Koleini, Mohammad; Paulsson, Magnus; Brandbyge, Mads

    2007-01-01

    We present a theoretical study of spin transport in a class of molecular systems consisting of an organometallic benzene-vanadium cluster placed in between graphene or single-wall carbon-nanotube-model contacts. Ab initio modeling is performed by combining spin density functional theory...

  7. Organometallic benzene-vanadium wire: A one-dimensional half-metallic ferromagnet

    DEFF Research Database (Denmark)

    Maslyuk, V.; Bagrets, A.; Meded, V.

    2006-01-01

    Using density functional theory we perform theoretical investigations of the electronic properties of a freestanding one-dimensional organometallic vanadium-benzene wire. This system represents the limiting case of multidecker V-n(C6H6)(n+1) clusters which can be synthesized with established meth...

  8. Development of a utility system for nuclear reaction data file: WinNRDF

    International Nuclear Information System (INIS)

    Aoyama, Shigeyoshi; Ohbayasi, Yosihide; Masui, Hiroshi; Chiba, Masaki; Kato, Kiyoshi; Ohnishi, Akira

    2000-01-01

    A utility system, WinNRDF, is developed for charged particle nuclear reaction data of NRDF (Nuclear Reaction Data File) on the Windows interface. By using this system, we can easily search the experimental data of a charged particle nuclear reaction in NRDF than old retrieval systems on the mainframe and also see graphically the experimental data on GUI (Graphical User Interface). We adopted a mechanism of making a new index of keywords to put to practical use of the time dependent properties of the NRDF database. (author)

  9. Development of laboratory apparatus dedicated to the study of hydride--dehydride reactions

    International Nuclear Information System (INIS)

    Wemple, R.P.; Kass, W.J.

    1979-07-01

    Hydrogen-compatible laboratory apparatus has been designed and developed to study hydride--dehydride reactions at elevated pressures and temperatures. The system has operated at pressures and temperatures up to 34 MPa and 550 0 C during experiments conducted on LiAlH 4 and NiZr. Instrumentation incorporated into the system also allows differential thermal analysis and acoustic emission data to be collected as the chemical reactions progress. 13 figures

  10. Recent developments in Cope-type hydroamination reactions of hydroxylamine and hydrazine derivatives.

    Science.gov (United States)

    Beauchemin, André M

    2013-11-07

    Cope-type hydroaminations are versatile for the direct amination of alkenes, alkynes and allenes using hydroxylamines and hydrazine derivatives. These reactions occur via a concerted, 5-membered cyclic transition state that is the microscopic reverse of the Cope elimination. This article focuses on recent developments, including intermolecular variants, directed reactions, and asymmetric variants using aldehydes as tethering catalysts, and their applications in target-oriented synthesis.

  11. Palladium-Catalyzed Cross-Coupling Reactions of Perfluoro Organic Compounds

    Directory of Open Access Journals (Sweden)

    Masato Ohashi

    2014-09-01

    Full Text Available In this review, we summarize our recent development of palladium(0-catalyzed cross-coupling reactions of perfluoro organic compounds with organometallic reagents. The oxidative addition of a C–F bond of tetrafluoroethylene (TFE to palladium(0 was promoted by the addition of lithium iodide, affording a trifluorovinyl palladium(II iodide. Based on this finding, the first palladium-catalyzed cross-coupling reaction of TFE with diarylzinc was developed in the presence of lithium iodide, affording α,β,β-trifluorostyrene derivatives in excellent yield. This coupling reaction was expanded to the novel Pd(0/PR3-catalyzed cross-coupling reaction of TFE with arylboronates. In this reaction, the trifluorovinyl palladium(II fluoride was a key reaction intermediate that required neither an extraneous base to enhance the reactivity of organoboronates nor a Lewis acid additive to promote the oxidative addition of a C–F bond. In addition, our strategy utilizing the synergetic effect of Pd(0 and lithium iodide could be applied to the C–F bond cleavage of unreactive hexafluorobenzene (C6F6, leading to the first Pd(0-catalyzed cross-coupling reaction of C6F6 with diarylzinc compounds.

  12. Atomic-Resolution Transmission Electron Microscopic Movies for Study of Organic Molecules, Assemblies, and Reactions: The First 10 Years of Development.

    Science.gov (United States)

    Nakamura, Eiichi

    2017-06-20

    A molecule is a quantum mechanical entity. "Watching motions and reactions of a molecule with our eyes" has therefore been a dream of chemists for a century. This dream has come true with the aid of the movies of atomic-resolution transmission electron microscopic (AR-TEM) molecular images through real-time observation of dynamic motions of single organic molecules (denoted hereafter as single-molecule atomic-resolution real-time (SMART) TEM imaging). Since 2007, we have reported movies of a variety of single organic molecules, organometallic molecules, and their assemblies, which are rotating, stretching, and reacting. Like movies in the theater, the atomic-resolution molecular movies provide us information on the 3-D structures of the molecules and also their time evolution. The success of the SMART-TEM imaging crucially depends on the development of "chemical fishhooks" with which fish (organic molecules) in solution can be captured on a single-walled carbon nanotube (CNT, serving as a "fishing rod"). The captured molecules are connected to a slowly vibrating CNT, and their motions are displayed on a monitor in real time. A "fishing line" connecting the fish and the rod may be a σ-bond, a van der Waals force, or other weak connections. Here, the molecule/CNT system behaves as a coupled oscillator, where the low-frequency anisotropic vibration of the CNT is transmitted to the molecules via the weak chemical connections that act as an energy filter. Interpretation of the observed motions of the molecules at atomic resolution needs us to consider the quantum mechanical nature of electrons as well as bond rotation, letting us deviate from the conventional statistical world of chemistry. What new horizons can we explore? We have so far carried out conformational studies of individual molecules, assigning anti or gauche conformations to each C-C bond in conformers that we saw. We can also determine the structures of van der Waals assemblies of organic molecules

  13. Using Outdoor Adventure Education to Develop Students' Groupwork Skills: A Quantitative Exploration of Reaction and Learning

    Science.gov (United States)

    Cooley, Sam J.; Burns, Victoria E.; Cumming, Jennifer

    2016-01-01

    This study investigates the initial development of groupwork skills through outdoor adventure education (OAE) and the factors that predict the extent of this development, using the first two levels of Kirkpatrick's model of training evaluation. University students (N = 238) completed questionnaires measuring their initial reactions to OAE (Level 1…

  14. Development of a robust and compact kerosene–diesel reaction mechanism for diesel engines

    International Nuclear Information System (INIS)

    Tay, Kun Lin; Yang, Wenming; Mohan, Balaji; An, Hui; Zhou, Dezhi; Yu, Wenbin

    2016-01-01

    Highlights: • An approach is used to develop a robust kerosene–diesel reaction mechanism. • Ignition delay of the kerosene sub-mechanism is well validated with experiments. • The kerosene sub-mechanism reproduces the flame lift-off lengths of Jet-A reasonably well. • The kerosene sub-mechanism performs reasonably well under engine conditions. - Abstract: The use of kerosene fuels in internal combustion engines is getting more widespread. The North Atlantic Treaty Organization military is pushing for the use of a single fuel on the battlefield in order to reduce logistical issues. Moreover, in some countries, fuel adulteration is a serious matter where kerosene is blended with diesel and used in diesel engines. So far, most investigations done regarding the use of kerosene fuels in diesel engines are experimental and there is negligible simulation work done in this area possibly because of the lack of a robust and compact kerosene reaction mechanism. This work focuses on the development of a small but reliable kerosene–diesel reaction mechanism, suitable to be used for diesel engine simulations. The new kerosene–diesel reaction mechanism consists only of 48 species and 152 reactions. Furthermore, the kerosene sub-mechanism in this new mechanism is well validated for its ignition delay times and has proven to replicate kerosene combustion well in a constant volume combustion chamber and an optical engine. Overall, this new kerosene–diesel reaction mechanism is proven to be robust and practical for diesel engine simulations.

  15. Synthesis and thermal behavior of new organometallic poly ketones and co-poly ketones based on diferrocenylidene piperidone

    International Nuclear Information System (INIS)

    Aly, K.I.

    2005-01-01

    A new interesting category of organometallic poly ketones and copolyketones were synthesized via Friedel - Crafts reaction through the polymerization of 2,6-[Bis (2-ferrocenyl )methylene] N-methylpiperidone (II) with different diacid chlorides. The model compound was synthesized by reacting the monomer (II) with benzoyl chloride and characterized by HNMR, IR and elemental analyses. The poly ketones and copolyketones were insoluble in most organic solvents but soluble easily in protic solvents. The thermal properties of these poly ketones and copolyketones were evaluated and correlated to their structural units by TGA and DSC measurements, and had inherent viscosity 0.34-0.52 dl g-1. Moreover, the electrical conductivity of one of the poly ketones, as selected example, Va and copolyketone VI were investigated above the temperature range (300-500 K) and showed that it followed an Arrhenius equation with activation energy 2.09 eV, also the morphological properties of selected examples of poly-and copolyketones were detected by SEM

  16. Development of charged particle nuclear reaction data retrieval system on IntelligentPad

    International Nuclear Information System (INIS)

    Ohbayashi, Yosihide; Masui, Hiroshi; Aoyama, Shigeyoshi; Kato, Kiyoshi; Chiba, Masaki

    1999-01-01

    An newly designed database retrieval system of charged particle nuclear reaction database system is developed with IntelligentPad architecture. We designed the network-based (server-client) data retrieval system, and a client system constructs on Windows95, 98/NT with IntelligentPad. We set the future aim of our database system toward the 'effective' use of nuclear reaction data: I. 'Re-produce, Re-edit, Re-use', II. 'Circulation, Evolution', III. 'Knowledge discovery'. Thus, further developments are under way. (author)

  17. Surface Reaction Kinetics of Ga(1-x)In(x)P Growth During Pulsed Chemical Beam Epitaxy

    National Research Council Canada - National Science Library

    Dietz, N; Beeler, S. C; Schmidt, J. W; Tran, H. T

    2000-01-01

    ... into the surface reaction kinetics during an organometallic deposition process. These insights will allow us to move the control point closer to the point where the growth occurs, which in a chemical been epitaxy process is a surface reaction layer (SRL...

  18. A silica-supported double-decker silsesquioxane provides a second skin for the selective generation of bipodal surface organometallic complexes

    KAUST Repository

    Espinas, Jeff

    2012-11-12

    A well-defined silica-based material with a homogeneous nanolayer presenting identical pairs of vicinal silanols has been prepared by reaction of the surface organometallic species [≡SiOZr(CH 2CMe 3) 3], obtained on a silica dehydroxylated at 900 °C, with the double-decker-shaped silsesquioxane (OH) 2DD(OH) 2. The surface structure has been established using extensive NMR characterization ( 1H, 13C, 29Si, HETCOR, double-quantum, triple-quantum). Treatment with Zr(CH 2CMe 3) 4 leads to the first well-defined single-site bipodal grafted bis-neopentyl zirconium complex. © 2012 American Chemical Society.

  19. A silica-supported double-decker silsesquioxane provides a second skin for the selective generation of bipodal surface organometallic complexes

    KAUST Repository

    Espinas, Jeff; Pelletier, Jeremie; Abou-Hamad, Edy; Emsley, Lyndon; Basset, Jean-Marie

    2012-01-01

    A well-defined silica-based material with a homogeneous nanolayer presenting identical pairs of vicinal silanols has been prepared by reaction of the surface organometallic species [≡SiOZr(CH 2CMe 3) 3], obtained on a silica dehydroxylated at 900 °C, with the double-decker-shaped silsesquioxane (OH) 2DD(OH) 2. The surface structure has been established using extensive NMR characterization ( 1H, 13C, 29Si, HETCOR, double-quantum, triple-quantum). Treatment with Zr(CH 2CMe 3) 4 leads to the first well-defined single-site bipodal grafted bis-neopentyl zirconium complex. © 2012 American Chemical Society.

  20. Development of LEAP-JET code for sodium-water reaction analysis. Validation by sodium-water reaction tests (SWAT-1R)

    International Nuclear Information System (INIS)

    Seino, Hiroshi; Hamada, Hirotsugu

    2004-03-01

    The sodium-water reaction event in an FBR steam generator (SG) has influence on the safety, economical efficiency, etc. of the plant, so that the selection of design base leak (DBL) of the SG is considered as one of the important matters. The clarification of the sodium-water reaction phenomenon and the development of an analysis model are necessary to estimate the sodium-water reaction event with high accuracy and rationality in selecting the DBL. The reaction jet model is pointed out as a part of the necessary improvements to evaluate the overheating tube rupture of large SGs, since the behavior of overheating tube rupture is largely affected by the reaction jet conditions outside the tube. Therefore, LEAP-JET has been developed as an analysis code for the simulation of sodium-water reactions. This document shows the validation of the LEAP-JET code by the Sodium-Water Reaction Test (SWAT-1R). The following results have been obtained: (1) The reaction rate constant, K, is estimated at between 0.001≤K≤0.1 from the LEAP-JET analysis of the SWAT-1R data. (2) The analytical results on the high-temperature region and the behaviors of reaction consumption (Na, H 2 O) and products (H 2 , NaOH, Na 2 O) are considered to be physically reasonable. (3) The LEAP-JET analysis shows the tendency of overestimation in the maximum temperature and temperature distribution of the reaction jet. (4) In the LEAP-JET analysis, the numerical calculation becomes unstably, especially in the mesh containing quite small sodium mass. Therefore, it is necessary to modify the computational algorism to stabilize it and obtain the optimum value of K in sodium-water reactions. (author)

  1. Energy and chemicals from the selective electrooxidation of renewable diols by organometallic fuel cells.

    Science.gov (United States)

    Bellini, Marco; Bevilacqua, Manuela; Filippi, Jonathan; Lavacchi, Alessandro; Marchionni, Andrea; Miller, Hamish A; Oberhauser, Werner; Vizza, Francesco; Annen, Samuel P; Grützmacher, H

    2014-09-01

    Organometallic fuel cells catalyze the selective electrooxidation of renewable diols, simultaneously providing high power densities and chemicals of industrial importance. It is shown that the unique organometallic complex [Rh(OTf)(trop2NH)(PPh3)] employed as molecular active site in an anode of an OMFC selectively oxidizes a number of renewable diols, such as ethylene glycol , 1,2-propanediol (1,2-P), 1,3-propanediol (1,3-P), and 1,4-butanediol (1,4-B) to their corresponding mono-carboxylates. The electrochemical performance of this molecular catalyst is discussed, with the aim to achieve cogeneration of electricity and valuable chemicals in a highly selective electrooxidation from diol precursors. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Development of the Automatic Modeling System for Reaction Mechanisms Using REX+JGG

    Science.gov (United States)

    Takahashi, Takahiro; Kawai, Kohei; Nakai, Hiroyuki; Ema, Yoshinori

    The identification of appropriate reaction models is very helpful for developing chemical vapor deposition (CVD) processes. In this study, we developed an automatic modeling system that analyzes experimental data on the cross- sectional shapes of films deposited on substrates with nanometer- or micrometer-sized trenches. The system then identifies a suitable reaction model to describe the film deposition. The inference engine used by the system to model the reaction mechanism was designed using real-coded genetic algorithms (RCGAs): a generation alternation model named "just generation gap" (JGG) and a real-coded crossover named "real-coded ensemble crossover" (REX). We studied the effect of REX+JGG on the system's performance, and found that the system with REX+JGG was the most accurate and reliable at model identification among the algorithms that we studied.

  3. Development of odd-Z-projectile reactions for transactinide element synthesis

    International Nuclear Information System (INIS)

    Folden III, Charles Marvin

    2004-01-01

    The development of new odd-Z-projectile reactions leading to the production of transactinide elements is described. The cross section of the even-Z-projectile 208Pb(64Ni, n)271Ds reaction was measured at two new energies using the Berkeley Gas-filled Separator at the Lawrence Berkeley National Laboratory 88-Inch Cyclotron. In total, seven decay chains attributable to 271Ds were observed. These data, combined with previous results, establish an excitation function for the production of 271Ds. The maximum cross section was 20 +15 -11 pb at a center-of-target energy of 311.5 MeV in the laboratory frame.The data from the 271Ds experiments were used to estimate the optimum beam energy for the new odd-Z-projectile 208Pb(65Cu, n)272-111 reaction using the Fusion by Diffusion theory proposed by Swiatecki, Siwek-Wilczynska, and Wilczynski. A cross section for this reaction was measured for the first time, at a center-of-target energy of 321.1 MeV in the laboratory frame. The excitation energy f or compound nuclei formed at the target center was 13.2 MeV. One decay chain was observed, resulting in a measured cross section of 1.7 +3.9 -1.4 pb. This decay chain is in good agreement with previously published data on the decay of 272-111.The new odd-Z-projectile 208Pb(55Mn, n)262Bh reaction was studied at three different projectile energies, and 33 decay chains of 262Bh were observed. The existence of a previously reported alpha-decaying isomeric state in this nuclide was confirmed. Production of the ground state was preferred at all three beam energies. The maximum cross section was 540 +180 -150 pb at a projectile center-of-target energy of 264.0 MeV. This cross section is much larger than that previously reported for the even-Z-projectile 209Bi(54Cr, n)262Bh reaction, which may be because the 54Cr projectile energies in the latter reaction were too high for optimum production of the 1n product. At the highest projectile energy of 268.0 MeV in the target center, two decay

  4. Organometallic halide perovskite single crystals having low deffect density and methods of preparation thereof

    KAUST Repository

    Bakr, Osman M.

    2016-02-18

    The present disclosure presents a method of making a single crystal organometallic halide perovskites, with the formula: AMX3, wherein A is an organic cation, M is selected from the group consisting of: Pb, Sn, Cu, Ni, Co, Fe, Mn, Pd, Cd, Ge, and Eu, and X is a halide. The method comprises the use of two reservoirs containing different precursors and allowing the vapor diffusion from one reservoir to the other one. A solar cell comprising said crystal is also disclosed.

  5. Induced-fit recognition of DNA by organometallic complexes with dynamic stereogenic centers

    Czech Academy of Sciences Publication Activity Database

    Chen, H.; Parkinson, J. A.; Nováková, Olga; Bella, J.; Wang, F.; Dawson, A.; Gould, R.; Parsons, S.; Brabec, Viktor; Sadler, P. J.

    2003-01-01

    Roč. 100, č. 25 (2003), s. 14623-14628 ISSN 0027-8424 R&D Projects: GA ČR GA305/02/1552; GA ČR GA305/01/0418; GA AV ČR IAA5004101 Institutional research plan: CEZ:AV0Z5004920 Keywords : organometallic complexes * platinum * DNA Subject RIV: BO - Biophysics Impact factor: 10.272, year: 2003

  6. Development and testing of a compartmentalized reaction network model for redox zones in contaminated aquifers

    Science.gov (United States)

    Abrams , Robert H.; Loague, Keith; Kent, Douglas B.

    1998-01-01

    The work reported here is the first part of a larger effort focused on efficient numerical simulation of redox zone development in contaminated aquifers. The sequential use of various electron acceptors, which is governed by the energy yield of each reaction, gives rise to redox zones. The large difference in energy yields between the various redox reactions leads to systems of equations that are extremely ill-conditioned. These equations are very difficult to solve, especially in the context of coupled fluid flow, solute transport, and geochemical simulations. We have developed a general, rational method to solve such systems where we focus on the dominant reactions, compartmentalizing them in a manner that is analogous to the redox zones that are often observed in the field. The compartmentalized approach allows us to easily solve a complex geochemical system as a function of time and energy yield, laying the foundation for our ongoing work in which we couple the reaction network, for the development of redox zones, to a model of subsurface fluid flow and solute transport. Our method (1) solves the numerical system without evoking a redox parameter, (2) improves the numerical stability of redox systems by choosing which compartment and thus which reaction network to use based upon the concentration ratios of key constituents, (3) simulates the development of redox zones as a function of time without the use of inhibition factors or switching functions, and (4) can reduce the number of transport equations that need to be solved in space and time. We show through the use of various model performance evaluation statistics that the appropriate compartment choice under different geochemical conditions leads to numerical solutions without significant error. The compartmentalized approach described here facilitates the next phase of this effort where we couple the redox zone reaction network to models of fluid flow and solute transport.

  7. Development of the system for excitation function automatic measurement of nuclear reactions

    International Nuclear Information System (INIS)

    Sapozhnikov, A.B.

    2004-01-01

    Full text: The resonance nuclear reaction method is applied at the tandem accelerator UKP-2-1 to determinate films thickness and obtain light element depth distribution. The system for automatic measurement of the nuclear reaction excitation curve has been developed. It allowed to obtain an excitation function of nuclear reaction using continuous changing potential of the target with energy step of 6 eV. Saw-tooth voltage with amplitude up to 6 kV from the block of scanning beam is fed to a target. The amplitude is determined by constant voltage from the scanning beam block control. Nal(Tl) detector detects gamma quanta - the products of a nuclear reaction and transforms they in voltage impulses. The impulses through the amplifier income in the single-channel analyzer which forms impulses to start the analog-to-digital converter. The value of saw-tooth voltage corresponding to the moment of gamma quantum detection is read by the analog-to-digital converter, where it is transformed to digital code and transmitted to the computer. The computer program has been developed to control the process of accumulation of excitation function. The dependence a detected γ-quanta yield from a target potential is automatically plotted by the program. This dependence corresponds to the nuclear reaction excitation function. If scanning amplitude is not enough in order to scan need depth of a sample, an operator increases energy of the proton beam changing high voltage potential of the terminal up 3 keV and measures the nuclear reaction excitation function with the new energy. This procedure can be repeated some times. After that 'sewing' of excitation functions is carried out by the program under the hypothesis that nuclear reaction yield in last points be identical

  8. Oxidative coupling of methane. Still a challenge for catalyst development and reaction engineering

    Energy Technology Data Exchange (ETDEWEB)

    Schomaecker, R.; Arnd, S.; Beck, B. [Technical Univ. of Berlin (Germany). Dept. of Chemistry] [and others

    2013-11-01

    The oxidative coupling of methane to ethylene offers great industrial potential, because it would broaden the feedstock basis for chemical industry. Because methane is the most stable hydrocarbon, its activation requires high temperatures and it is a great scientific challenge to overcome the apparent yield limit of about 25%. This barrier has never been exceeded since the beginning of OCM research more than 20 years ago. Results and Discussion: This challenge is one of the key projects of the Cluster of Excellence UNICAT and requires joined efforts and contributions from many disciplines, because this reaction shows a combined surface/gas phase reaction mechanism which results in very unusual and complex dependencies on the reaction conditions. Although dozens of materials are known to catalyze the reaction, the selection of a catalyst suitable for an industrial process is difficult, due to severe stability problems of many materials. Li/MgO was chosen by the UNICAT-team as model catalyst, because of the extended literature about it. But it shows uncontrollable deactivation, no matter what precursor and method were used for its preparation. Nevertheless, it is a suitable catalyst for fundamental studies, due to its formal chemical simplicity. A key result of the joined research activities was the disproval of the Lunsford mechanism and the elucidation of the real function of lithium as a surface modifier creating a rough and defect-rich surface. For the development of an OCM process another catalyst, Na{sub 2}WO{sub 4}/Mn/SiO{sub 2}, was chosen from the rich literature on OCM. Although less is known about its structure and the reaction mechanism at this catalyst, its stability was the most important reason to select it for further engineering studies. Kinetic isotope measurements and studies in a TAP reactor demonstrate the similarity of the reaction mechanisms at both catalysts, despite the completely different materials. The selectivity is largely controlled by

  9. Water-soluble diphosphadiazacyclooctanes as ligands for aqueous organometallic catalysis

    KAUST Repository

    Boulanger, Jérôme

    2012-12-01

    Two new water-soluble diphosphacyclooctanes been synthesized and characterized by NMR and surface tension measurements. Both phosphanes proved to coordinate rhodium in a very selective way as well-defined bidentates were obtained. When used in Rh-catalyzed hydroformylation of terminal alkenes, both ligands positively impacted the reaction chemoselectivity. © 2012 Elsevier B.V.

  10. Water-soluble diphosphadiazacyclooctanes as ligands for aqueous organometallic catalysis

    KAUST Repository

    Boulanger, Jé rô me; Bricout, Hervé ; Tilloy, Sé bastien; Fihri, Aziz; Len, Christophe; Hapiot, Fré dé ric; Monflier, É ric

    2012-01-01

    Two new water-soluble diphosphacyclooctanes been synthesized and characterized by NMR and surface tension measurements. Both phosphanes proved to coordinate rhodium in a very selective way as well-defined bidentates were obtained. When used in Rh-catalyzed hydroformylation of terminal alkenes, both ligands positively impacted the reaction chemoselectivity. © 2012 Elsevier B.V.

  11. Development of blow down and sodium-water reaction jet analysis codes-Validation by sodium-water reaction tests (SWAT-1R)

    International Nuclear Information System (INIS)

    Hiroshi Seino; Akikazu Kurihara; Isao Ono; Koji Jitsu

    2005-01-01

    Blow down analysis code (LEAP-BLOW) and sodium-water reaction jet analysis code (LEAP-JET) have been developed in order to improve the evaluation method on sodium-water reaction event in the steam generator (SG) of a sodium cooled fast breeder reactor (FBR). The validation analyses by these two codes were carried out using the data of Sodium-Water Reaction Test (SWAT-1R). The following main results have been obtained through this validation: (1) The calculational results by LEAP-BLOW such as internal pressure and water flow rate show good agreement with the results of the SWAT- 1R test. (2) The LEAP-JET code can qualitatively simulate the behavior of sodium-water reaction. However, it is found that the code has tendency to overestimate the maximum temperature of the reaction jet. (authors)

  12. Development of a prediction model of severe reaction in boiled egg challenges.

    Science.gov (United States)

    Sugiura, Shiro; Matsui, Teruaki; Nakagawa, Tomoko; Sasaki, Kemal; Nakata, Joon; Kando, Naoyuki; Ito, Komei

    2016-07-01

    We have proposed a new scoring system (Anaphylaxis SCoring Aichi: ASCA) for a quantitative evaluation of the anaphylactic reaction that is observed in an oral food challenge (OFC). Furthermore, the TS/Pro (Total Score of ASCA/cumulative protein dose) can be a marker to represent the overall severity of a food allergy. We aimed to develop a prediction model for a severe allergic reaction that is provoked in a boiled egg white challenge. We used two separate datasets to develop and validate the prediction model, respectively. The development dataset included 198 OFCs, that tested positive. The validation dataset prospectively included 140 consecutive OFCs, irrespective of the result. A 'severe reaction' was defined as a TS/Pro higher than 31 (the median score of the development dataset). A multivariate logistic regression analysis was performed to identify the factors associated with a severe reaction and develop the prediction model. The following four factors were independently associated with a severe reaction: ovomucoid specific IgE class (OM-sIgE: 0-6), aged 5 years or over, a complete avoidance of egg, and a total IgE prediction model. The model showed good discrimination in a receiver operating characteristic analysis; area under the curve (AUC) = 0.84 in development dataset, AUC = 0.85 in validation dataset. The prediction model significantly improved the AUC in both datasets compared to OM-sIgE alone. This simple scoring prediction model was useful for avoiding risky OFC. Copyright © 2016 Japanese Society of Allergology. Production and hosting by Elsevier B.V. All rights reserved.

  13. Influence of impairment of the immune system on hepatic biotransformation reactions, their postnatal development and inducibility

    International Nuclear Information System (INIS)

    Klinger, W.; Mueller, D.

    1983-01-01

    Neither destruction of thymus by N-methylnitrosourea or by X-rays nor thymectomy or splenectomy in rats of different ages affected hexobarbital sleeping time, ethylmorphine N-demethylation or ethoxycoumarin O-deethylation significantly and systematically. Thymectomy or thymus destruction by X-rays of newborn rats did not significantly influence postnatal development or inducibility by phenobarbital of the monooxygenase reactions. (author)

  14. Adverse Reactions in Allogeneic Blood Donors: A Tertiary Care Experience from a Developing Country

    Directory of Open Access Journals (Sweden)

    Sadia Sultan

    2016-03-01

    Full Text Available Objectives: Fragmented blood transfusion services along with an unmotivated blood donation culture often leads to blood shortage. Donor retention is crucial to meet the increasing blood demand, and adverse donor reactions have a negative impact on donor return. The aim of this study was to estimate adverse donor reactions and identify any demographic association.   Methods: We conducted a prospective study between January 2011 and December 2013. A total of 41,759 healthy donors were enrolled. Professionally trained donor attendants drew blood and all donors were observed during and following donation for possible adverse events for 20 minutes. Blood donors were asked to report if they suffered from any delayed adverse consequences.   Results: Out of 41,759 blood donors, 537 (1.3% experienced adverse reactions. The incidence was one in every 78 donations. The mean age of donors who experienced adverse events was 26.0±6.8 years, and all were male. Out of 537 donors, 429 (80% developed vasovagal reaction (VVR, 133 (25% had nausea, 63 (12% fainted, 35 (6% developed hyperventilation, 9 (2% had delayed syncope, and 9 (2% developed hematoma. Arterial prick, nerve injury, cardiac arrest, and seizures were not observed. Donors aged less than < 30 years and weighing < 70 kg were significantly associated with VVR, hyperventilation, and nausea (p < 0.005. Undergraduates and Urdu speaking donors also had a significant association with fainting and nausea, respectively (p < 0.05.   Conclusion: The prevalence of adverse events was low at our tertiary center. A VVR was the predominant adverse reaction and was associated with age and weight. Our study highlights the importance of these parameters in the donation process. A well-trained and experienced phlebotomist and pre-evaluation counseling of blood donors could further minimize the adverse reactions.

  15. Adverse Reactions in Allogeneic Blood Donors: A Tertiary Care Experience from a Developing Country.

    Science.gov (United States)

    Sultan, Sadia; Baig, Mohammad Amjad; Irfan, Syed Mohammed; Ahmed, Syed Ijlal; Hasan, Syeda Faiza

    2016-03-01

    Fragmented blood transfusion services along with an unmotivated blood donation culture often leads to blood shortage. Donor retention is crucial to meet the increasing blood demand, and adverse donor reactions have a negative impact on donor return. The aim of this study was to estimate adverse donor reactions and identify any demographic association.  . We conducted a prospective study between January 2011 and December 2013. A total of 41,759 healthy donors were enrolled. Professionally trained donor attendants drew blood and all donors were observed during and following donation for possible adverse events for 20 minutes. Blood donors were asked to report if they suffered from any delayed adverse consequences.  . Out of 41,759 blood donors, 537 (1.3%) experienced adverse reactions. The incidence was one in every 78 donations. The mean age of donors who experienced adverse events was 26.0±6.8 years, and all were male. Out of 537 donors, 429 (80%) developed vasovagal reaction (VVR), 133 (25%) had nausea, 63 (12%) fainted, 35 (6%) developed hyperventilation, 9 (2%) had delayed syncope, and 9 (2%) developed hematoma. Arterial prick, nerve injury, cardiac arrest, and seizures were not observed. Donors aged less than donors also had a significant association with fainting and nausea, respectively (p adverse events was low at our tertiary center. A VVR was the predominant adverse reaction and was associated with age and weight. Our study highlights the importance of these parameters in the donation process. A well-trained and experienced phlebotomist and pre-evaluation counseling of blood donors could further minimize the adverse reactions.

  16. Organometallic photovoltaics: a new and versatile approach for harvesting solar energy using conjugated polymetallaynes.

    Science.gov (United States)

    Wong, Wai-Yeung; Ho, Cheuk-Lam

    2010-09-21

    Energy remains one of the world's great challenges. Growing concerns about limited fossil fuel resources and the accumulation of CO(2) in the atmosphere from burning those fuels have stimulated tremendous academic and industrial interest. Researchers are focusing both on developing inexpensive renewable energy resources and on improving the technologies for energy conversion. Solar energy has the capacity to meet increasing global energy needs. Harvesting energy directly from sunlight using photovoltaic technology significantly reduces atmospheric emissions, avoiding the detrimental effects of these gases on the environment. Currently inorganic semiconductors dominate the solar cell production market, but these materials require high technology production and expensive materials, making electricity produced in this manner too costly to compete with conventional sources of electricity. Researchers have successfully fabricated efficient organic-based polymer solar cells (PSCs) as a lower cost alternative. Recently, metalated conjugated polymers have shown exceptional promise as donor materials in bulk-heterojunction solar cells and are emerging as viable alternatives to the all-organic congeners currently in use. Among these metalated conjugated polymers, soluble platinum(II)-containing poly(arylene ethynylene)s of variable bandgaps (∼1.4-3.0 eV) represent attractive candidates for a cost-effective, lightweight solar-energy conversion platform. This Account highlights and discusses the recent advances of this research frontier in organometallic photovoltaics. The emerging use of low-bandgap soluble platinum-acetylide polymers in PSCs offers a new and versatile strategy to capture sunlight for efficient solar power generation. Properties of these polyplatinynes--including their chemical structures, absorption coefficients, bandgaps, charge mobilities, accessibility of triplet excitons, molecular weights, and blend film morphologies--critically influence the device

  17. Enantioselective Decarboxylative Alkylation Reactions: Catalyst Development, Substrate Scope, and Mechanistic Studies

    KAUST Repository

    Behenna, Douglas C.; Mohr, Justin T.; Sherden, Nathaniel H.; Marinescu, Smaranda C.; Harned, Andrew M.; Tani, Kousuke; Seto, Masaki; Ma, Sandy; Nová k, Zoltá n; Krout, Michael R.; McFadden, Ryan M.; Roizen, Jennifer L.; Enquist, John A.; White, David E.; Levine, Samantha R.; Petrova, Krastina V.; Iwashita, Akihiko; Virgil, Scott C.; Stoltz, Brian M.

    2011-01-01

    α-Quaternary ketones are accessed through novel enantioselective alkylations of allyl and propargyl electrophiles by unstabilized prochiral enolate nucleophiles in the presence of palladium complexes with various phosphinooxazoline (PHOX) ligands. Excellent yields and high enantiomeric excesses are obtained from three classes of enolate precursor: enol carbonates, enol silanes, and racemic β-ketoesters. Each of these substrate classes functions with nearly identical efficiency in terms of yield and enantioselectivity. Catalyst discovery and development, the optimization of reaction conditions, the exploration of reaction scope, and applications in target-directed synthesis are reported. Experimental observations suggest that these alkylation reactions occur through an unusual inner-sphere mechanism involving binding of the prochiral enolate nucleophile directly to the palladium center.

  18. Enantioselective Decarboxylative Alkylation Reactions: Catalyst Development, Substrate Scope, and Mechanistic Studies

    Science.gov (United States)

    Behenna, Douglas C.; Mohr, Justin T.; Sherden, Nathaniel H.; Marinescu, Smaranda C.; Harned, Andrew M.; Tani, Kousuke; Seto, Masaki; Ma, Sandy; Novák, Zoltán; Krout, Michael R.; McFadden, Ryan M.; Roizen, Jennifer L.; Enquist, John A.; White, David E.; Levine, Samantha R.; Petrova, Krastina V.; Iwashita, Akihiko; Virgil, Scott C.; Stoltz, Brian M.

    2012-01-01

    α-Quaternary ketones are accessed through novel enantioselective alkylations of allyl and propargyl electrophiles by unstabilized prochiral enolate nucleophiles in the presence of palladium complexes with various phosphinooxazoline (PHOX) ligands. Excellent yields and high enantiomeric excesses are obtained from three classes of enolate precursors: enol carbonates, enol silanes, and racemic β-ketoesters. Each of these substrate classes functions with nearly identical efficiency in terms of yield and enantioselectivity. Catalyst discovery and development, the optimization of reaction conditions, the exploration of reaction scope, and applications in target-directed synthesis are reported. Experimental observations suggest that these alkylation reactions occur through an unusual inner-sphere mechanism involving binding of the prochiral enolate nucleophile directly to the palladium center. PMID:22083969

  19. Enantioselective Decarboxylative Alkylation Reactions: Catalyst Development, Substrate Scope, and Mechanistic Studies

    KAUST Repository

    Behenna, Douglas C.

    2011-11-14

    α-Quaternary ketones are accessed through novel enantioselective alkylations of allyl and propargyl electrophiles by unstabilized prochiral enolate nucleophiles in the presence of palladium complexes with various phosphinooxazoline (PHOX) ligands. Excellent yields and high enantiomeric excesses are obtained from three classes of enolate precursor: enol carbonates, enol silanes, and racemic β-ketoesters. Each of these substrate classes functions with nearly identical efficiency in terms of yield and enantioselectivity. Catalyst discovery and development, the optimization of reaction conditions, the exploration of reaction scope, and applications in target-directed synthesis are reported. Experimental observations suggest that these alkylation reactions occur through an unusual inner-sphere mechanism involving binding of the prochiral enolate nucleophile directly to the palladium center.

  20. Periodic precipitation a microcomputer analysis of transport and reaction processes in diffusion media, with software development

    CERN Document Server

    Henisch, H K

    1991-01-01

    Containing illustrations, worked examples, graphs and tables, this book deals with periodic precipitation (also known as Liesegang Ring formation) in terms of mathematical models and their logical consequences, and is entirely concerned with microcomputer analysis and software development. Three distinctive periodic precipitation mechanisms are included: binary diffusion-reaction; solubility modulation, and competitive particle growth. The book provides didactic illustrations of a valuable investigational procedure, in the form of hypothetical experimentation by microcomputer. The development

  1. Development of D-allose sensor on the basis of three strategic enzyme reactions.

    Science.gov (United States)

    Miyanishi, Nobumitsu; Nakakita, Shin-Ichi; Sumiyoshi, Wataru; Okuma, Hirokazu; Izumori, Ken; Hirabayashi, Jun

    2010-09-15

    Rare sugars are defined as monosaccharides and their derivatives that rarely exist in nature, according to the International Society of Rare Sugars. D-Allose (3-epi d-glucose) is one of the rare sugars, for which various physiological activities have recently been found, with increasing attention to its applications to bio-industry. Until now, however, there is no convenient method of measuring these sugars in a specific manner. For detecting D-allose, three consecutive enzyme reactions were devised by fabricating of a reaction batch chamber packed with L-rhamnose isomerase (LRI), D-tagatose 3-epimerase (DTE) and a screen-printed electrode, on which D-fructose dehydrogenase (DFDH) was immobilized. To obtain a substantial sensing system, extensive experimental parameters were optimized. These included the concentration of photo-crosslinkable poly (vinyl alcohol) bearing stilbazolium groups (PVA-SbQ), reaction ratios, and temperature of the batch chamber. By adopting the three consecutive enzyme reactions, an undesirable reverse reaction was minimized. As a result, the developed sensor system exhibited a good linear response on D-allose in the range from 0.1 to 50 mM (r(2)=0.998). The system has an apparent advantage over the previous chromatography approach in terms of simplicity and inexpensiveness. Copyright 2010 Elsevier B.V. All rights reserved.

  2. Development of a reaction cell for in-situ/operando studies of surface of a catalyst under a reaction condition and during catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen, Luan; Tao, Franklin, E-mail: franklin.tao.2011@gmail.com [Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556 (United States); Department of Chemical and Petroleum Engineering, University of Kansas, Lawrence, Kansas 66045 (United States)

    2016-06-15

    Tracking surface chemistry of a catalyst during catalysis is significant for fundamental understanding of catalytic performance of the catalyst since it allows for establishing an intrinsic correlation between surface chemistry of a catalyst at its working status and its corresponding catalytic performance. Ambient pressure X-ray photoelectron spectroscopy can be used for in-situ studies of surfaces of different materials or devices in a gas. To simulate the gaseous environment of a catalyst in a fixed-bed a flowing gaseous environment of reactants around the catalyst is necessary. Here, we report the development of a new flowing reaction cell for simulating in-situ study of a catalyst surface under a reaction condition in gas of one reactant or during catalysis in a mixture of reactants of a catalytic reaction. The homemade reaction cell is installed in a high vacuum (HV) or ultrahigh vacuum (UHV) environment of a chamber. The flowing gas in the reaction cell is separated from the HV or UHV environment through well sealings at three interfaces between the reaction cell and X-ray window, sample door and aperture of front cone of an energy analyzer. Catalyst in the cell is heated through infrared laser beam introduced through a fiber optics interfaced with the reaction cell through a homemade feedthrough. The highly localized heating on the sample holder and Au-passivated internal surface of the reaction cell effectively minimizes any unwanted reactions potentially catalyzed by the reaction cell. The incorporated laser heating allows a fast heating and a high thermal stability of the sample at a high temperature. With this cell, a catalyst at 800 °C in a flowing gas can be tracked readily.

  3. Development of a reaction cell for in-situ/operando studies of surface of a catalyst under a reaction condition and during catalysis

    International Nuclear Information System (INIS)

    Nguyen, Luan; Tao, Franklin

    2016-01-01

    Tracking surface chemistry of a catalyst during catalysis is significant for fundamental understanding of catalytic performance of the catalyst since it allows for establishing an intrinsic correlation between surface chemistry of a catalyst at its working status and its corresponding catalytic performance. Ambient pressure X-ray photoelectron spectroscopy can be used for in-situ studies of surfaces of different materials or devices in a gas. To simulate the gaseous environment of a catalyst in a fixed-bed a flowing gaseous environment of reactants around the catalyst is necessary. Here, we report the development of a new flowing reaction cell for simulating in-situ study of a catalyst surface under a reaction condition in gas of one reactant or during catalysis in a mixture of reactants of a catalytic reaction. The homemade reaction cell is installed in a high vacuum (HV) or ultrahigh vacuum (UHV) environment of a chamber. The flowing gas in the reaction cell is separated from the HV or UHV environment through well sealings at three interfaces between the reaction cell and X-ray window, sample door and aperture of front cone of an energy analyzer. Catalyst in the cell is heated through infrared laser beam introduced through a fiber optics interfaced with the reaction cell through a homemade feedthrough. The highly localized heating on the sample holder and Au-passivated internal surface of the reaction cell effectively minimizes any unwanted reactions potentially catalyzed by the reaction cell. The incorporated laser heating allows a fast heating and a high thermal stability of the sample at a high temperature. With this cell, a catalyst at 800 °C in a flowing gas can be tracked readily.

  4. Application of enantioselective radical reactions: synthesis of (+)-ricciocarpins A and B.

    Science.gov (United States)

    Sibi, Mukund P; He, Liwen

    2004-05-27

    Enantioselective synthesis of (+)-ricciocarpins A and B has been achieved in 41 and 45% overall yields, respectively, starting from a beta-substituted oxazolidinone. The key steps in the strategy are an enantioselective conjugate radical addition and the addition of a furyl organometallic to a key aldehyde intermediate. [reaction--see text

  5. Regularities of development of unspecific reaction of cells, and modification of chemical protection

    International Nuclear Information System (INIS)

    Veksler, A.M.; Korystov, Yu.N.; Kublik, L.N.; Ehjdus, L.Kh.

    1979-01-01

    Regularities of development of a unspecific reaction of cells under the effect of different substances belonging to weak electrolytes have been studied. It was demonstrated that the rate of the unspecific reaction development under the effect of cysteamine and caffeine-benzoate depends on the agent concentration, temperature and pH of a medium. It was established that the response of a cell is determined by the overall intracellular concentration of the agent rather than by its specific character. The total concentration of the substance inside the cell depends on its physico-chemical characteristics and, with a pH gradient between cell and medium, can markedly vary from that in the medium. With similar intracellular content, both substances proved to be virtually equally effective. This suggests that it is possible to assess the effectiveness of some other biologically active substances many of which are weak electrolytes

  6. Development of wide area reaction system for Reel-to-Reel TFA-MOD process

    International Nuclear Information System (INIS)

    Nomoto, Sukeharu; Aoki, Yuji; Teranishi, Ryo; Sato, Akihiro; Izumi, Teruo; Shiohara, Yuh

    2006-01-01

    The previously developed numerical simulation method for the TFA-MOD process, which calculated the YBCO growth kinetics, gas element diffusion and gas flow, was applied to study the suitable gas flow mode for a multi-turning Reel-to-Reel tape conveyance system of a long YBCO coated conductors. The high YBCO production rate with uniform J c distribution among tape lines is desired in the system. It was found by the numerical simulation for the vertical gas flow onto the tape surface to realize the above demands even in a wider reaction area. We developed a new wide area reaction tube for the Reel-to-Reel TFA-MOD process according to the numerically designed gas flow configuration. The demand for the new tube was confirmed to be satisfied by experiments

  7. Catalysis by Design Using Surface Organometallic Nitrogen-Containing Fragments

    KAUST Repository

    Hamzaoui, Bilel

    2016-06-14

    The aim of this thesis is to explore the chemistry of well-defined silica-supported group 4 and group 5 complexes that contain one or more multiply-bonded nitrogen atoms. Such species have been recognized as crucial intermediates in many catalytic reactions (e.g. hydroaminoalkylation, olefin hydrogenation, imine metathesis…). The first chapter provided a bibliographic overview of the preparation and the reactivity of group 4 and 5 complexes towards hydroaminoalkylation and imine metathesis catalysis. The second chapter deals with the isolation and the characterization of a series of well-defined group 4 ƞ2-imine complexes surfaces species. 2D solid-state NMR (1H–13C HETCOR, Multiple Quantum) experiments have revealed consistently a unique structural rearrangement, viz azametallacycle occurring on the immobilized metal-amido ligands. Hydrogenolysis of the sole Zr-C bond in such species gives selectively a silica-supported zirconium monohydride that can perform the catalytic hydrogenation of olefins. The third chapter examines the mechanistic studies of the intermolecular hydroaminoalkylation using SOMC to identify the key metallacyclic surface intermediates (silica-supported three-membred and five-membered). The catalyst was regenerated by protonolysis and afforded pure amine. Catalytic testing of a selection of amine compounds with variable electronic properties was carried out. The fourth chapter deals with the generation and the characterization of well-defined silica-supported zirconium-imido complexes. The resulting species effectively catalyzes imine/imine cross-metathesis and thus considered as the first heterogeneous catalysts active for imine metathesis reaction. The fifth chapter studies the reaction of SBA15.1100 ºC with dry aniline and derivatives leading to opening strained siloxane bridges into acid-base paired functionalities (formation of N-phenylsilanamine-silanol pairs). This approach was successfully applied to the design of a series of

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

    International Nuclear Information System (INIS)

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

    2004-01-01

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

  9. Recent developments in heavy-ion fusion reactions around the Coulomb barrier

    Directory of Open Access Journals (Sweden)

    Hagino K.

    2016-01-01

    Full Text Available The nuclear fusion is a reaction to form a compound nucleus. It plays an important role in several circumstances in nuclear physics as well as in nuclear astrophysics, such as synthesis of superheavy elements and nucleosynthesis in stars. Here we discuss two recent theoretical developments in heavy-ion fusion reactions at energies around the Coulomb barrier. The first topic is a generalization of the Wong formula for fusion cross sections in a single-channel problem. By introducing an energy dependence to the barrier parameters, we show that the generalized formula leads to results practically indistinguishable from a full quantal calculation, even for light symmetric systems such as 12C+12C, for which fusion cross sections show an oscillatory behavior. We then discuss a semi-microscopic modeling of heavy-ion fusion reactions, which combine the coupled-channels approach to the state-of-the-art nuclear structure calculations for low-lying collective motions. We apply this method to subbarrier fusion reactions of 58Ni+58Ni and 40Ca+58Ni systems, and discuss the role of anharmonicity of the low-lying vibrational motions.

  10. Organometallic complex chemistry of plutonium and selected lanthanides

    International Nuclear Information System (INIS)

    Seemann, U.

    1987-01-01

    This study deals with the metallo-organic chemistry of plutonium and also with that of some lanthanides. For plutonium, the conversion of Cs 2 PuCl 6 with four equivalents KCp is investigated. In the series Sm, Gd, Dy and Er, compounds of the type Cp 2 LnX and the base adducts with acetonitrile are analysed. The ligand X passes the series Cl, N 3 , NCS and NCO. Both, the thermal and the vibrational spectroscopic behaviour is investigated. In addition, the effect of a changed ligand sphere on the optical spectrum is discussed. The adduct-free compounds are described by a ternary reaction not yet known from literature. For the first time, force constant calculations are carried out on metallo-organic compounds of lanthanides. With the exception of Cp 2 LnCl compounds, all compouds are presented for the first time in the framework of this study. (orig.) [de

  11. Theoretical study of the structure and reactivity of lanthanide and actinide based organometallic complexes; Etude theorique de la structure et de la reactivite de complexes organometalliques de lanthanides et d'actinides

    Energy Technology Data Exchange (ETDEWEB)

    Barros, N

    2007-06-15

    In this PhD thesis, lanthanide and actinide based organometallic complexes are studied using quantum chemistry methods. In a first part, the catalytic properties of organo-lanthanide compounds are evaluated by studying two types of reactions: the catalytic hydro-functionalization of olefins and the polymerisation of polar monomers. The reaction mechanisms are theoretically determined and validated, and the influence of possible secondary non productive reactions is envisaged. A second part focuses on uranium-based complexes. Firstly, the electronic structure of uranium metallocenes is analysed. An analogy with the uranyl compounds is proposed. In a second chapter, two isoelectronic complexes of uranium IV are studied. After validating the use of DFT methods for describing the electronic structure and the reactivity of these compounds, it is shown that their reactivity difference can be related to a different nature of chemical bonding in these complexes. (author)

  12. Horizons of organic and organoelemental chemistry. 7. All-Russian conference on organometallic chemistry. Program and summaries of communications. V. 1

    International Nuclear Information System (INIS)

    1999-01-01

    Abstracts of the seventh All-Russian conference on organometallic chemistry are presented. The synthesis of organometallic compounds of rare earth, transition elements, the synthesis of organic boron compounds are played an important role in modern organic chemistry and the main part of reports are devoted to these problems. Methods of labelling by radioactive isotopes of organic compounds used in medicine are discussed

  13. Strategies for method development for an inductively coupled plasma mass spectrometer with bandpass reaction cell. Approaches with different reaction gases for the determination of selenium

    International Nuclear Information System (INIS)

    Hattendorf, Bodo; Guenther, Detlef

    2003-01-01

    An inductively coupled plasma mass spectrometer with dynamic reaction cell (DRC) was used to investigate different approaches for chemical resolution of Ar 2 + ions and to improve the determination of Se. Hydrogen, methane, oxygen and nitrous oxide were used as reaction gases. The method development for each approach consists of the acquisition of spectra for blank and spiked samples at different operating parameters, including reaction gas flow and transmission settings, of the DRC. Isotope ratio studies and the analytes signal to background ratio (SBR), were used as criteria to determine the operating conditions of the DRC where spectral interferences from the ion source or from polyatomic ions formed inside the DRC are minimized. Methane was found to provide the highest reaction efficiency for determination of Se. Nitrous oxide and oxygen also very efficiently suppress the Ar 2 + interference but reaction or scattering losses of Se + and SeO + are significant. Hydrogen is the least efficient gas for Ar 2 + reduction but little scattering or reactive loss lead to a good SBR. The determination of Se as SeO + was investigated with oxygen and nitrous oxide as reaction gases. The efficiency when using the oxygenation reaction was found to be similar to the efficiency for the charge transfer reactions but the slow oxygenation of the potentially interfering Mo + renders this approach less useful for analytical purposes. Using a natural water sample it could be shown that very good agreement is obtained using methane or hydrogen for analysis of 80 Se + at the μg/l level. Limits of detection are lowest (2 ng/l) when methane is used to suppress the Ar 2 + ion and when 80 Se + is used for analysis

  14. Application of imaging spectroscopic reflectometry for characterization of gold reduction from organometallic compound by means of plasma jet technology

    Energy Technology Data Exchange (ETDEWEB)

    Vodák, Jiří, E-mail: jiri.vodak@yahoo.com [Institute of Physical Engineering, Faculty of Mechanical Engineering, Brno University of Technology, Technická 2, 616 69 Brno (Czech Republic); Nečas, David [RG Plasma Technologies, CEITEC Masaryk University, Kamenice 5, 625 00 Brno (Czech Republic); Pavliňák, David [Department of Physical Electronics, Masaryk University, Kotlářská 2, 611 37 Brno (Czech Republic); Macak, Jan M [Center of Materials and Nanotechnologies, Faculty of Chemical Technology, University of Pardubice, Nám. Čs. Legií 565, 530 02 Pardubice (Czech Republic); Řičica, Tomáš; Jambor, Roman [Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, Studentská 573, 532 10 Pardubice (Czech Republic); Ohlídal, Miloslav [Institute of Physical Engineering, Faculty of Mechanical Engineering, Brno University of Technology, Technická 2, 616 69 Brno (Czech Republic); Institute of Physics, Faculty of Mining and Geology, VŠB – Technical University of Ostrava (Czech Republic)

    2017-02-28

    Highlights: • Metallic gold is reduced from an organometallic compound layer using a plasma jet. • Imaging spectroscopic reflectometry is used to locate areas with metallic gold. • The results are completed with XPS and optical microscopy observations. - Abstract: This work presents a new application of imaging spectroscopic reflectometry to determine a distribution of metallic gold in a layer of an organogold precursor which was treated by a plasma jet. Gold layers were prepared by spin coating from a solution of the precursor containing a small amount of polyvinylpyrrolidone on a microscopy glass, then they were vacuum dried. A difference between reflectivity of metallic gold and the precursor was utilized by imaging spectroscopic reflectometry to create a map of metallic gold distribution using a newly developed model of the studied sample. The basic principle of the imaging spectroscopic reflectometry is also shown together with the data acquisition principles. XPS measurements and microscopy observations were made to complete the imaging spectroscopic reflectometry results. It is proved that the imaging spectroscopic reflectometry represents a new method for quantitative evaluation of local reduction of metallic components from metaloorganic compounds.

  15. Systems and methods for solar energy storage, transportation, and conversion utilizing photochemically active organometallic isomeric compounds and solid-state catalysts

    Science.gov (United States)

    Vollhardt, K. Peter C.; Segalman, Rachel A; Majumdar, Arunava; Meier, Steven

    2015-02-10

    A system for converting solar energy to chemical energy, and, subsequently, to thermal energy includes a light-harvesting station, a storage station, and a thermal energy release station. The system may include additional stations for converting the released thermal energy to other energy forms, e.g., to electrical energy and mechanical work. At the light-harvesting station, a photochemically active first organometallic compound, e.g., a fulvalenyl diruthenium complex, is exposed to light and is photochemically converted to a second, higher-energy organometallic compound, which is then transported to a storage station. At the storage station, the high-energy organometallic compound is stored for a desired time and/or is transported to a desired location for thermal energy release. At the thermal energy release station, the high-energy organometallic compound is catalytically converted back to the photochemically active organometallic compound by an exothermic process, while the released thermal energy is captured for subsequent use.

  16. Development of a skeletal multi-component fuel reaction mechanism based on decoupling methodology

    International Nuclear Information System (INIS)

    Mohan, Balaji; Tay, Kun Lin; Yang, Wenming; Chua, Kian Jon

    2015-01-01

    Highlights: • A compact multi-component skeletal reaction mechanism was developed. • Combined bio-diesel and PRF mechanism was proposed. • The mechanism consists of 68 species and 183 reactions. • Well validated against ignition delay times, flame speed and engine results. - Abstract: A new coupled bio-diesel surrogate and primary reference fuel (PRF) oxidation skeletal mechanism has been developed. The bio-diesel surrogate sub-mechanism consists of oxidation sub-mechanisms of Methyl decanoate (MD), Methyl 9-decenoate (MD9D) and n-Heptane fuel components. The MD and MD9D are chosen to represent the saturated and unsaturated methyl esters respectively in bio-diesel fuels. Then, a reduced iso-Octane oxidation sub-mechanism is added to the bio-diesel surrogate sub-mechanism. Then, all the sub-mechanisms are integrated to a reduced C_2–C_3 mechanism, detailed H_2/CO/C_1 mechanism and reduced NO_x mechanism based on decoupling methodology. The final mechanism consisted of 68 species and 183 reactions. The mechanism was well validated with shock-tube ignition delay times, laminar flame speed and 3D engine simulations.

  17. Polymerase Chain Reaction/Rapid Methods Are Gaining a Foothold in Developing Countries.

    Science.gov (United States)

    Ragheb, Suzan Mohammed; Jimenez, Luis

    Detection of microbial contamination in pharmaceutical raw materials and finished products is a critical factor to guarantee their safety, stability, and potency. Rapid microbiological methods-such as polymerase chain reaction-have been widely applied to clinical and food quality control analysis. However, polymerase chain reaction applications to pharmaceutical quality control have been rather slow and sporadic. Successful implementation of these methods in pharmaceutical companies in developing countries requires important considerations to provide sensitive and robust assays that will comply with good manufacturing practices. In recent years several publications have encouraged the application of molecular techniques in the microbiological assessment of pharmaceuticals. One of these techniques is polymerase chain reaction (PCR). The successful application of PCR in the pharmaceutical industry in developing countries is governed by considerable factors and requirements. These factors include the setting up of a PCR laboratory and the choice of appropriate equipment and reagents. In addition, the presence of well-trained analysts and establishment of quality control and quality assurance programs are important requirements. The pharmaceutical firms should take into account these factors to allow better chances for regulatory acceptance and wide application of this technique. © PDA, Inc. 2014.

  18. Spectroscopic studies of organometallic compounds on single crystal metal surfaces: Surface acetylides of silver (110)

    Science.gov (United States)

    Madix, Robert J.

    The nature of compounds formed by the reaction of organic molecules with metal surfaces can be studied with a battery of analytical methods based on both physicals and chemical understanding. In this paper the application of UPS, XPS, LEED and EELS as well as temperature programmed reaction spectroscopy (TPRS) and chemical titration methods to the characterization of surface complexes is discussed. Particular emphasis is given to the reaction of acetylene with a single crystal surface of silver, Ag(110). Previous work has shown that this surface, when clean, is unreactive to hydrocarbons, alcohols and carboxylic acids under ultra high vacuum conditions. Preadsorption of oxygen, however, renders the surface reactive, and a wide variety of organometallic surface compounds can be formed. As expected then, no stable adsorption state and no reaction was observed with clean Ag(110) following room temperature exposure to acetylene. Following exposure at 150 K, however, a weekly bound chemisorption state was observed to desorb at 195 K, indicating a binding energy to the surface of approximately 12 kcal/gmole. Reaction with preadsorbed oxygen gave water formulation upon dosing and produced surface intermediates which yeilded two acetylene desorption states at 195 and 175 K. Heating above 300 K to completely desorb the higher temperature state produced new, well-defined LEED Features due to residual surface carbon which disappeared when the surface was heated above 550 K. Clearly, there were distinc changes in the nature of the absorbed layer at 195, 300 and 550 K. These changes were reflected in XPS. For the weakly chemisorbed acetylene a large C(ls) peak at 285.6 eV with a small, broad, indistinc shoulder at higher binding energy (288.2) was observed. The spectrum of the species following acetylene desorption at 275 K, however, showed the formulation of a large C(ls) peak at 283.6 eV in addition to peaks characteristics of the weakly chemisorbed state. This result

  19. Development of computer code on sodium-water reaction products transport

    International Nuclear Information System (INIS)

    Arikawa, H.; Yoshioka, N.; Suemori, M.; Nishida, K.

    1988-01-01

    The LMFBR concept eliminating the secondary sodium system has been considered to be one of the most promissing concepts for offering cost reductions. In this reactor concept, the evaluation of effects on reactor core by the sodium-water reaction products (SWRPs) during sodium-water reaction at primary steam generator becomes one of the major safety issues. In this study, the calculation code was developed as the first step of the processes of establishing the evaluation method for SWRP effects. The calculation code, called SPROUT, simulates the SWRPs transport and distribution in primary sodium system using the system geometry, thermal hydraulic data and sodium-water reacting conditions as input. This code principally models SWRPs behavior. The paper contain the modelings for SWRPs behaviors, with solution, precipation, deposition and so on, and the results and discussions of the demonstration calculation for a typical FBR plant eliminating the secondary sodium system

  20. Waterhammer modeling for the Ares I Upper Stage Reaction Control System cold flow development test article

    Science.gov (United States)

    Williams, Jonathan Hunter

    The Upper Stage Reaction Control System provides in-flight three-axis attitude control for the Ares I Upper Stage. The system design must accommodate rapid thruster firing to maintain proper launch trajectory and thus allow for the possibility to pulse multiple thrusters simultaneously. Rapid thruster valve closure creates an increase in static pressure, known as waterhammer, which propagates throughout the propellant system at pressures exceeding nominal design values. A series of development tests conducted at Marshall Space Flight Center in 2009 were performed using a water-flow test article to better understand fluid characteristics of the Upper Stage Reaction Control System. A subset of the tests examined the waterhammer pressure and frequency response in the flight-representative system and provided data to anchor numerical models. This thesis presents a comparison of waterhammer test results with numerical model and analytical results. An overview of the flight system, test article, modeling and analysis are also provided.

  1. The Palladium-Catalyzed Aerobic Kinetic Resolution of Secondary Alcohols: Reaction Development, Scope, and Applications

    KAUST Repository

    Ebner, Davidâ C.

    2009-12-07

    The first palladium-catalyzed enantioselective oxidation of secondary alcohols has been developed, utilizing the readily available diamine (-)-sparteine as a chiral ligand and molecular oxygen as the stoichiometric oxidant. Mechanistic insights regarding the role of the base and hydrogen-bond donors have resulted in several improvements to the original system. Namely, addition of cesium carbonate and tert-butyl alcohol greatly enhances reaction rates, promoting rapid resolutions. The use of chloroform as solvent allows the use of ambient air as the terminal oxidant at 23 degrees C, resulting in enhanced catalyst selectivity. These improved reaction conditions have permitted the successful kinetic resolution of benzylic, allylic, and cyclopropyl secondary alcohols to high enantiomeric excess with good-to-excellent selectivity factors. This catalyst system has also been applied to the desymmetrization of meso-diols, providing high yields of enantioenriched hydroxyketones.

  2. The Palladium-Catalyzed Aerobic Kinetic Resolution of Secondary Alcohols: Reaction Development, Scope, and Applications

    KAUST Repository

    Ebner, Davidâ C.; Bagdanoff, Jeffreyâ T.; Ferreira, Ericâ M.; McFadden, Ryanâ M.; Caspi, Danielâ D.; Trend, Raissaâ M.; Stoltz, Brianâ M.

    2009-01-01

    The first palladium-catalyzed enantioselective oxidation of secondary alcohols has been developed, utilizing the readily available diamine (-)-sparteine as a chiral ligand and molecular oxygen as the stoichiometric oxidant. Mechanistic insights regarding the role of the base and hydrogen-bond donors have resulted in several improvements to the original system. Namely, addition of cesium carbonate and tert-butyl alcohol greatly enhances reaction rates, promoting rapid resolutions. The use of chloroform as solvent allows the use of ambient air as the terminal oxidant at 23 degrees C, resulting in enhanced catalyst selectivity. These improved reaction conditions have permitted the successful kinetic resolution of benzylic, allylic, and cyclopropyl secondary alcohols to high enantiomeric excess with good-to-excellent selectivity factors. This catalyst system has also been applied to the desymmetrization of meso-diols, providing high yields of enantioenriched hydroxyketones.

  3. Thermal lens and all optical switching of new organometallic compound doped polyacrylamide gel

    Science.gov (United States)

    Badran, Hussain Ali

    In this work thermal lens spectrometry (TLS) is applied to investigate the thermo-optical properties of new organometallic compound containing azomethine group, Dichloro bis [2-(2-hydroxybenzylideneamino)-5-methylphenyl] telluride platinum(II), doped polyacrylamide gel using transistor-transistor logic (TTL) modulated cw 532 nm laser beam as an excitation beam modulated at 10 Hz frequency and probe beam wavelength 635 nm at 14 mW. The technique is applied to determine the thermal diffusivities, ds/dT and the linear thermal expansion coefficient of the sample. All-optical switching effects with low background and high stability are demonstrated.

  4. Luminescent Organometallic Nanomaterials with Aggregation-Induced Emission.

    Science.gov (United States)

    Shu, Tong; Wang, Jianxing; Su, Lei; Zhang, Xueji

    2018-07-04

    Recent researches in metal nanoclusters (NCs) have prompted their promising practical applications in biomedical fields as novel inorganic luminophores. More recently, to further improve the photoluminescence (PL) performance of NCs, the aggregation-induced emission (AIE) effect has been introduced to develop highly luminescent metal NCs and metal complex materials. In this review, we start our discussion from recent progresses on AIE materials developments. Then, we address our understandings on the PL properties of thiolated metal NCs. Subsequently, we link thiolated metal NCs with AIE effect. We also highlight some recent advances in synthesizing the AIE-type metal complex nanomaterials. We finally discuss visions and directions for future development of AIE-type metal complex nanomaterials.

  5. Development of styrene divinyl benzene catalyst in isotopic exchange reaction of water and hydrogen

    International Nuclear Information System (INIS)

    Morishita, Teizo; Noda, Shigeyuki; Tan, Tsutomu; Noguchi, Hiroshi

    1982-01-01

    Styrene divinyl benzene copolymer (SDBC) is hydrophobic, and porous with large specific surface area. Utilizing these properties, the SDBC was used for the carrier of catalyst in water-hydrogen exchange reaction process, and the hydrophobic platinum catalyst with very high performance was able to be developed. However, the SDBC is usually fine particles smaller than 1 mm, and is not suitable as the filling catalyst for exchange reaction towers. Therefore, in this study, using only platinum as a catalyst metal, the improvement of the property of carriers was emphatically examined, and platinum bearing was proved with an optical or electron microscope. As the result, it was found that the SDBC catalyst showed high activity practically usable as the hydrophobic catalyst for heavy water or tritium exchange reaction. The characteristics of SDBC are explained. The manufacturing processes of the catalyst by making SDBC carriers with fine particles and letting them bear platinum are described. The results of the trial manufacture of spherical, extrusion-formed and honeycomb carrier catalysts are reported. Platinum must be dispersed over the large specific surface area of SDBC carriers. (Kako, I.)

  6. Development of Capillary Loop Convective Polymerase Chain Reaction Platform with Real-Time Fluorescence Detection

    Directory of Open Access Journals (Sweden)

    Wen-Pin Chou

    2017-02-01

    Full Text Available Polymerase chain reaction (PCR has been one of the principal techniques of molecular biology and diagnosis for decades. Conventional PCR platforms, which work by rapidly heating and cooling the whole vessel, need complicated hardware designs, and cause energy waste and high cost. On the other hand, partial heating on the various locations of vessels to induce convective solution flows by buoyancy have been used for DNA amplification in recent years. In this research, we develop a new convective PCR platform, capillary loop convective polymerase chain reaction (clcPCR, which can generate one direction flow and make the PCR reaction more stable. The U-shaped loop capillaries with 1.6 mm inner diameter are designed as PCR reagent containers. The clcPCR platform utilizes one isothermal heater for heating the bottom of the loop capillary and a CCD device for detecting real-time amplifying fluorescence signals. The stable flow was generated in the U-shaped container and the amplification process could be finished in 25 min. Our experiments with different initial concentrations of DNA templates demonstrate that clcPCR can be applied for precise quantification. Multiple sample testing and real-time quantification will be achieved in future studies.

  7. Synthesis and purification of some main group organometallic ...

    Indian Academy of Sciences (India)

    Unknown

    Novel Materials and Structural Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400 085, India. Abstract. Metal–organic ... of AsH3 in GaAs synthesis; ~ 4 h half life of SbH3 at room temperature) has been a driving force to develop new molecular ... pound). Thermal dissociation of these adducts at an appro-.

  8. Patterns of development of unspecific reaction of cells and modification of chemical protection

    International Nuclear Information System (INIS)

    Veksler, A.M.; Korystov, Yu.N.; Kublik, L.N.; Ehjdus, L.Kh.

    1980-01-01

    A study was made of a correlation between radioprotective efficiency of different chemical agents (weak electrolytes) and conditions of treatment. It was demonstrated that the pattern of changes in the protection efficiency, with modification thereof, is similar to that of the development of unspecific reaction and determined by the intracellular concentration of the chemical agents, which, in turn, is function of physicochemical parameters of the substance and pH gradient between cell and medium. With similar intracellular concentration, caffeine-benzoate, thioglicolic acid and caffeine proved to be equally effective, while the protective effect of cysteamine was appreciably higher

  9. A multi-component reaction towards the development of highly modular hydrogelators.

    Science.gov (United States)

    Sundén, Henrik; Sauvée, Claire; Haukka, Matti; Stöm, Anna

    2018-04-16

    Herein we report a multi-component reaction approach for the development of a new class of hydrogelators based on the OxoTriphenylHexanOate (OTHO) backbone. A focused library of OTHOs has been synthesized and their hydrogelation features evaluated. The two most potent hydrogelators were studied by rheology revealing different gel strengths, appearances and thixotropic behaviours. The new gelators showcase the versatility of the OTHO backbone as a platform for the design of functionalized hydrogels with tunable gel properties. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Characterization and development of an active scintillating target for nuclear reaction studies on actinides

    Energy Technology Data Exchange (ETDEWEB)

    Belier, Gilbert, E-mail: gilbert.belier@cea.fr [CEA, DAM, DIF, DPTA, Centre du Grand Rue, 91297 Arpajon (France); Aupiais, Jean; Varignon, Cyril; Vayre, Sylvain [CEA, DAM, DIF, DPTA, Centre du Grand Rue, 91297 Arpajon (France)

    2012-02-01

    This article presents the development of a new kind of active actinide target, based on organic liquid scintillators containing the dissolved isotope. Amongst many advantages one can mention the very high detection efficiency, the Pulse Shape Discrimination capability, the fast response allowing high count rates and good time resolution and the ease of fabrication. The response of this target to fission fragments has been studied. The discrimination of alpha, fission and proton recoil events is demonstrated. The alpha decay and fission detection efficiencies are simulated and compared to measurements. Finally the use of such a target in the context of fast neutron induced reactions is discussed.

  11. Characterization and development of an active scintillating target for nuclear reaction studies on actinides

    International Nuclear Information System (INIS)

    Belier, Gilbert; Aupiais, Jean; Varignon, Cyril; Vayre, Sylvain

    2012-01-01

    This article presents the development of a new kind of active actinide target, based on organic liquid scintillators containing the dissolved isotope. Amongst many advantages one can mention the very high detection efficiency, the Pulse Shape Discrimination capability, the fast response allowing high count rates and good time resolution and the ease of fabrication. The response of this target to fission fragments has been studied. The discrimination of alpha, fission and proton recoil events is demonstrated. The alpha decay and fission detection efficiencies are simulated and compared to measurements. Finally the use of such a target in the context of fast neutron induced reactions is discussed.

  12. Toxicology of organic-inorganic hybrid molecules: bio-organometallics and its toxicology.

    Science.gov (United States)

    Fujie, Tomoya; Hara, Takato; Kaji, Toshiyuki

    2016-01-01

    Bio-organometallics is a research strategy of biology that uses organic-inorganic hybrid molecules. The molecules are expected to exhibit useful bioactivities based on the unique structure formed by interaction between the organic structure and intramolecular metal(s). However, studies on both biology and toxicology of organic-inorganic hybrid molecules have been incompletely performed. There can be two types of toxicological studies of bio-organometallics; one is evaluation of organic-inorganic hybrid molecules and the other is analysis of biological systems from the viewpoint of toxicology using organic-inorganic hybrid molecules. Our recent studies indicate that cytotoxicity of hybrid molecules containing a metal that is nontoxic in inorganic forms can be more toxic than that of hybrid molecules containing a metal that is toxic in inorganic forms when the structure of the ligand is the same. Additionally, it was revealed that organic-inorganic hybrid molecules are useful for analysis of biological systems important for understanding the toxicity of chemical compounds including heavy metals.

  13. The optical characterization of organometallic complex thin films by spectroscopic ellipsometry and photovoltaic diode application

    Energy Technology Data Exchange (ETDEWEB)

    Özaydın, C. [Batman University, Engineering Faculty, Department of Computer Eng., Batman (Turkey); Güllü, Ö., E-mail: omergullu@gmail.com [Batman University, Science and Art Faculty, Department of Physics, Batman (Turkey); Pakma, O. [Batman University, Science and Art Faculty, Department of Physics, Batman (Turkey); Ilhan, S. [Siirt University, Science and Art Faculty, Department of Chemistry, Siirt (Turkey); Akkılıç, K. [Dicle University, Education Faculty, Department of Physics Education, Diyarbakır (Turkey)

    2016-05-15

    Highlights: • Optical properties and thickness of the A novel organometallic complex (OMC) film were investigated by spectroscopic ellipsometry (SE). • Au/OMC/n-Si metal/interlayer/semiconductor (MIS) diode has been fabricated • This paper presents the I–V analysis of Au/OMC/n-Si MIS diode. • Current–voltage and photovoltaic properties of the diode were investigated. - Abstract: In this work, organometallic complex (OMC) films have been deposited onto glass or silicon substrates by spin coating technique and their photovoltaic application potential has been investigated. Optical properties and thickness of the film have been investigated by spectroscopic ellipsometry (SE). Also, transmittance spectrum has been taken by UV/vis spectrophotometer. The optical method has been used to determine the band gap value of the films. Also, Au/OMC/n-Si metal/interlayer/semiconductor (MIS) diode has been fabricated. Current–voltage and photovoltaic properties of the structure were investigated. The ideality factor (n) and barrier height (Φ{sub b}) values of the diode were found to be 2.89 and 0.79 eV, respectively. The device shows photovoltaic behavior with a maximum open-circuit voltage of 396 mV and a short circuit current of 33.8 μA under 300 W light.

  14. The optical characterization of organometallic complex thin films by spectroscopic ellipsometry and photovoltaic diode application

    International Nuclear Information System (INIS)

    Özaydın, C.; Güllü, Ö.; Pakma, O.; Ilhan, S.; Akkılıç, K.

    2016-01-01

    Highlights: • Optical properties and thickness of the A novel organometallic complex (OMC) film were investigated by spectroscopic ellipsometry (SE). • Au/OMC/n-Si metal/interlayer/semiconductor (MIS) diode has been fabricated • This paper presents the I–V analysis of Au/OMC/n-Si MIS diode. • Current–voltage and photovoltaic properties of the diode were investigated. - Abstract: In this work, organometallic complex (OMC) films have been deposited onto glass or silicon substrates by spin coating technique and their photovoltaic application potential has been investigated. Optical properties and thickness of the film have been investigated by spectroscopic ellipsometry (SE). Also, transmittance spectrum has been taken by UV/vis spectrophotometer. The optical method has been used to determine the band gap value of the films. Also, Au/OMC/n-Si metal/interlayer/semiconductor (MIS) diode has been fabricated. Current–voltage and photovoltaic properties of the structure were investigated. The ideality factor (n) and barrier height (Φ_b) values of the diode were found to be 2.89 and 0.79 eV, respectively. The device shows photovoltaic behavior with a maximum open-circuit voltage of 396 mV and a short circuit current of 33.8 μA under 300 W light.

  15. Interplay between experiments and calculations for organometallic clusters and caged clusters

    International Nuclear Information System (INIS)

    Nakajima, Atsushi

    2015-01-01

    Clusters consisting of 10-1000 atoms exhibit size-dependent electronic and geometric properties. In particular, composite clusters consisting of several elements and/or components provide a promising way for a bottom-up approach for designing functional advanced materials, because the functionality of the composite clusters can be optimized not only by the cluster size but also by their compositions. In the formation of composite clusters, their geometric symmetry and dimensionality are emphasized to control the physical and chemical properties, because selective and anisotropic enhancements for optical, chemical, and magnetic properties can be expected. Organometallic clusters and caged clusters are demonstrated as a representative example of designing the functionality of the composite clusters. Organometallic vanadium-benzene forms a one dimensional sandwich structure showing ferromagnetic behaviors and anomalously large HOMO-LUMO gap differences of two spin orbitals, which can be regarded as spin-filter components for cluster-based spintronic devices. Caged clusters of aluminum (Al) are well stabilized both geometrically and electronically at Al 12 X, behaving as a “superatom”

  16. Iptycenes with an acridinone motif developed through [4+2] cycloaddition of tethered naphthalene and iminoquinone via a radical reaction.

    Science.gov (United States)

    Raju, Selvam; Annamalai, Pratheepkumar; Chen, Pei-Ling; Liu, Yi-Hung; Chuang, Shih-Ching

    2017-06-06

    A new class of iptycenes was developed by combining 2-(naphthalen-1-yl)anilines and p-benzoquinones through copper(ii)-mediated radical cyclisation. This unusual cyclisation reaction resulted in the robust and efficient syntheses of iptycenes with an acridinone motif. These iptycenes can be further transformed into planar acridinone heterocyclics through the Diels-Alder reaction.

  17. A reaction time experiment on adult attachment: The development of a measure for neurophysiological settings

    Directory of Open Access Journals (Sweden)

    Theresia Wichmann

    2016-11-01

    Full Text Available In the last decades, there has been an increase of experimental research on automatic unconscious processes concerning the evaluation of the self and others. Previous research investigated implicit aspects of romantic attachment using self-report measures as explicit instruments for assessing attachment style. There is a lack of experimental procedures feasible for neurobiological settings. We developed a reaction time experiment (RT using a narrative attachment measure with an implicit nature and were interested to capture automatic processes, when the individuals’ attachment system is activated. We aimed to combine attachment methodology with knowledge from implicit measures by using a decision reaction time paradigm. This should serve as a means to capture implicit aspects of attachment. This experiment evaluated participants’ response to prototypic attachment sentences in association with their own attachment classification, measured with the Adult Attachment Projective Picture System (AAP.First the AAP was administered as the standardized interview procedure to 30 healthy participants, which were classified into a secure or insecure group. In the following experimental session, both experimenter and participants were blind with respect to classifications. 128 prototypically secure or insecure sentences related to the 8 pictures of the AAP were presented to the participants. Their response and reaction times were recorded. Based on the response (accept, reject a continuous security scale was defined. Both the AAP classification and security scale were related to the reaction times. Differentiated study hypotheses were confirmed for insecure sentences, which were accepted faster by participants from the insecure attachment group (or with lower security scale, and rejected faster by participants form secure attachment group (or with higher security scale. The elaborating unconscious processes were more activated by insecure sentences with

  18. [The possibility of acute inflammatory reaction affects the development of pressure ulcers in bedridden elderly patients].

    Science.gov (United States)

    Matsuyama, N; Takano, K; Mashiko, T; Jimbo, S; Shimetani, N; Ohtani, H

    1999-11-01

    To test the hypothesis that acute inflammatory reaction associates with the development of pressure ulcers in bedridden elderly patients, 40 hospitalized elderly patients suffering from bacterial pneumonia, cerebrovascular disease, and femoral bone fracture were enrolled in this study. All of them were divided into two groups with pressure ulcers (group P; 17 patients) and without one (group N; 23 patients). The blood samples were taken from them within 5 days after the patients being bedridden. Although no significant difference exist in pressure ulcer risk factors (age, gender, Braden scale, underlying diseases, blood pressure, and heart rate) between the two groups, white blood cell, plasma C-reactive protein and fibrinogen in group P increased significantly as compared with those in group N. Besides number of platelets and maximum platelet aggregation rate were significantly higher in group P than in group N. Serum albumin and hemoglobin of both groups decreased after being bedridden, especially hemoglobin in group P was significantly lower than that in group N. While the concentration of serum IL-6 did not indicate a significant difference between both the groups, serum IL-1 beta increased significantly in group P. In conclusion, we suggested that acute inflammatory reaction releasing proinflammatory cytokines affected the development of pressure ulcer in bedridden elderly patients.

  19. Design of supported bi-metallic nanoparticles based on Platinum and Palladium using Surface Organometallic Chemistry (SOMC)

    KAUST Repository

    Al-Shareef, Reem A.

    2017-01-01

    Well-defined silica supported bimetallic catalysts Pt100-x Pdx (where x is the molar ratio of Pd) are prepared by Surface Organometallic Chemistry (SOMC) via controlled decomposition of Pd2(allyl)2Cl2 on Pt/SiO2. For comparison purposes, Pt100-x Pdx

  20. Organometallic model complexes elucidate the active gallium species in alkane dehydrogenation catalysts based on ligand effects in Ga K-edge XANES

    Energy Technology Data Exchange (ETDEWEB)

    Getsoian, Andrew “Bean”; Das, Ujjal; Camacho-Bunquin, Jeffrey; Zhang, Guanghui; Gallagher, James R.; Hu, Bo; Cheah, Singfoong; Schaidle, Joshua A.; Ruddy, Daniel A.; Hensley, Jesse E.; Krause, Theodore R.; Curtiss, Larry A.; Miller, Jeffrey T.; Hock, Adam S.

    2016-01-01

    Gallium-modified zeolites are known catalysts for the dehydrogenation of alkanes, reactivity that finds industrial application in the aromatization of light alkanes by Ga-ZSM5. While the role of gallium cations in alkane activation is well known, the oxidation state and coordination environment of gallium under reaction conditions has been the subject of debate. Edge shifts in Ga K-edge XANES spectra acquired under reaction conditions have long been interpreted as evidence for reduction of Ga(III) to Ga(I). However, a change in oxidation state is not the only factor that can give rise to a change in the XANES spectrum. In order to better understand the XANES spectra of working catalysts, we have synthesized a series of molecular model compounds and grafted surface organometallic Ga species and compared their XANES spectra to those of gallium-based catalysts acquired under reducing conditions. We demonstrate that changes in the identity and number of gallium nearest neighbors can give rise to changes in XANES spectra similar to those attributed in literature to changes in oxidation state. Specifically, spectral features previously attributed to Ga(I) may be equally well interpreted as evidence for low-coordinate Ga(III) alkyl or hydride species. These findings apply both to gallium-impregnated zeolite catalysts and to silica-supported single site gallium catalysts, the latter of which is found to be active and selective for dehydrogenation of propane and hydrogenation of propylene.

  1. Development and implementation of a critical pathway for prevention of adverse reactions to contrast media for computed tomography

    Energy Technology Data Exchange (ETDEWEB)

    Jang, Keun Jo [Presbyterian Medical Center, Seoul (Korea, Republic of); Kweon, Dae Cheol; Kim, Myeong Goo [Seoul National University Hospital, Seoul (Korea, Republic of); Yoo, Beong Gyu [Wonkwang Health Science College, Iksan (Korea, Republic of)

    2007-03-15

    The purpose of this study is to develop a critical pathway (CP) for the prevention of adverse reactions to contrast media for computed tomography. The CP was developed and implemented by a multidisciplinary group is Seoul National University Hospital. The CP was applied to CT patients. Patients who underwent CT scanning were included in the CP group from March in 2004. The satisfaction of the patients with CP was compared with non-CP groups. We also investigated the degree of satisfaction among the radiological technologists and nurses. The degree of patient satisfaction with the care process increased patient information (24%), prevention of adverse reactions to contrast media (19%), pre-cognitive effect of adverse reactions to contrast media (39%) and information degree of adverse reactions to contrast media (19%). This CP program can be used as one of the patient care tools for reducing the adverse reactions to contrast media and increasing the efficiency of care process in CT examination settings.

  2. Development and implementation of a critical pathway for prevention of adverse reactions to contrast media for computed tomography

    International Nuclear Information System (INIS)

    Jang, Keun Jo; Kweon, Dae Cheol; Kim, Myeong Goo; Yoo, Beong Gyu

    2007-01-01

    The purpose of this study is to develop a critical pathway (CP) for the prevention of adverse reactions to contrast media for computed tomography. The CP was developed and implemented by a multidisciplinary group is Seoul National University Hospital. The CP was applied to CT patients. Patients who underwent CT scanning were included in the CP group from March in 2004. The satisfaction of the patients with CP was compared with non-CP groups. We also investigated the degree of satisfaction among the radiological technologists and nurses. The degree of patient satisfaction with the care process increased patient information (24%), prevention of adverse reactions to contrast media (19%), pre-cognitive effect of adverse reactions to contrast media (39%) and information degree of adverse reactions to contrast media (19%). This CP program can be used as one of the patient care tools for reducing the adverse reactions to contrast media and increasing the efficiency of care process in CT examination settings

  3. Design of supported bi-metallic nanoparticles based on Platinum and Palladium using Surface Organometallic Chemistry (SOMC)

    KAUST Repository

    Al-Shareef, Reem A.

    2017-11-01

    Well-defined silica supported bimetallic catalysts Pt100-x Pdx (where x is the molar ratio of Pd) are prepared by Surface Organometallic Chemistry (SOMC) via controlled decomposition of Pd2(allyl)2Cl2 on Pt/SiO2. For comparison purposes, Pt100-x Pdx bimetallic catalysts is also prepared by ion-exchange (IE). According to the results of STEM, XAS and H2 chemisorption, all bimetallic nanoparticles, prepared using neither SOMC nor IE, produce discrete formation of monometallic species (either Pt or Pd). Most catalysts exhibit a narrow particle size distribution with an average diameter ranging from 1 to 3 nm for samples prepared by IE and from 2 to 5 nm for the ones synthesized by SOMC. For all catalysts investigated in the present work, iso-butane reaction with hydrogen under differential conditions (conversions below 5%) leads to the formation of methane and propane (hydrogenolysis), n-butane (isomerization), and traces of iso-butylene (dehydrogenation). The total rate of reaction decreases with increasing the Pd loading for both catalysts series as a result of decreasing turnover rate (expressed as moles converted per total surface metal per second) of both isomerization and hydrogenolysis. In the case of Pt100-x Pdx(SOMC) catalysts, the results suggest a selective coverage of Pt (100) surface by a Pd layer, followed by a buildup of Pd overcoat onto a Pd layer assuming that each metal keeps its intrinsic catalytic properties. There is no mutual electronic charge transfer between the two metals (DFT). For the PtPd catalysts prepared by IE, the catalytic behavior cannot simply be explained by a surface coverage of highly active Pt metal by less active Pd (not observed), suggesting there is formation of a surface alloy between Pt and Pd collaborated by EXAFS and DFT. The catalytic results are explained by a simple structure activity relationship based on the previously proposed mechanism of C-H bond and C-C Bond activation and cleavage for iso-butane hydrogenolysis

  4. Generation of semicarbazide from natural azine development in foods, followed by reaction with urea compounds.

    Science.gov (United States)

    Abernethy, Grant A

    2015-01-01

    This paper proposes a mechanism to explain the trace levels of natural semicarbazide occasionally observed in foods. The analytical derivative of semicarbazide, 2-nitrobenzaldehyde semicarbazone, is often measured as a metabolite marker to detect the widely banned antibiotic nitrofurazone. However, this marker is not specific as semicarbazide may be present in foods for several reasons other than exposure to nitrofurazone. In some cases, an entirely natural origin of semicarbazide is suspected, although up until now there was no explanation about how semicarbazide could occur naturally. In this work, semicarbazide is proposed as being generated from natural food compounds via an azine intermediate. Hydrazine, in the form of azines or hydrazones, may be generated in dilute aqueous solution from the natural food compounds ammonia, hydrogen peroxide and acetone, following known oxidation chemistry. When this mixture was prepared in the presence of ureas such as allantoin, urea, biuret or hydroxyurea, and then analysed by the standard method for the determination of semicarbazide, 2-nitrobenzaldehyde semicarbazone was detected. 2-Nitrobenzaldehyde aldazine was also found, and it may be a general marker for azines in foods. This proposal, that azine formation is central to semicarbazide development, provides a convergence of the published mechanisms for semicarbazide. The reaction starts with hydrogen peroxide, peracetic acid, atmospheric oxygen or hypochlorite; generates hydrazine either by an oxaziridine intermediate or via the chlorination of ammonia; and then either route may converge on azine formation, followed by reaction with a urea compound. Additionally, carbamate ion may speculatively generate semicarbazide by reaction with hydrazine, which might be a significant route in the case of the hypochlorite treatment of foods or food contact surfaces. Significantly, detection of 2-nitrobenzaldehyde semicarbazone may be somewhat artefactual because semicarbazide can

  5. Development of the SPIKE code for analysis of the sodium-water reaction

    Energy Technology Data Exchange (ETDEWEB)

    Hwang, Sung Tai; Park, Jin Ho; Choi, Jong Hyeun; Kim, Tae Joon [Korea Atomic Energy Research Institute, Taejon (Korea)

    1998-08-01

    In the secondary loop of liquid metal reactors, including SG, water leak into sodium causes the sudden increase of pressure by the H{sub 2} and heat generated from reaction. At few miliseconds after leak, a sharp and short-lived increase of pressure is generated and its propagation depends on the acoustic constraint characteristics of secondary loop. As increasing leak amount of water, another pressure increase is caused by H{sub 2} and its transients depends on the resistance of pressure opening system, such as rupture disc. For prediction of the transients of initial spike pressure, a code of SPIKE was developed. The code was based on the following simplifications and assumptions: combination of total and half release of H{sub 2} rate, spherical shape of H{sub 2} bubble, compressible and Newtonian fluid for sodium. The program was built in FOTRAN language and consisted of 5 modules. Several sample calculations were performed to test the code and to determine the scale down factor of experimental facilities for experimental verification of the code: parameter study of the variables in chemical reaction model, comparison study with results calculated by superposition methods for simple piping structures, comparison study with results calculated by previous researchers, and calculation for KALIMER models of various size. With these calculation results, the generally predicted phenomena of sodium water reaction can be explained and the calculated ones by SPIKE code were well agreed with the previous study. And the scale down factor can be determined. (author). 88 refs., 99 figs., 39 tabs.

  6. Nuclear reactions

    International Nuclear Information System (INIS)

    Lane, A.M.

    1980-01-01

    In reviewing work at Harwell over the past 25 years on nuclear reactions it is stated that a balance has to be struck in both experiment and theory between work on cross-sections of direct practical relevance to reactors and on those relevant to an overall understanding of reaction processes. The compound nucleus and direct process reactions are described. Having listed the contributions from AERE, Harwell to developments in nuclear reaction research in the period, work on the optical model, neutron capture theory, reactions at doorway states with fine structure, and sum-rules for spectroscopic factors are considered in more detail. (UK)

  7. Development of a reduced model of formation reactions in Zr-Al nanolaminates

    KAUST Repository

    Vohra, Manav

    2014-12-15

    A computational model of anaerobic reactions in metallic multilayered systems with an equimolar composition of zirconium and aluminum is developed. The reduced reaction formalism of M. Salloum and O. M. Knio, Combust. Flame 157(2): 288–295 (2010) is adopted. Attention is focused on quantifying intermixing rates based on experimental measurements of uniform ignition as well as measurements of self-propagating front velocities. Estimates of atomic diffusivity are first obtained based on a regression analysis. A more elaborate Bayesian inference formalism is then applied in order to assess the impact of uncertainties in the measurements, potential discrepancies between predictions and observations, as well as the sensitivity of predictions to inferred parameters. Intermixing rates are correlated in terms of a composite Arrhenius law, which exhibits a discontinuity around the Al melting temperature. Analysis of the predictions indicates that Arrhenius parameters inferred for the low-temperature branch lie within a tight range, whereas the parameters of the high-temperature branch are characterized by higher uncertainty. The latter is affected by scatter in the experimental measurements, and the limited range of bilayers where observations are available. For both branches, the predictions exhibit higher sensitivity to the activation energy than the pre-exponent, whose posteriors are highly correlated.

  8. Waterhammer Modeling for the Ares I Upper Stage Reaction Control System Cold Flow Development Test Article

    Science.gov (United States)

    Williams, Jonathan H.

    2010-01-01

    The Upper Stage Reaction Control System provides three-axis attitude control for the Ares I launch vehicle during active Upper Stage flight. The system design must accommodate rapid thruster firing to maintain the proper launch trajectory and thus allow for the possibility to pulse multiple thrusters simultaneously. Rapid thruster valve closure creates an increase in static pressure, known as waterhammer, which propagates throughout the propellant system at pressures exceeding nominal design values. A series of development tests conducted in the fall of 2009 at Marshall Space Flight Center were performed using a water-flow test article to better understand fluid performance characteristics of the Upper Stage Reaction Control System. A subset of the tests examined waterhammer along with the subsequent pressure and frequency response in the flight-representative system and provided data to anchor numerical models. This thesis presents a comparison of waterhammer test results with numerical model and analytical results. An overview of the flight system, test article, modeling and analysis are also provided.

  9. Development of automatic nuclear emulsion plate analysis system and its application to elementary particle reactions, 2

    International Nuclear Information System (INIS)

    Ushida, Noriyuki; Otani, Masashi; Kumazaki, Noriyasu

    1984-01-01

    This system is composed of precise coordinate measuring apparatuses, a stage controller and various peripherals, employing NOVA 4/C as the host computer. The analyzed results are given as the output to a printer or an XY plotter. The data required for experiment, sent from Nagoya University and others, are received by the host computer through an acoustic coupler, and stored in floppy disks. This paper contains simple explanation on the monitor for the events which occur immediately after the on-line measurement ''MTF 1'', the XY plotter and the acoustic coupler, which hold important position in the system in spite of low cost, due to the development of useful program, as those were not described in the previous paper. The three-dimensional reconstruction of tracks and various errors, corrective processing and analytical processing after corrective processing as off-line processing are also described. In addition, the application of the system was made to the E-531 neutrino experiment in Fermi National Accelerator Laboratory, which attempted to measure the life of the charm particles generated in neutrino reaction with a composite equipment composed of nuclear plates and various counters. First, the outline of the equipment, next, the location of neutrino reaction and the surveillance of charm particle decay using MTF program as the analyzing method at the target, and thirdly, the emulsion-counter data fitting are explained, respectively. (Wakatsuki, Y.)

  10. Review on modeling development for multiscale chemical reactions coupled transport phenomena in solid oxide fuel cells

    International Nuclear Information System (INIS)

    Andersson, Martin; Yuan, Jinliang; Sunden, Bengt

    2010-01-01

    A literature study is performed to compile the state-of-the-art, as well as future potential, in SOFC modeling. Principles behind various transport processes such as mass, heat, momentum and charge as well as for electrochemical and internal reforming reactions are described. A deeper investigation is made to find out potentials and challenges using a multiscale approach to model solid oxide fuel cells (SOFCs) and combine the accuracy at microscale with the calculation speed at macroscale to design SOFCs, based on a clear understanding of transport phenomena, chemical reactions and functional requirements. Suitable methods are studied to model SOFCs covering various length scales. Coupling methods between different approaches and length scales by multiscale models are outlined. Multiscale modeling increases the understanding for detailed transport phenomena, and can be used to make a correct decision on the specific design and control of operating conditions. It is expected that the development and production costs will be decreased and the energy efficiency be increased (reducing running cost) as the understanding of complex physical phenomena increases. It is concluded that the connection between numerical modeling and experiments is too rare and also that material parameters in most cases are valid only for standard materials and not for the actual SOFC component microstructures.

  11. Strategies for catalyst development: possibilities of the ``rational approach`` illustrated with partial oxidation reactions

    Energy Technology Data Exchange (ETDEWEB)

    Weiss, W.; Schedel-Niedrig, T.; Schloegl, R. [Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin (Germany). Abt. Oberflaechenphysik

    1998-12-31

    The paper discusses two petrochemical selective oxidation reactions namely the practised formation of styrene (STY) and the desired oxidative functionalisation of propane. The present knowledge about the mode of operation of oxide catalysts is critically considered. The dehydrogenation of ethylbenzene (EB) should be described by an oxidehydration with water acting as oxidant. The potential role of the coke formed during catalytic reaction as co-catalyst will be discussed. Selective oxidation is connected with the participation of lattice oxygen mechanism which transforms unselective gas phase oxygen into selective oxygen. The atomistic description of this process is still quite unclear as well as the electron structural properties of the activated oxygen atom. The Role of solid state acidity as compared to the role of lattice oxygen is much less well investigated modern multiphase-multielement oxide (MMO) catalysts. The rationale is that the significant efforts made to improve current MMO systems by chemical modifications can be very much more fruitful when in a first step the mode of action of a catalyst is clarified on the basis of suitable experiments. Such time-consuming experiments at the beginning of a campaign for catalyst improvement pay back their investment in later stages of the project when strategies of chemical development can be derived on grounds of understanding. (orig.)

  12. Recent progress in the development of a polarized proton target for reactions with radioactive ion beams

    International Nuclear Information System (INIS)

    Urrego-Blanco, J.P.; Bingham, C.R.; Brandt, B. van den; Galindo-Uribarri, A.; Gomez del Campo, J.; Hautle, P.; Konter, J.A.; Padilla-Rodal, E.; Schmelzbach, P.A.

    2007-01-01

    Polarization observables in nuclear reactions with stable beams have provided important information concerning structural properties of nuclei and reaction mechanisms and hold great promise in the context of exotic nuclei. We report on the development of a polarized target based on plastic foils of 20-200 μm thickness to be used with radioactive ion beams. The operation of such a target requires a moderately high magnetic field and very low temperatures. The plastic foil is placed inside a chamber attached to the mixing chamber of a 3 He- 4 He dilution refrigerator. Cooling of the foil is achieved via a superfluid film of 4 He that can be supplied through two capillaries. The chamber has two thin, highly uniform silicon nitride windows. An NMR coil is attached to the target to monitor the polarization. Results of a first test to characterize the target system, using the elastic scattering of 38 MeV 12 C by protons in inverse kinematics are presented

  13. Development of a reduced model of formation reactions in Zr-Al nanolaminates

    KAUST Repository

    Vohra, Manav; Winokur, Justin; Overdeep, Kyle R.; Marcello, Paul; Weihs, Timothy P.; Knio, Omar

    2014-01-01

    A computational model of anaerobic reactions in metallic multilayered systems with an equimolar composition of zirconium and aluminum is developed. The reduced reaction formalism of M. Salloum and O. M. Knio, Combust. Flame 157(2): 288–295 (2010) is adopted. Attention is focused on quantifying intermixing rates based on experimental measurements of uniform ignition as well as measurements of self-propagating front velocities. Estimates of atomic diffusivity are first obtained based on a regression analysis. A more elaborate Bayesian inference formalism is then applied in order to assess the impact of uncertainties in the measurements, potential discrepancies between predictions and observations, as well as the sensitivity of predictions to inferred parameters. Intermixing rates are correlated in terms of a composite Arrhenius law, which exhibits a discontinuity around the Al melting temperature. Analysis of the predictions indicates that Arrhenius parameters inferred for the low-temperature branch lie within a tight range, whereas the parameters of the high-temperature branch are characterized by higher uncertainty. The latter is affected by scatter in the experimental measurements, and the limited range of bilayers where observations are available. For both branches, the predictions exhibit higher sensitivity to the activation energy than the pre-exponent, whose posteriors are highly correlated.

  14. Water Use for Unconventional Energy Development: How Much, What Kind, and to What Reaction?

    Science.gov (United States)

    Grubert, E.

    2017-12-01

    Water resources—access to water, protection of water, and allocation of water in particular—are a major priority for Americans, but water use for the energy sector has not previously been well characterized. Water use and management associated with unconventional energy development is of special interest, in part because it is often new to the locations and contexts where it occurs. This presentation focuses on three major questions about water use for unconventional energy development, drawing on both engineering and anthropological research. First, using results from a recent study of water use for energy in the entire United States, how much water does the US use for unconventional energy resources, and how does that compare with water use for more mature fuel cycles? Second, based on that same study, what kind of water is used for these unconventional energy resource fuel cycles? Specifically, where does the water come from, and what is its quality? Finally, drawing on recent case studies in the US and elsewhere, what has the reaction been to these water uses, and why does that matter? Case studies focused on oil and natural gas resources illustrate societal reactions to issues of both water management, particularly related to induced seismicity associated with produced water injection, and water allocation, particularly related to hydraulic fracturing. Overall, recent work finds that public concern about water used for unconventional energy resources is often better explained by observed or anticipated local impacts and the uncertainty surrounding these impacts than by specifics about quantities, allocation, and management techniques. This work provides both quantitative and qualitative characterization of water management and allocation for unconventional energy development.

  15. Chemiluminescence development after initiation of Maillard reaction in aqueous solutions of glycine and glucose: nonlinearity of the process and cooperative properties of the reaction system

    Science.gov (United States)

    Voeikov, Vladimir L.; Naletov, Vladimir I.

    1998-06-01

    Nonenzymatic glycation of free or peptide bound amino acids (Maillard reaction, MR) plays an important role in aging, diabetic complications and atherosclerosis. MR taking place at high temperatures is accompanied by chemiluminescence (CL). Here kinetics of CL development in MR proceeding in model systems at room temperature has been analyzed for the first time. Brief heating of glycine and D-glucose solutions to t greater than 93 degrees Celsius results in their browning and appearance of fluorescencent properties. Developed In solutions rapidly cooled down to 20 degrees Celsius a wave of CL. It reached maximum intensity around 40 min after the reaction mixture heating and cooling it down. CL intensity elevation was accompanied by certain decoloration of the solution. Appearance of light absorbing substances and development of CL depended critically upon the temperature of preincubation (greater than or equal to 93 degrees Celsius), initial pH (greater than or equal to 11,2), sample volume (greater than or equal to 0.5 ml) and reagents concentrations. Dependence of total counts accumulation on a system volume over the critical volume was non-monotonous. After reaching maximum values CL began to decline, though only small part of glucose and glycin had been consumed. Brief heating of such solutions to the critical temperature resulted in emergence of a new CL wave. This procedure could be repeated in one and the same reaction system for several times. Whole CL kinetic curve best fitted to lognormal distribution. Macrokinetic properties of the process are characteristic of chain reactions with delayed branching. Results imply also, that self-organization occurs in this system, and that the course of the process strongly depends upon boundary conditions and periodic interference in its course.

  16. Development of the Fischer-Tropsch Process: From the Reaction Concept to the Process Book

    Directory of Open Access Journals (Sweden)

    Boyer C.

    2016-05-01

    Full Text Available The process development by IFP Energies nouvelles (IFPEN/ENI/Axens of a Fischer-Tropsch process is described. This development is based on upstream process studies to choose the process scheme, reactor technology and operating conditions, and downstream to summarize all development work in a process guide. A large amount of work was devoted to the catalyst performances on one hand and the scale-up of the slurry bubble reactor with dedicated complementary tools on the other hand. Finally, an original approach was implemented to validate both the process and catalyst on an industrial scale by combining a 20 bpd unit in ENI’s Sannazzaro refinery, with cold mock-ups equivalent to 20 and 1 000 bpd at IFPEN and a special “Large Validation Tool” (LVT which reproduces the combined effect of chemical reaction condition stress and mechanical stress equivalent to a 15 000 bpd industrial unit. Dedicated analytical techniques and a dedicated model were developed to simulate the whole process (reactor and separation train, integrating a high level of complexity and phenomena coupling to scale-up the process in a robust reliable base on an industrial scale.

  17. Development of a system of measuring double-differential cross sections for proton-induced reactions

    Energy Technology Data Exchange (ETDEWEB)

    Harada, M.; Watanabe, Y.; Sato, K. [Kyushu Univ., Fukuoka (Japan); Meigo, S.

    1997-03-01

    We report the present status of a counter telescope and a data acquisition system which are being developed for the measurement of double-differential cross sections of all light-charged particles emitted from proton-induced reactions on {sup 12}C at incident energies less than 90 MeV. The counter telescope consists of an active collimator made of a plastic scintillator, two thin silicon {Delta}E-detectors and a CsI(Tl) E-detectors with photo-diode readout. Signals from each detector are processed using the data acquisition system consisting of the front-end electronics (CAMAC) and two computers connected with the ethernet LAN: a personal computer as the data collector and server, and a UNIX workstation as the monitor and analyzer. (author)

  18. Prevention, development, and control of psychophysical false reactions in cases of imminent or existing catastrophes

    International Nuclear Information System (INIS)

    Brickenstein, R.

    1981-01-01

    If a random group of people or a solid community feel threatened in their economical, ideologic-religious, or physical existences, individual reactions which occur frequently, such as pathologically increased fear, dread can become new common symptoms, the so-called summation phenomenous. Especially general uneasiness, emotional conditions indicating crises and tendency to panic belong to these symptoms. In a mass of people, all preconditions of the development of a panic are existing. This can be acute in the abortive form, but also chronic. Measures of preventing or controlling a panic can be successful only if they take into consideration the genesis and the art of the different sorts of panic. Therefore, it is urgently necessary for any organisatory or political or military leader to know these in order to be able to prevent a catastrophe. (orig.) [de

  19. The preparation of highly active antimicrobial silver nanoparticles by an organometallic approach

    Energy Technology Data Exchange (ETDEWEB)

    Fernandez, Eduardo J; Garcia-Barrasa, Jorge; Lopez-de-Luzuriaga, Jose M; Monge, Miguel [Departamento de Quimica Grupo de SIntesis Quimica de La Rioja, UA-CSIC, Universidad de La Rioja, Complejo CientIfico-Tecnologico, E-26004 Logrono (Spain); Laguna, Antonio [Departamento de Quimica Inorganica, Instituto de Ciencia de Materiales de Aragon, Universidad de Zaragoza-CSIC, E-50009 Zaragoza (Spain); Torres, Carmen [Departamento de Agricultura y Alimentacion, Universidad de La Rioja, Complejo Cientifico-Tecnologico, E-26004 Logrono (Spain)], E-mail: eduardo.fernandez@unirioja.es

    2008-05-07

    Silver nanoparticles of small size with a high surface to volume ratio have been prepared using an organometallic approach. For this, the complex NBu{sub 4}[Ag(C{sub 6}F{sub 5}){sub 2}] has been treated with AgClO{sub 4} in a 1:1 molar ratio, giving rise to the nanoparticle precursor [Ag(C{sub 6}F{sub 5})] in solution. Addition of one equivalent of hexadecylamine (HDA) and 5 h of reflux in toluene leads to a deep yellow solution containing monodisperse silver nanoparticles (Ag NPs) of ca. 10 nm. This approach leads to nanoparticles with almost uncontaminated surfaces which make them very reactive. Antimicrobial studies show that these nanoparticles are very active as antimicrobial agents. Very low concentrations between 12 and 25 {mu}g ml{sup -1} of Ag NPs are enough to produce bacteriostatic and bactericidal effectiveness.

  20. Synthetic strategies for efficient conjugation of organometallic complexes with pendant protein reactive markers

    KAUST Repository

    Jantke, Dominik

    2013-11-01

    Site-directed conjugation of metal centers to proteins is fundamental for biological and bioinorganic applications of transition metals. However, methods for the site-selective introduction of metal centers remain scarce. Herein, we present broadly applicable synthetic strategies for the conjugation of bioactive molecules with a range of organometallic complexes. Following three different synthetic strategies, we were able to synthesize a small library of metal conjugated protein markers featuring different types of protein reactive sites (epoxides, phenylphosphonates, fluorosulfonates and fluorophosphonate groups) as well as different late transition metals (iron, ruthenium, rhodium, palladium and platinum). The products were isolated in moderate to excellent yields and high purity. Furthermore, X-ray diffraction of the metalated protein markers corroborates structural integrity of the metal complex and the protein reactive site. © 2013 Elsevier B.V. All rights reserved.

  1. Zigzag-shaped nickel nanowires via organometallic template-free route

    Energy Technology Data Exchange (ETDEWEB)

    Shviro, Meital; Paszternak, Andras [Bar Ilan Institute of Nanotechnology and Advanced Materials (BINA), Bar Ilan University, Department of Chemistry (Israel); Chelly, Avraham [Bar Ilan Institute of Nanotechnology and Advanced Materials (BINA), Bar Ilan University, Department of Engineering (Israel); Zitoun, David, E-mail: david.zitoun@biu.ac.il [Bar Ilan Institute of Nanotechnology and Advanced Materials (BINA), Bar Ilan University, Department of Chemistry (Israel)

    2013-08-15

    In this manuscript, the formation of nickel nanowires of 10-20 nm in diameter (average size: several tens to hundreds of {mu}m long and 1.0-1.5 {mu}m wide) at low temperature is found to be driven by dewetting of liquid organometallic precursors during spin-coating process and by self-assembly of Ni clusters. Elaboration of metallic thin films by low-temperature deposition technique makes the preparation process compatible with most of the substrates. The use of iron and cobalt precursor shows that the process could be extended to other metallic systems. In this work, AFM and SEM are used to follow the assembly of Ni clusters into straight or zigzag lines. The formation of zigzag structure is specific to the Ni precursor at appropriate preparation parameters. This template-free process allows a control of anisotropic structures with homogeneous sizes and angles on the standard Si/SiO{sub 2} surface.

  2. Organometallics and quaternary ammonium salts affect calcium ion desorption from lecithin liposome membranes

    International Nuclear Information System (INIS)

    Kral, T.E.; Kuczera, J.; Przestalski, S.

    2001-01-01

    The objective of the present work was to compare the effects of groups of tin and lead organometallic compounds and their mixtures with amphiphilic quaternary ammonium salts (QAS) on the process of calcium ion desorption from lecithin liposome membranes, as dependent on the properties of the hydrophilic and hydrophobic parts of QAS. In the investigations the method of radioactive labels was applied. Synergism and antagonism in the action of both groups of compounds were found. The effectiveness of the cooperation depended more on chain length of QAS compounds than on the size and polarity of their hydrophobic parts. The most effective of all compounds studied was a the mixture of benzyldimethylammonium chloride in a mixture with tripropyltin. Since the rate of calcium desorption proved to be a good measure of efficacy of biologically active surfactants, it seems that the conclusions reached in this paper may be useful for choosing compounds which are able to decontaminate the environment polluted with heavy metals. (orig.)

  3. Synthetic strategies for efficient conjugation of organometallic complexes with pendant protein reactive markers

    KAUST Repository

    Jantke, Dominik; Marziale, Alexander N.; Reiner, Thomas; Kraus, Florian; Herdtweck, Eberhardt; Raba, Andreas; Eppinger, Jö rg

    2013-01-01

    Site-directed conjugation of metal centers to proteins is fundamental for biological and bioinorganic applications of transition metals. However, methods for the site-selective introduction of metal centers remain scarce. Herein, we present broadly applicable synthetic strategies for the conjugation of bioactive molecules with a range of organometallic complexes. Following three different synthetic strategies, we were able to synthesize a small library of metal conjugated protein markers featuring different types of protein reactive sites (epoxides, phenylphosphonates, fluorosulfonates and fluorophosphonate groups) as well as different late transition metals (iron, ruthenium, rhodium, palladium and platinum). The products were isolated in moderate to excellent yields and high purity. Furthermore, X-ray diffraction of the metalated protein markers corroborates structural integrity of the metal complex and the protein reactive site. © 2013 Elsevier B.V. All rights reserved.

  4. Hybrid Organometallic-Inorganic Nanomaterial: Acetyl Ferrocene Schiff base Immobilized on Silica Coated Magnetite Nanoparticles

    Directory of Open Access Journals (Sweden)

    M. Masteri-Farahani

    2015-10-01

    Full Text Available In  this  work,  a  new  hybrid  organometallic-inorganic  hybrid nanomaterial was prepared by immobilization of acetyl ferrocene on the  surface  of magnetite  nanoparticles. Covalent  grafting of silica coated magnetite nanoparticles (SCMNPs with 3-aminopropyl triethoxysilane gave aminopropyl-modified magnetite nanoparticles (AmpSCMNPs. Then, Schiff base condensation  of AmpSCMNPs with acetyl  ferrocene resulted in the preparation of acferro-SCMNPs hybrid nanomaterial. Characterization of the prepared nanomaterial was performed with different physicochemical methods such as Fourier transform infrared spectroscopy (FT-IR, X-ray diffraction (XRD, vibrating sample magnetometry (VSM, thermogravimetric analysis (TGA, scanning electron microscopy (SEM, and transmission electron microscopy (TEM. VSM analysis showed superparamagnetic properties of the prepared nanomaterial and TEM and SEM analyses indicated the relatively spherical nanoparticles with 15 nm average size.

  5. The preparation of highly active antimicrobial silver nanoparticles by an organometallic approach

    International Nuclear Information System (INIS)

    Fernandez, Eduardo J; Garcia-Barrasa, Jorge; Lopez-de-Luzuriaga, Jose M; Monge, Miguel; Laguna, Antonio; Torres, Carmen

    2008-01-01

    Silver nanoparticles of small size with a high surface to volume ratio have been prepared using an organometallic approach. For this, the complex NBu 4 [Ag(C 6 F 5 ) 2 ] has been treated with AgClO 4 in a 1:1 molar ratio, giving rise to the nanoparticle precursor [Ag(C 6 F 5 )] in solution. Addition of one equivalent of hexadecylamine (HDA) and 5 h of reflux in toluene leads to a deep yellow solution containing monodisperse silver nanoparticles (Ag NPs) of ca. 10 nm. This approach leads to nanoparticles with almost uncontaminated surfaces which make them very reactive. Antimicrobial studies show that these nanoparticles are very active as antimicrobial agents. Very low concentrations between 12 and 25 μg ml -1 of Ag NPs are enough to produce bacteriostatic and bactericidal effectiveness

  6. Control and Characterization of Titanium Dioxide Morphology: Applications in Surface Organometallic Chemistry

    KAUST Repository

    Jeantelot, Gabriel

    2014-05-01

    Surface Organometallic Chemistry leads to the combination of the high activity and specificity of homogeneous catalysts with the recoverability and practicality of heterogeneous catalysts. Most metal complexes used in this chemistry are grafted on metal oxide supports such as amorphous silica (SiO2) and γ-alumina (Al2O3). In this thesis, we sought to enable the use of titania (TiO2) as a new support for single-site well-defined grafting of metal complexes. This was achieved by synthesizing a special type of anatase-TiO2, bearing a high density of identical hydroxyl groups, through hydrothermal synthesis then post-treatment under high vacuum followed by oxygen flow, and characterized by several analytical techniques including X-ray diffraction, transmission electron microscopy, infrared spectroscopy and nuclear magnetic resonance. Finally, as a proof of concept, the grafting of vanadium oxychloride (VOCl3) was successfully attempted.

  7. Reactive surface organometallic complexes observed using dynamic nuclear polarization surface enhanced NMR spectroscopy

    KAUST Repository

    Pump, Eva; Viger-Gravel, Jasmine; Abou-Hamad, Edy; Samantaray, Manoja; Hamzaoui, Bilel; Gurinov, Andrei; Anjum, Dalaver H.; Gajan, David; Lesage, Anne; Bendjeriou-Sedjerari, Anissa; Emsley, Lyndon; Basset, Jean-Marie

    2016-01-01

    Dynamic Nuclear Polarization Surface Enhanced NMR Spectroscopy (DNP SENS) is an emerging technique that allows access to high-sensitivity NMR spectra from surfaces. However, DNP SENS usually requires the use of radicals as an exogenous source of polarization, which has so far limited applications for organometallic surface species to those that do not react with the radicals. Here we show that reactive surface species can be studied if they are immobilized inside porous materials with suitably small windows, and if bulky nitroxide bi-radicals (here TEKPol) are used as the polarization source and which cannot enter the pores. The method is demonstrated by obtaining significant DNP enhancements from highly reactive complelxes [(equivalent to Si-O-)W(Me)(5)] supported on MCM-41, and effects of pore size (6.0, 3.0 and 2.5 nm) on the performance are discussed.

  8. Reactive surface organometallic complexes observed using dynamic nuclear polarization surface enhanced NMR spectroscopy

    KAUST Repository

    Pump, Eva

    2016-08-15

    Dynamic Nuclear Polarization Surface Enhanced NMR Spectroscopy (DNP SENS) is an emerging technique that allows access to high-sensitivity NMR spectra from surfaces. However, DNP SENS usually requires the use of radicals as an exogenous source of polarization, which has so far limited applications for organometallic surface species to those that do not react with the radicals. Here we show that reactive surface species can be studied if they are immobilized inside porous materials with suitably small windows, and if bulky nitroxide bi-radicals (here TEKPol) are used as the polarization source and which cannot enter the pores. The method is demonstrated by obtaining significant DNP enhancements from highly reactive complelxes [(equivalent to Si-O-)W(Me)(5)] supported on MCM-41, and effects of pore size (6.0, 3.0 and 2.5 nm) on the performance are discussed.

  9. Nitrogen doping of ZnSe by OMVPE using a novel organometallic precursor

    International Nuclear Information System (INIS)

    Akram, S.; Bhat, I.B.; Melas, A.A.

    1994-01-01

    We have investigated phenylhydrazine (PhHz) as a potential nitrogen dopant source in organometallic vapor phase epitaxial growth of ZnSe. Dimethylzinc and dimethylselenide were the zinc and selenium precursors, respectively. Photoluminescence and secondary ion mass spectroscopy measurements indicate that high incorporation efficiency compared to ammonia can be achieved using this dopant source. For example, nitrogen incorporation in the 2.5 x 10 18 /cm -3 level was achieved at 350 degrees C under ultraviolet excitation when the PhHz partial pressure was 1 x 10 -8 atm. These layers had 1-2 x 10 15 /cm -3 electrically active acceptors. Films grown at higher partial pressures of PhHz were highly compensated. 9 refs., 5 figs

  10. Precision design of ethylene- and polar-monomer-based copolymers by organometallic-mediated radical polymerization

    Science.gov (United States)

    Kermagoret, Anthony; Debuigne, Antoine; Jérôme, Christine; Detrembleur, Christophe

    2014-03-01

    The copolymerization of ethylene with polar monomers is a major challenge when it comes to the manufacture of materials with potential for a wide range of commercial applications. In the chemical industry, free-radical polymerization is used to make a large proportion of such copolymers, but the forcing conditions result in a lack of fine control over the architecture of the products. Herein we introduce a synthetic tool, effective under mild experimental conditions, for the precision design of unprecedented ethylene- and polar-monomer-based copolymers. We demonstrate how an organocobalt species can control the growth of the copolymer chains, their composition and the monomer distribution throughout the chain. By fine tuning the ethylene pressure during polymerization and by exploiting a unique reactive mode of the end of the organometallic chain, novel block-like copolymer structures can be prepared. This highly versatile synthetic platform provides access to a diverse range of polymer materials.

  11. Iron-Mediated Homogeneous ICAR ATRP of Methyl Methacrylate under ppm Level Organometallic Catalyst Iron(III Acetylacetonate

    Directory of Open Access Journals (Sweden)

    Jian Wu

    2016-01-01

    Full Text Available Atom Transfer Radical Polymerization (ATRP is an important polymerization process in polymer synthesis. However, a typical ATRP system has some drawbacks. For example, it needs a large amount of transition metal catalyst, and it is difficult or expensive to remove the metal catalyst residue in products. In order to reduce the amount of catalyst and considering good biocompatibility and low toxicity of the iron catalyst, in this work, we developed a homogeneous polymerization system of initiators for continuous activator regeneration ATRP (ICAR ATRP with just a ppm level of iron catalyst. Herein, we used oil-soluble iron (III acetylacetonate (Fe(acac3 as the organometallic catalyst, 1,1′-azobis (cyclohexanecarbonitrile (ACHN with longer half-life period as the thermal initiator, ethyl 2-bromophenylacetate (EBPA as the initiator, triphenylphosphine (PPh3 as the ligand, toluene as the solvent and methyl methacrylate (MMA as the model monomer. The factors related with the polymerization system, such as concentration of Fe(acac3 and ACHN and polymerization kinetics, were investigated in detail at 90 °C. It was found that a polymer with an acceptable molecular weight distribution (Mw/Mn = 1.43 at 45.9% of monomer conversion could be obtained even with 1 ppm of Fe(acac3, making it needless to remove the residual metal in the resultant polymers, which makes such an ICAR ATRP process much more industrially attractive. The “living” features of this polymerization system were further confirmed by chain-extension experiment.

  12. Development of fast reactor containment safety analysis code, CONTAIN-LMR. (3) Improvement of sodium-concrete reaction model

    International Nuclear Information System (INIS)

    Kawaguchi, Munemichi; Doi, Daisuke; Seino, Hiroshi; Miyahara, Shinya

    2015-01-01

    A computer code, CONTAIN-LMR, is an integrated analysis tool to predict the consequence of severe accident in a liquid metal fast reactor. Because a sodium-concrete reaction behavior is one of the most important phenomena in the accident, a Sodium-Limestone Concrete Ablation Model (SLAM) has been developed and installed into the original CONTAIN code at Sandia National Laboratories (SNL) in the U.S. The SLAM treats chemical reaction kinetics between the sodium and the concrete compositions mechanistically using a three-region model, containing a pool (sodium and reaction debris) region, a dry (boundary layer (B/L) and dehydrated concrete) region, and a wet (hydrated concrete) region, the application is limited to the reaction between sodium and limestone concrete. In order to apply SLAM to the reaction between sodium and siliceous concrete which is an ordinary structural concrete in Japan, the chemical reaction kinetics model has been improved to consider the new chemical reactions between sodium and silicon dioxide. The improved model was validated to analyze a series of sodium-concrete experiments which were conducted in Japan Atomic Energy Agency (JAEA). It has been found that relatively good agreement between calculation and experimental results is obtained and the CONTAIN-LMR code has been validated with regard to the sodium-concrete reaction phenomena. (author)

  13. Subsequent development of the normal temperature fusion reaction. Joon kakuyugo sonogo no shinten

    Energy Technology Data Exchange (ETDEWEB)

    Matsumoto, T. (Hokkaido University, Sapporo (Japan). Faculty of Engineering)

    1991-04-24

    This paper reports on a NATTOH model made public in May 1989 by T. Matsumoto who took notice of abnormality of the normal temperature fusion reaction. The NATTO model is based on a chain reaction by hydrogen with a hydrogen-catalyzed fusion reaction which is the normal temperature fusion reaction as an elementary process. If a high temperature fusion reaction is a small-size simulation of the fusion reaction rising on the surface of the sparkling star like the sun, the normal temperature fusion reaction can be a small-size simulation of the phenomena in the last years of the star in the far distance of the space. This gives reality to the normal temperature fusion reaction. The reaction mechanism of the normal temperature fusion reaction is almost being clarified by a NATTOH model. There remain problems on a possibility of generation of unknown radioactive rays and identification of radioactive wastes, but it seems that a prospect of commercialization can be talked about now. As for the utilization as energy, sea water may be used as it is. 10 ref., 5 figs.

  14. Development of 99mTc extraction techniques from 99Mo by (n,γ) reaction

    International Nuclear Information System (INIS)

    Kimura, Akihiro; Hori, Naohiko; Tsuchiya, Kunihiko; Ishihara, Masahiro; Yamabayashi, Hisamichi; Tanase, Masakazu; Fujisaki, Saburo; Sato, Yuichi

    2010-11-01

    Investigation of production method of 99 Mo by (n, γ) reaction, where the processing is relatively simple and generating less amount of radioactive waste, is conducted in the Neutron Irradiation and Testing Reactor Center. The 99 Mo is adsorbed to highly efficient adsorbent PZC after neutron irradiation and 99m Tc is eluted. However, radioactivity concentration of the 99m Tc solution obtained from PZC column loaded with 99 Mo derived by (n, γ) method is lower than that obtained from alumina column with 99 Mo by (n, f) method due to extremely low specific activity of (n, f) 99 Mo. Therefore, it is necessary to develop technique for increasing the amount of 99 Mo and the 99m Tc solution of high radioactivity concentration (minimum: 1Ci/ cm 3 ). In this study, the preliminary fabrication tests using high density MoO 3 pellets were carried out to increase the production of 99 Mo. The method of concentrating 99m Tc solution through solvent extraction with MEK was investigated and a device for this concentration process was also developed. In the preliminary tests of the MoO 3 pellets, the pellets having high density were successfully fabricated by the SPS method. Additionally, it was ascertained that the pellets can be dissolved with 6M-NaOH solution completely. The test for 99 Mo adsorption followed by 99m Tc elution using PZC was carried out. As the result, amount of Mo adsorbed to 1g-PZC was about 250mg, and 99m Tc yield was about 80%. In the concentration test using Re solution instead of 99m Tc solution, it was ascertained that the concentration efficiency is higher than 80% of the theoretical value. A concentration device for 99m Tc solution could be realized based on the method employed in the present experiments. The outcomes of development of 99m Tc extraction techniques from 99 Mo by (n,γ) reaction was reviewed in this paper, and the contents were presented in the 3rd International Symposium on Material Test Reactors. (author)

  15. Development of interactive graphic user interfaces for modeling reaction-based biogeochemical processes in batch systems with BIOGEOCHEM

    Science.gov (United States)

    Chang, C.; Li, M.; Yeh, G.

    2010-12-01

    The BIOGEOCHEM numerical model (Yeh and Fang, 2002; Fang et al., 2003) was developed with FORTRAN for simulating reaction-based geochemical and biochemical processes with mixed equilibrium and kinetic reactions in batch systems. A complete suite of reactions including aqueous complexation, adsorption/desorption, ion-exchange, redox, precipitation/dissolution, acid-base reactions, and microbial mediated reactions were embodied in this unique modeling tool. Any reaction can be treated as fast/equilibrium or slow/kinetic reaction. An equilibrium reaction is modeled with an implicit finite rate governed by a mass action equilibrium equation or by a user-specified algebraic equation. A kinetic reaction is modeled with an explicit finite rate with an elementary rate, microbial mediated enzymatic kinetics, or a user-specified rate equation. None of the existing models has encompassed this wide array of scopes. To ease the input/output learning curve using the unique feature of BIOGEOCHEM, an interactive graphic user interface was developed with the Microsoft Visual Studio and .Net tools. Several user-friendly features, such as pop-up help windows, typo warning messages, and on-screen input hints, were implemented, which are robust. All input data can be real-time viewed and automated to conform with the input file format of BIOGEOCHEM. A post-processor for graphic visualizations of simulated results was also embedded for immediate demonstrations. By following data input windows step by step, errorless BIOGEOCHEM input files can be created even if users have little prior experiences in FORTRAN. With this user-friendly interface, the time effort to conduct simulations with BIOGEOCHEM can be greatly reduced.

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

    International Nuclear Information System (INIS)

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

    2010-01-01

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

  17. Development of reaction-sintered SiC mirror for space-borne optics

    Science.gov (United States)

    Yui, Yukari Y.; Kimura, Toshiyoshi; Tange, Yoshio

    2017-11-01

    We are developing high-strength reaction-sintered silicon carbide (RS-SiC) mirror as one of the new promising candidates for large-diameter space-borne optics. In order to observe earth surface or atmosphere with high spatial resolution from geostationary orbit, larger diameter primary mirrors of 1-2 m are required. One of the difficult problems to be solved to realize such optical system is to obtain as flat mirror surface as possible that ensures imaging performance in infrared - visible - ultraviolet wavelength region. This means that homogeneous nano-order surface flatness/roughness is required for the mirror. The high-strength RS-SiC developed and manufactured by TOSHIBA is one of the most excellent and feasible candidates for such purpose. Small RS-SiC plane sample mirrors have been manufactured and basic physical parameters and optical performances of them have been measured. We show the current state of the art of the RS-SiC mirror and the feasibility of a large-diameter RS-SiC mirror for space-borne optics.

  18. Recent developments of nano-structured materials as the catalysts for oxygen reduction reaction

    Science.gov (United States)

    Kang, SungYeon; Kim, HuiJung; Chung, Yong-Ho

    2018-04-01

    Developments of high efficient materials for electrocatalyst are significant topics of numerous researches since a few decades. Recent global interests related with energy conversion and storage lead to the expansion of efforts to find cost-effective catalysts that can substitute conventional catalytic materials. Especially, in the field of fuel cell, novel materials for oxygen reduction reaction (ORR) have been noticed to overcome disadvantages of conventional platinum-based catalysts. Various approaching methods have been attempted to achieve low cost and high electrochemical activity comparable with Pt-based catalysts, including reducing Pt consumption by the formation of hybrid materials, Pt-based alloys, and not-Pt metal or carbon based materials. To enhance catalytic performance and stability, numerous methods such as structural modifications and complex formations with other functional materials are proposed, and they are basically based on well-defined and well-ordered catalytic active sites by exquisite control at nanoscale. In this review, we highlight the development of nano-structured catalytic materials for ORR based on recent findings, and discuss about an outlook for the direction of future researches.

  19. Bipodal surface organometallic complexes with surface N-donor ligands and application to the catalytic cleavage of C-H and C-C bonds in n -Butane

    KAUST Repository

    Bendjeriou-Sedjerari, Anissa

    2013-11-27

    We present a new generation of "true vicinal" functions well-distributed on the inner surface of SBA15: [(Sî - Si-NH 2)(≡Si-OH)] (1) and [(≡Si-NH2)2] (2). From these amine-modified SBA15s, two new well-defined surface organometallic species [(≡Si-NH-)(≡Si-O-)]Zr(CH2tBu) 2 (3) and [(≡Si-NH-)2]Zr(CH2tBu) 2 (4) have been obtained by reaction with Zr(CH2tBu) 4. The surfaces were characterized with 2D multiple-quantum 1H-1H NMR and infrared spectroscopies. Energy-filtered transmission electron microscopy (EFTEM), mass balance, and elemental analysis unambiguously proved that Zr(CH2tBu)4 reacts with these vicinal amine-modified surfaces to give mainly bipodal bis(neopentyl)zirconium complexes (3) and (4), uniformly distributed in the channels of SBA15. (3) and (4) react with hydrogen to give the homologous hydrides (5) and (6). Hydrogenolysis of n-butane catalyzed by these hydrides was carried out at low temperature (100 C) and low pressure (1 atm). While (6) exhibits a bis(silylamido)zirconium bishydride, [(≡Si-NH-)2]Zr(H) 2 (6a) (60%), and a bis(silylamido)silyloxozirconium monohydride, [(≡Si-NH-)2(≡Si-O-)]ZrH (6b) (40%), (5) displays a new surface organometallic complex characterized by an 1H NMR signal at 14.46 ppm. The latter is assigned to a (silylimido)(silyloxo)zirconium monohydride, [(≡Si-Nî)(≡Si-O-)]ZrH (5b) (30%), coexistent with a (silylamido)(silyloxo)zirconium bishydride, [(≡Si-NH-)(≡Si-O-)] Zr(H)2 (5a) (45%), and a silylamidobis(silyloxo)zirconium monohydride, [(≡Si-NH-)(≡Si-O-)2]ZrH (5c) (25%). Surprisingly, nitrogen surface ligands possess catalytic properties already encountered with silicon oxide surfaces, but interestingly, catalyst (5) with chelating [N,O] shows better activity than (6) with chelating [N,N]. © 2013 American Chemical Society.

  20. Bipodal surface organometallic complexes with surface N-donor ligands and application to the catalytic cleavage of C-H and C-C bonds in n -Butane

    KAUST Repository

    Bendjeriou-Sedjerari, Anissa; Azzi, Joachim; Abou-Hamad, Edy; Anjum, Dalaver H.; Pasha, Fahran A.; Huang, Kuo-Wei; Emsley, Lyndon; Basset, Jean-Marie

    2013-01-01

    We present a new generation of "true vicinal" functions well-distributed on the inner surface of SBA15: [(Sî - Si-NH 2)(≡Si-OH)] (1) and [(≡Si-NH2)2] (2). From these amine-modified SBA15s, two new well-defined surface organometallic species [(≡Si-NH-)(≡Si-O-)]Zr(CH2tBu) 2 (3) and [(≡Si-NH-)2]Zr(CH2tBu) 2 (4) have been obtained by reaction with Zr(CH2tBu) 4. The surfaces were characterized with 2D multiple-quantum 1H-1H NMR and infrared spectroscopies. Energy-filtered transmission electron microscopy (EFTEM), mass balance, and elemental analysis unambiguously proved that Zr(CH2tBu)4 reacts with these vicinal amine-modified surfaces to give mainly bipodal bis(neopentyl)zirconium complexes (3) and (4), uniformly distributed in the channels of SBA15. (3) and (4) react with hydrogen to give the homologous hydrides (5) and (6). Hydrogenolysis of n-butane catalyzed by these hydrides was carried out at low temperature (100 C) and low pressure (1 atm). While (6) exhibits a bis(silylamido)zirconium bishydride, [(≡Si-NH-)2]Zr(H) 2 (6a) (60%), and a bis(silylamido)silyloxozirconium monohydride, [(≡Si-NH-)2(≡Si-O-)]ZrH (6b) (40%), (5) displays a new surface organometallic complex characterized by an 1H NMR signal at 14.46 ppm. The latter is assigned to a (silylimido)(silyloxo)zirconium monohydride, [(≡Si-Nî)(≡Si-O-)]ZrH (5b) (30%), coexistent with a (silylamido)(silyloxo)zirconium bishydride, [(≡Si-NH-)(≡Si-O-)] Zr(H)2 (5a) (45%), and a silylamidobis(silyloxo)zirconium monohydride, [(≡Si-NH-)(≡Si-O-)2]ZrH (5c) (25%). Surprisingly, nitrogen surface ligands possess catalytic properties already encountered with silicon oxide surfaces, but interestingly, catalyst (5) with chelating [N,O] shows better activity than (6) with chelating [N,N]. © 2013 American Chemical Society.

  1. Structure of organometallic compounds obtained by plasma of titanium isopropoxide; Estructura de compuestos organometalicos obtenidos por plasma de isopropoxido de titanio

    Energy Technology Data Exchange (ETDEWEB)

    Arreola R, M. L.

    2012-07-01

    This work presents a study on the synthesis and characterization of organometallic compounds of titanium oxide obtained from glow discharges of titanium tetraisopropoxide (TTIP) and water on glass and polyethylene. The objective is the synthesis of titanium oxide particles which can be fixed on different supports for use in further studies of contaminants degradation in effluent streams. The synthesis was carried out by plasma in a glass tubular reactor of 750 cm{sup 3} and 15 cm length at 10{sup -1} mbar with power between 100 and 150 W during 2, 3 and 4 h. The precursors were TTIP and water vapor. TTIP is an organometallic compound composed of a central atom of Ti surrounded by 4 O atoms, which in turn are connected with chains of 3 C (propane s). The objective is the use of plasma collisions to separate the organic and inorganic phases of TTIP, so that both structure independently in a single material. The result was the formation of white titanium oxide powder composed with agglomerates of spherical particles with average diameter between 160 and 452 nm adhered to small films. The agglomerates have a tendency to change from film to particles with the energy applied to the synthesis. The study of the chemical structure showed a great presence of O{sub 2}-Ti-O{sub 2} (Ti surrounded by O) which can be found in most titanium oxides. Other chemical groups belonging to the organic phase were C=C=C, C=C=O and C{sub 2}-C-Ch appearing from the dehydrogenation of TTIP, which can be a possible precursor of this reactions kind. The structural superficial analyses showed that the atomic composition varies according to type of substrate used. The greatest content of Ti was obtained on glass substrates. However, the synthesis conditions had not evident effect in the participation of chemical states found in the inorganic phase. The crystalline studies indicated that the material is amorphous, although the de convoluted X-ray spectra showed that the synthesized titanium oxides

  2. Development and implementation of a three-choice serial reaction time task for zebrafish (Danio rerio).

    Science.gov (United States)

    Parker, Matthew O; Millington, Mollie E; Combe, Fraser J; Brennan, Caroline H

    2012-02-01

    Zebrafish are an established and widely utilized developmental genetic model system, but limitations in developed behavioral assays have meant that their potential as a model in behavioral neuroscience has yet to be fully realized. Here, we describe the development of a novel operant behavioral assay to examine a variety of aspects of stimulus control in zebrafish using a 3 choice serial reaction time task (3 CSRTT). Fish were briefly exposed to three spatially distinct, but perceptually identical stimuli, presented in a random order after a fixed-time inter-trial interval (ITI). Entries to the correct response aperture either during the stimulus presentation, or within a brief limited hold period following presentation, were reinforced with illumination of the magazine light and delivery of a small food reward. Following training, premature responding was probed with a long-ITI session three times; once at baseline, once following a saline injection and once following an injection of a low dose of amphetamine (AMPH; 0.025 mg/kg). We predicted that if premature responding was related to impulsivity (as in rodents) it would be reduced following the AMPH injection. Results confirmed that zebrafish could learn to perform a complex operant task similar to tasks developed for rodents which are used to probe sustained attention and impulsivity, but the results from the AMPH trials were inconclusive. This study provides the foundations for development and further validation of this species as a model for some aspects of human attentional and impulse control disorders, such as substance abuse disorder. Copyright © 2011 Elsevier B.V. All rights reserved.

  3. Thermally-induced amphibole reaction rim development: EBSD insights into microlite orientation

    Science.gov (United States)

    De Angelis, Sarah; Lavallée, Yan; Larsen, Jessica; Mariani, Elisabetta

    2014-05-01

    Amphibole is an important mineral present in many calc-alkaline volcanic deposits. A hydrous phase, volcanic amphibole is only stable at pressures greater than 100 MPa (approx. 4 km), temperature less than ~860-870 oC, and in melts containing at least 4 wt % H2O. When removed from their thermal and barometric stability field, amphiboles decompose to form aggregate rims of anhydrous minerals. The thickness, texture, and mineralogy of these rims are thought to be reflective of the process driving amphibole disequilibrium (e.g. heating, decompression, etc). However, significant overlap in rim thicknesses and microlite textures means that distinguishing between processes it not simple. This study employed backscatter diffraction (EBSD) to examine both experimental heating-indced amphibole reaction rims and natural amphibole reaction rim from Augustine Volcano. We collected crystal orientation maps of amphibole reaction rims to investigate if different types of disequilibrium produce different patterns of microlite orientation. We identified two types of reaction rim: Type 1- reaction rim microlites are generally oriented at random and share little or no systematic relationship with the crystallographic orientation of the host amphibole, and; Type 2- reaction rim microlites exhibit a topotactic relationship with the host amphibole (they share the same crystallographic orientation). Experimentally produced heating reaction rims are without exception Type 2. However the natural reaction rims are evenly distributed between Types 1 and 2. Further experimental data on decompression induced reaction rim formation is needed to investigate if Type 1 reaction rims resemble the breakdown of amphibole due to decompression. If so, reaction rim microlite orientation could provide a clear method for distinguishing between heating and decompression processes in amphibole bearing magmas.

  4. Ni-O4 species anchored on N-doped graphene-based materials as molecular entities and electrocatalytic performances for oxygen reduction reaction

    Science.gov (United States)

    Jang, Dawoon; Lee, Seungjun; Shin, Yunseok; Ohn, Saerom; Park, Sunghee; Lim, Donggyu; Park, Gilsoo; Park, Sungjin

    2017-12-01

    The generation of molecular active species on the surface of nano-materials has become promising routes to produce efficient electrocatalysts. Development of cost-effective catalysts with high performances for oxygen reduction reaction (ORR) is an important challenge for fuel cell and metal-air battery applications. In this work, we report a novel hybrid produced by room-temperature solution processes using Ni-based organometallic molecules and N-doped graphene-based materials. Chemical and structural characterizations reveal that Ni-containing species are well-dispersed on the surface of graphene network as molecular entity. The hybrid shows excellent electrocatalytic performances for ORR in basic medium with an onset potential of 0.87 V (vs. RHE), superior durability and good methanol tolerance.

  5. Proceedings of the Fifth AASPP Workshop on Asian Nuclear Reaction Database Development

    International Nuclear Information System (INIS)

    Saxena, Alok

    2015-02-01

    The Fifth AASPP Workshop on Asian Nuclear Reaction Database Development was organized by Nuclear Data Physics Centre of India in cooperation with the IAEA and the Board of Research in Nuclear Sciences, Department of Atomic Energy from 22-24 Sept., 2014 at Bhabha Atomic Research Centre, Mumbai, India. Over seventy participants took part in the workshop representing India, Japan, Republic of Korea, Vietnam, Kazakhstan, Uzbekistan, Mongolia and a representative from the IAEA. The workshop covered the overview of nuclear data activities in different countries and covered the topics related to experiments performed using various facilities, the upcoming and existing accelerators and experimental facilities, EXFOR compilation activities, reactor sensitivity studies to nuclear data, criticality benchmarking studies, nuclear data requirement of nuclear power reactors, theoretical calculations using various codes, and covariances in nuclear data. About thirty five talks were delivered by participants from various countries on these topics. The concluding session had a panel discussion on possible future collaboration involving participants from different countries. The present report gives summary of each presentation. (author)

  6. Polymerase chain reaction as a tool for developing stress protein probes

    Energy Technology Data Exchange (ETDEWEB)

    Cochrane, B.J.; Mattley, Y.D. (Univ. of South Florida, Tampa, FL (United States). Dept. of Biology); Snell, T.W. (Georgia Inst. of Tech., Atlanta, GA (United States). Div. of Biology)

    1994-08-01

    Because of the high degree of evolutionary conservation of stress proteins, potential exists for the development of nucleic acid probes from particular species that could be used to monitor stress-related changes in mRNA abundance. The polymerase chain reaction (PCR) is a powerful tool that can be applied to the generation of these probes, provided that primer sequences can be identified that specifically amplify sequences of interest from a wide variety of organisms. The authors identified such sequences from multiple alignments of published chaperonin and stress-70 sequences, and tested their ability to amplify appropriately sized fragments from genomic DNA from a variety of vertebrates and invertebrates. Although no primer pair could be used successfully with all species, the authors were able to derive specific products from most species by testing different pairs. One primer pair for chaperonin proved particularly useful. Products were obtained from all tested species, and with a single exception (human), these primers appeared to amplify a single copy sequence. The authors determined the nucleotide sequence of the product obtained from the rotifer Brachionus plicatilis and determined by phylogenetic analysis of the inferred protein product that the product obtained is most likely derived from a rotifer DNA template. Finally, the authors show that this product can be used to detect changes in abundance of homologous mRNA in heat-stressed rotifers.

  7. Non-Toxic Dual Thrust Reaction Control Engine Development for On-Orbit APS Applications

    Science.gov (United States)

    Robinson, Philip J.; Veith, Eric M.

    2003-01-01

    A non-toxic dual thrust proof-of-concept demonstration engine was successfully tested at the Aerojet Sacramento facility under a technology contract sponsored by the National Aeronautics and Space Administration's (NASA) Marshall Space Flight Center (MSFC). The goals of the NASA MSFC contract (NAS8-01109) were to develop and expand the technical maturity of a non-toxic, on-orbit auxiliary propulsion system (APS) thruster under the Next Generation Launch Technology (NGLT) program. The demonstration engine utilized the existing Kistler K-1 870 lbf LOX/Ethanol orbital maneuvering engine ( O m ) coupled with some special test equipment (STE) that enabled engine operation at 870 lbf in the primary mode and 25 lbf in the vernier mode. Ambient testing in primary mode varied mixture ratio (MR) from 1.28 to 1.71 and chamber pressure (P(c) from 110 to 181 psia, and evaluated electrical pulse widths (EPW) of 0.080, 0.100 and 0.250 seconds. Altitude testing in vernier mode explored igniter and thruster pulsing characteristics, long duration steady state operation (greater than 420 sec) and the impact of varying the percent fuel film cooling on vernier performance and chamber thermal response at low PC (4 psia). Data produced from the testing provided calibration of the performance and thermal models used in the design of the next version of the dual thrust Reaction Control Engine (RCE).

  8. Development of a real time polymerase chain reaction for quantitation of Schistosoma mansoni DNA

    Directory of Open Access Journals (Sweden)

    Ana Lisa do Vale Gomes

    2006-10-01

    Full Text Available This report describes the development of a SYBR Green I based real time polymerase chain reaction (PCR protocol for detection on the ABI Prism 7000 instrument. Primers targeting the gene encoding the SSU rRNA were designed to amplify with high specificity DNA from Schistosoma mansoni, in a real time quantitative PCR system. The limit of detection of parasite DNA for the system was 10 fg of purified genomic DNA, that means less than the equivalent to one parasite cell (genome ~580 fg DNA. The efficiency was 0.99 and the correlation coefficient (R² was 0.97. When different copy numbers of the target amplicon were used as standards, the assay could detect at least 10 copies of the specific target. The primers used were designed to amplify a 106 bp DNA fragment (Tm 83ºC. The assay was highly specific for S. mansoni, and did not recognize DNA from closely related non-schistosome trematodes. The real time PCR allowed for accurate quantification of S. mansoni DNA and no time-consuming post-PCR detection of amplification products by gel electrophoresis was required. The assay is potentially able to quantify S. mansoni DNA (and indirectly parasite burden in a number of samples, such as snail tissue, serum and feces from patients, and cercaria infested water. Thus, these PCR protocols have potential to be used as tools for monitoring of schistosome transmission and quantitative diagnosis of human infection.

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

    Directory of Open Access Journals (Sweden)

    Yang Gao

    2014-01-01

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

  10. Progress in biocatalysis with immobilized viable whole cells: systems development, reaction engineering and applications

    Czech Academy of Sciences Publication Activity Database

    Polakovič, M.; Švitel, J.; Bučko, M.; Filip, J.; Neděla, Vilém; Ansorge-Schumacher, M.B.; Gemeiner, P.

    2017-01-01

    Roč. 39, č. 5 (2017), s. 667-683 ISSN 0141-5492 Institutional support: RVO:68081731 Keywords : biocatalysis * immobilization methods * immobilized whole-cell biocatalyst * multienzyme cascade reactions * process economics * reaction engineering Subject RIV: JA - Electronics ; Optoelectronics, Electrical Engineering OBOR OECD: Bioprocessing technologies (industrial processes relying on biological agents to drive the process) biocatalysis, fermentation Impact factor: 1.730, year: 2016

  11. Adverse Reactions in Allogeneic Blood Donors: A Tertiary Care Experience from a Developing Country

    OpenAIRE

    Sultan, Sadia; Baig, Mohammad Amjad; Irfan, Syed Mohammed; Ahmed, Syed Ijlal; Hasan, Syeda Faiza

    2016-01-01

    Objectives: Fragmented blood transfusion services along with an unmotivated blood donation culture often leads to blood shortage. Donor retention is crucial to meet the increasing blood demand, and adverse donor reactions have a negative impact on donor return. The aim of this study was to estimate adverse donor reactions and identify any demographic association.   Methods: We conducted a prospective study between January 2011 and December 2013. A total of 41,759 healthy donors were enrol...

  12. 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.

  13. Development, improvement and calibration of neutronic reaction rates measurements: elaboration of a standard techniques basis

    International Nuclear Information System (INIS)

    Hudelot, J.P.

    1998-06-01

    In order to improve and to validate the neutronics calculation schemes, perfecting integral measurements of neutronics parameters is necessary. This thesis focuses on the conception, the improvement and the development of neutronics reaction rates measurements, and aims at building a base of standard techniques. Two subjects are discussed. The first one deals with direct measurements by fission chambers. A short presentation of the different usual techniques is given. Then, those last ones are applied through the example of doubling time measurements on the EOLE facility during the MISTRAL 1 experimental programme. Two calibration devices of fission chambers are developed: a thermal column located in the central part of the MINERVE facility, and a calibration cell using a pulsed high flux neutron generator and based on the discrimination of the energy of the neutrons with a time-of-flight method. This second device will soon allow to measure the mass of fission chambers with a precision of about 1 %. Finally, the necessity of those calibrations will be shown through spectral indices measurements in core MISTRAL 1 (UO 2 ) and MISTRAL 2 (MOX) of the EOLE facility. In each case, the associated calculation schemes, performed using the Monte Carlo MCNP code with the ENDF-BV library, will be validated. Concerning the second one, the goal is to develop a method for measuring the modified conversion ratio of 238 U (defined as the ratio of 238 U capture rate to total fission rate) by gamma-ray spectrometry of fuel rods. Within the framework of the MISTRAL 1 and MISTRAL 2 programmes, the measurement device, the experimental results and the spectrometer calibration are described. Furthermore, the MCNP calculations of neutron self-shielding and gamma self-absorption are validated. It is finally shown that measurement uncertainties are better than 1 %. The extension of this technique to future modified conversion ratio measurements for 242 Pu (on MOX rods) and 232 Th (on

  14. Development, improvement and calibration of neutronic reaction rate measurements: elaboration of a base of standard techniques

    International Nuclear Information System (INIS)

    Hudelot, J.P.

    1998-01-01

    In order to improve and to validate the neutronic calculation schemes, perfecting integral measurements of neutronic parameters is necessary. This thesis focuses on the conception, the improvement and the development of neutronic reaction rates measurements, and aims at building a base of standard techniques. Two subjects are discussed. The first one deals with direct measurements by fission chambers. A short presentation of the different usual techniques is given. Then, those last ones are applied through the example of doubling time measurements on the EOLE facility during the MISTRAL 1 experimental programme. Two calibration devices of fission chambers are developed: a thermal column located in the central part of the MINERVE facility, and a calibration cell using a pulsed high flux neutron generator and based on the discrimination of the energy of the neutrons with a time-of-flight method. This second device will soon allow to measure the mass of fission chambers with a precision of about 1 %. Finally, the necessity of those calibrations will be shown through spectral indices measurements in core MISTRAL 1 (UO 2 ) and MISTRAL 2 (MOX) of the EOLE facility. In each case, the associated calculation schemes, performed using the Monte Carlo MCNP code with the ENDF-BV library, will be validated. Concerning the second one, the goal is to develop a method for measuring the modified conversion ratio of 238 U (defined as the ratio of 238 U capture rate to total fission rate) by gamma-ray spectrometry of fuel rods. Within the framework of the MISTRAL 1 and MISTRAL 2 programmes, the measurement device, the experimental results and the spectrometer calibration are described. Furthermore, the MCNP calculations of neutron self-shielding and gamma self-absorption are validated. It is finally shown that measurement uncertainties are better than 1 %. The extension of this technique to future modified conversion ratio measurements for 242 Pu (on MOX rods) and 232 Th (on Thorium

  15. Development, validation, and standardization of polymerase chain reaction-based detection of E-coli O157

    DEFF Research Database (Denmark)

    Abdulmawjood, A.; Bulte, M.; Roth, S.

    2004-01-01

    A diagnostic polymerase chain reaction assay was developed for the detection of E. coli O157 as the first part of a multicenter validation and standardization project. The assay is based on amplification of sequences of the rfbE O157 gene and includes an internal amplification control. The select...

  16. Development of field-deployable instrumentation based on “antigen–antibody” reactions for detection of hemorrhagic disease in ruminants

    Science.gov (United States)

    Development of field-deployable methodology utilizing antigen–antibody reactions and the surface Plasmon resonance (SPR) effect to provide a rapid diagnostic test for recognition of the blue tongue virus (BTV) and epizootic hemorrhage disease virus (EHDV) in wild and domestic ruminants is reported. ...

  17. CVD of SiC and AlN using cyclic organometallic precursors

    Science.gov (United States)

    Interrante, L. V.; Larkin, D. J.; Amato, C.

    1992-01-01

    The use of cyclic organometallic molecules as single-source MOCVD precursors is illustrated by means of examples taken from our recent work on AlN and SiC deposition, with particular focus on SiC. Molecules containing (AlN)3 and (SiC)2 rings as the 'core structure' were employed as the source materials for these studies. The organoaluminum amide, (Me2AlNH2)3, was used as the AlN source and has been studied in a molecular beam sampling apparatus in order to determine the gas phase species present in a hot-wall CVD reactor environment. In the case of SiC CVD, a series of disilacyclobutanes (Si(XX')CH2)2 (with X and X' = H, CH3, and CH2SiH2CH3), were examined in a cold-wall, hot-stage CVD reactor in order to compare their relative reactivities and prospective utility as single-source CVD precursors. The parent compound, disilacyclobutane, (SiH2CH2)2, was found to exhibit the lowest deposition temperature (ca. 670 C) and to yield the highest purity SiC films. This precursor gave a highly textured, polycrystalline film on the Si(100) substrates.

  18. Dissolved oxygen sensing using organometallic dyes deposited within a microfluidic environment

    Science.gov (United States)

    Chen, Q. L.; Ho, H. P.; Jin, L.; Chu, B. W.-K.; Li, M. J.; Yam, V. W.-W.

    2008-02-01

    This work primarily aims to integrate dissolved oxygen sensing capability with a microfluidic platform containing arrays of micro bio-reactors or bio-activity indicators. The measurement of oxygen concentration is of significance for a variety of bio-related applications such as cell culture and gene expression. Optical oxygen sensors based on luminescence quenching are gaining much interest in light of their low power consumption, quick response and high analyte sensitivity in comparison to similar oxygen sensing devices. In our microfluidic oxygen sensor device, a thin layer of oxygen-sensitive luminescent organometallic dye is covalently bonded to a glass slide. Micro flow channels are formed on the glass slide using patterned PDMS (Polydimethylsiloxane). Dissolved oxygen sensing is then performed by directing an optical excitation probe beam to the area of interest within the microfluidic channel. The covalent bonding approach for sensor layer formation offers many distinct advantages over the physical entrapment method including minimizing dye leaching, ensuring good stability and fabrication simplicity. Experimental results confirm the feasibility of the device.

  19. High quality long-wavelength lasers grown by atmospheric organometallic vapor phase epitaxy using tertiarybutylarsine

    International Nuclear Information System (INIS)

    Miller, B.I.; Young, M.G.; Oron, M.; Koren, U.; Kisker, D.

    1990-01-01

    High quality long-wavelength InGaAsP/InP lasers were grown by atmospheric organometallic vapor phase epitaxy using tertiarybutylarsine (TBA) as a substitute for AsH 3 . Electrical and photoluminescence measurements on InGaAs and InGaAsP showed that TBA-grown material was at least as good as AsH 3 material in terms of suitability for lasers. From two wafers grown by TBA, current thresholds I th as low as 11 mA were obtained for a 2-μm-wide semi-insulating blocking planar buried heterostructure laser lasing near 1.3 μm wavelength. The differential quantum efficiencies η D were as high as 21%/facet with a low internal loss α=21 cm -1 . In addition I th as low as 18 mA and η D as high as 18% have been obtained for multiplequantum well lasers at 1.54 μm wavelength. These results show that TBA might be used to replace AsH 3 without compromising on laser performance

  20. Photophysics of organometallic platinum(II) derivatives of the diketopyrrolopyrrole chromophore

    KAUST Repository

    Goswami, Subhadip

    2014-12-18

    A pair of diketopyrrolopyrrole (DPP) chromophores that are end-functionalized with platinum containing "auxochromes" were subjected to electrochemical and photophysical study. The chromophores contain either platinum acetylide or ortho-metalated 2-thienylpyridinyl(platinum) end-groups (DPP-Pt(CC) and DPP-Pt(acac), respectively). The ground state redox potentials of the chromophores were determined by solution electrochemistry, and the HOMO and LUMO levels were estimated. The chromophores\\' photophysical properties were characterized by absorption, photoluminescence, and time-resolved absorption spectroscopy on time scales from sub-picoseconds to microseconds. Density functional theory (DFT) computations were performed to understand the molecular orbitals involved in both the singlet and triplet excited state photophysics. The results reveal that in both platinum DPP derivatives the organometallic auxochromes have a significant effect on the chromophores\\' photophysics. The most profound effect is a reduction in the fluorescence yields accompanied by enhanced triplet yields due to spin-orbit coupling induced by the metal centers. The effects are most pronounced in DPP-Pt(acac), indicating that the orthometalated platinum auxochrome is able to induce spin-orbital coupling to a greater extent compared to the platinum acetylide units. (Figure Presented).

  1. Photophysics of organometallic platinum(II) derivatives of the diketopyrrolopyrrole chromophore

    KAUST Repository

    Goswami, Subhadip; Winkel, Russell W.; Alarousu, Erkki; Ghiviriga, Ion; Mohammed, Omar F.; Schanze, Kirk S.

    2014-01-01

    A pair of diketopyrrolopyrrole (DPP) chromophores that are end-functionalized with platinum containing "auxochromes" were subjected to electrochemical and photophysical study. The chromophores contain either platinum acetylide or ortho-metalated 2-thienylpyridinyl(platinum) end-groups (DPP-Pt(CC) and DPP-Pt(acac), respectively). The ground state redox potentials of the chromophores were determined by solution electrochemistry, and the HOMO and LUMO levels were estimated. The chromophores' photophysical properties were characterized by absorption, photoluminescence, and time-resolved absorption spectroscopy on time scales from sub-picoseconds to microseconds. Density functional theory (DFT) computations were performed to understand the molecular orbitals involved in both the singlet and triplet excited state photophysics. The results reveal that in both platinum DPP derivatives the organometallic auxochromes have a significant effect on the chromophores' photophysics. The most profound effect is a reduction in the fluorescence yields accompanied by enhanced triplet yields due to spin-orbit coupling induced by the metal centers. The effects are most pronounced in DPP-Pt(acac), indicating that the orthometalated platinum auxochrome is able to induce spin-orbital coupling to a greater extent compared to the platinum acetylide units. (Figure Presented).

  2. Development of multiplex polymerase chain reaction for detection of Ehrlichia canis, Babesia spp and Hepatozoon canis in canine blood.

    Science.gov (United States)

    Kledmanee, Kan; Suwanpakdee, Sarin; Krajangwong, Sakranmanee; Chatsiriwech, Jarin; Suksai, Parut; Suwannachat, Pongpun; Sariya, Ladawan; Buddhirongawatr, Ruangrat; Charoonrut, Phingphol; Chaichoun, Kridsada

    2009-01-01

    A multiplex polymerase chain reaction (PCR) has been developed for simultaneous detection of canine blood parasites, Ehrlichia canis, Babesia spp and Hepatozoon canis, from blood samples in a single reaction. The multiplex PCR primers were specific to E. canis VirB9, Babesia spp 16S rRNA and H. canis 16S rRNA genes. Specificity of the amplicons was confirmed by DNA sequencing. The assay was evaluated using normal canine and infected blood samples, which were detected by microscopic examination. This multiplex PCR offers scope for simultaneous detection of three important canine blood parasites and should be valuable in monitoring parasite infections in dogs and ticks.

  3. Laser-induced chemical vapor deposition reactions

    International Nuclear Information System (INIS)

    Teslenko, V.V.

    1990-01-01

    The results of investigation of chemical reactions of deposition of different substances from the gas phase when using the energy of pulse quasicontinuous and continuous radiation of lasers in the wave length interval from 0.193 to 10.6 μm are generalized. Main attetion is paid to deposition of inorganic substances including nonmetals (C, Si, Ge and others), metals (Cu, Au, Zn, Cd, Al, Cr, Mo, W, Ni) and some simple compounds. Experimental data on the effect of laser radiation parameters and reagent nature (hydrides, halogenides, carbonyls, alkyl organometallic compounds and others) on the deposition rate and deposit composition are described in detail. Specific features of laser-chemical reactions of deposition and prospects of their application are considered

  4. The Link between Hypersensitivity Syndrome Reaction Development and Human Herpes Virus-6 Reactivation

    Directory of Open Access Journals (Sweden)

    Joshua C. Pritchett

    2012-01-01

    Data Sources and Extraction. Drugs identified as causes of (i idiosyncratic reactions, (ii drug-induced hypersensitivity, drug-induced hepatotoxicity, acute liver failure, and Stevens-Johnson syndrome, and (iii human herpes virus reactivation in PubMed since 1997 have been collected and discussed. Results. Data presented in this paper show that HHV-6 reactivation is associated with more severe organ involvement and a prolonged course of disease. Conclusion. This analysis of HHV-6 reactivation associated with drug-induced severe cutaneous reactions and hepatotoxicity will aid in causality assessment and clinical diagnosis of possible life-threatening events and will provide a basis for further patient characterization and therapy.

  5. The association between Bacillus Calmette-Guérin vaccination (1331 SSI) skin reaction and subsequent scar development in infants

    DEFF Research Database (Denmark)

    Birk, Nina Marie; Nissen, Thomas Nørrelykke; Ladekarl, Monica

    2017-01-01

    BACKGROUND: The Bacillus Calmette-Guérin vaccine (BCG) against tuberculosis is administered intradermally, and vaccination is often followed by a scar at the injection site. Among BCG-vaccinated individuals, having a scar has been associated with lower mortality. We aimed to examine the impact...... of vaccination technique for scarring in a high income setting, by assessing the associations between the post injection reaction, the wheal size, and the probability of developing a scar, and scar size. METHODS: This study was nested within a clinical multicenter study randomizing 4262 infants to either BCG...... vaccination (BCG 1331 SSI) or no intervention. In this substudy, including 492 vaccinated infants, the immediate post BCG vaccination reaction was registered as either wheal (a raised, blanched papule at the injection site), bulge (a palpable element at the injection site), or no reaction. The presence...

  6. Reaction of Aldehydes/Ketones with Electron-Deficient 1,3,5-Triazines Leading to Functionalized Pyrimidines as Diels-Alder/Retro-Diels-Alder Reaction Products: Reaction Development and Mechanistic Studies.

    Science.gov (United States)

    Yang, Kai; Dang, Qun; Cai, Pei-Jun; Gao, Yang; Yu, Zhi-Xiang; Bai, Xu

    2017-03-03

    Catalytic inverse electron demand Diels-Alder (IEDDA) reactions of heterocyclic aza-dienes are rarely reported since highly reactive and electron-rich dienophiles are often found not compatible with strong acids such as Lewis acids. Herein, we disclose that TFA-catalyzed reactions of electron-deficient 1,3,5-triazines and electron-deficient aldehydes/ketones can take place. These reactions led to highly functionalized pyrimidines as products in fair to good yields. The reaction mechanism was carefully studied by the combination of experimental and computational studies. The reactions involve a cascade of stepwise inverse electron demand hetero-Diels-Alder (ihDA) reactions, followed by retro-Diels-Alder (rDA) reactions and elimination of water. An acid was required for both ihDA and rDA reactions. This mechanism was further verified by comparing the relative reactivity of aldehydes/ketones and their corresponding vinyl ethers in the current reaction system.

  7. Role of DNA damage and repair as predeterminant factor in the development of radiotherapy induced acute adverse reactions

    International Nuclear Information System (INIS)

    Satish Rao, B.S.; Kamalesh, D.M.; Goutham, H.V.; Donald, J.F.; Sharan, Krishna; Vadhiraja, B.M.; Satyamoorthy, K.

    2013-01-01

    Radiotherapy induced normal tissue toxicity is one of the major limitations for the compromised the therapeutic outcome and also worsens the quality of life of survivors. Further, the clinical experience demonstrated inter-individual variability with respect to their normal tissue toxicity. Therefore, the discovery of contributing key factors of variability or predicting the risk of developing acute reactions before the initiation of radiation therapy may serve as a powerful predictive biomarker for individualizing radiotherapy, anticipating increased therapeutic effect. DNA double-strand break (DSB) induction and its repair in lymphocytes of head-and-neck and breast cancer patients undergoing chemoradiation or radiation therapy alone were analyzed by performing γ-H2AX foci, neutral comet and a modified neutral filter elution assays. Treatment induced normal tissue adverse reactions (acute skin reaction, oral mucositis) were assessed by the criteria of Radiation Therapy Oncology Group. The residual damage (RD) at 6 hrs of post irradiation was used as parameters to measure cellular radiosensitivity and for its correlation with radiotherapy induced acute reactions in patients stratified as non-over responders (NOR) and over responders (OR). A large inter-individual variation in the radiosensitivity was observed in the cancer individuals with respect to their lymphocyte radiosensitivity and the severity of normal tissue adverse reactions. There was a significant difference in RD (p<0.05) between the NOR and OR in breast cancer radiotherapy. Further, the increased normal tissue toxicity such as oral mucositis and skin reactions was associated with the reduced DSB repair (p<0.05) in head-and-neck cancer patients. The percentile analysis was found to be useful in predicting the OR amongst the head-and-neck cancer patients. Our results suggest that γ-H2AX analysis may have its potential to be developed into a clinically useful predictive assay for identifying the

  8. Reaction calorimetry for the development of ultrasound-induced polymerization processes in CO2-expanded fluids

    NARCIS (Netherlands)

    Kemmere, M.F.; Kuijpers, M.W.A.; Keurentjes, J.T.F.

    2007-01-01

    A strong viscosity increase upon polymn. hinders radical formation during an ultrasound-induced bulk polymn. Since CO2 acts as a strong anti-solvent for most polymers, it can be used to reduce the viscosity of the reaction mixt. In this work, a process for the ultrasound-induced polymn. in

  9. Employee reactions to human resource management and performance in a developing country

    NARCIS (Netherlands)

    Karsten, Luchien; Ghebregiorgis, F.

    2007-01-01

    Purpose - This paper seeks to examine employee reactions to human resource management (HRM) and performance. It placed employees on a centre stage in analysing HRM to provide theoretical insights. Design/methodology/approach - To explore the theme, a survey of 252 employees drawn from eight

  10. Polymerase chain Reaction in molecular biotechnology; appropriate technology for developing countries

    NARCIS (Netherlands)

    Felice, A. E.; Alshinawi, C.

    1996-01-01

    The product of the Polymerase Chain Reaction (PCR) may be generically suitable for four types of investigations: Discovery PCR, Analytical PCR, Modification by PCR, and Synthetic PCR. Despite the potential problem of contamination with extraneous DNA, PCR is relatively simple and inexpensive, and

  11. Resonances and fusion in heavy ion reactions: new models and developments

    International Nuclear Information System (INIS)

    Cindro, N.

    1982-01-01

    Several aspects of the problem of the resonant behaviour of heavy-ion induced reactions are discussed. First, the problem is set in its relation to fundamental nuclear physics and our understanding of nuclear structure. It is suggested that, if the resonant behaviour of heavy-ion reactions is indeed due to the presence of particular configurations in the composite systems, these configurations must have a very specific nature which prevents their mixing with the adjacent states or else other conditons (e.g. low level density) should be met. Further on, the problem of resonant behaviour observed in back-angle elastic scattering and in forward-angle reaction data is discussed. Collisions between heavy ions leading to the composite systems 36 Ar and 40 Ca are used to discuss the apparent lack of correlation between these two sets of data. A way to understand it, based on the fragmentation of broad resonances, is suggested. In the third part the relation between structure in the fusion cross section excitation functions and that in reaction channel cross sections is discussed. Finally, in the fourth part, the orbiting-cluster model of heavy-ion resonances is briefly described and its predictions discussed. Based on this model a list is given of colliding heavy-ion systems where resonances are expected. (author)

  12. Regio- and stereoselective carbometallation reactions of N-alkynylamides and sulfonamides

    Directory of Open Access Journals (Sweden)

    Yury Minko

    2013-03-01

    Full Text Available The carbocupration reactions of heterosubstituted alkynes allow the regio- and stereoselective formation of vinyl organometallic species. N-Alkynylamides (ynamides are particularly useful substrates for the highly regioselective carbocupration reaction, as they lead to the stereodefined formation of vinylcopper species geminated to the amide moiety. The latter species are involved in numerous synthetically useful transformations leading to valuable building blocks in organic synthesis. Here we describe in full the results of our studies related to the carbometallation reactions of N-alkynylamides.

  13. Combining Organometallic Catalysis and Organocatalysis for the Synthesis of Heterocyclic Scaffolds

    DEFF Research Database (Denmark)

    Hansen, Casper Lykke

    The main work presented in this thesis describes the development of efficient and novel methodologies for the synthesis of pharmaceutically interesting indolecontaining alkaloids, i.e., the 1,2,3,4-tetrahydro-β-carboline and the 1,2,3,4-tetrahydrocarbazole scaffolds. The synthesis of 1...... to the nitrogen in the allylic system proved to be highly important for the enantioselectivity. Enantiomeric excesses up to 57% was obtained. The synthesis of 1,2,3,4-tetrahydrocarbazole relied on novel Brønsted acidcatalyzed Friedel-Crafts-type reactions. Three different kinds of 1,2,3,4-tetrahydrocarbazole...

  14. Impact of chemical reaction in fully developed radiated mixed convective flow between two rotating disk

    Science.gov (United States)

    Hayat, T.; Khan, M. Waleed Ahmed; Khan, M. Ijaz; Waqas, M.; Alsaedi, A.

    2018-06-01

    Flow of magnetohydrodynamic (MHD) viscous fluid between two rotating disks is modeled. Angular velocities of two disks are different. Flow is investigated for nonlinear mixed convection. Heat transfer is analyzed for nonlinear thermal radiation and heat generation/absorption. Chemical reaction is also implemented. Convective conditions of heat and mass transfer are studied. Transformations used lead to reduction of PDEs into the ODEs. The impacts of important physical variables like Prandtl number, Reynold number, Hartman number, mixed convection parameter, chemical reaction and Schmidt number on velocities, temperature and concentration are elaborated. In addition velocity and temperature gradients are physically interpreted. Our obtained results indicate that radial, axial and tangential velocities decrease for higher estimation of Hartman number.

  15. Development and validation of a reduced combined biodiesel–diesel reaction mechanism

    DEFF Research Database (Denmark)

    Ng, Hoon Kiat; Gan, Suyin; Ng, Jo-Han

    2013-01-01

    In this study, a compact combined biodiesel–diesel (CBD) reaction mechanism for diesel engine simulations is proposed through the combination of three component mechanisms using a chemical class-based approach. The proposed mechanism comprises the reaction mechanisms of methyl crotonate (MC...... to characterise the combustion of fossil diesel. Here, the MC and MB mechanisms are reduced before integrating with a compact n-heptane mechanism. CHEMKIN-PRO is used as the solver for the zero-dimensional, closed homogenous reactor with a constant volume in this study. In the first phase, the mechanisms of MC...... ranging from initial temperatures of 750–1350 K, pressures of 40–60 bar and equivalence ratios of 0.4–1.5. The mechanism is generally found to accurately predict the timing and duration of ID for the combustion of each surrogate fuel. This model is also shown to be feasible for use with multidimensional...

  16. Recent developments of the quantum chemical cluster approach for modeling enzyme reactions.

    Science.gov (United States)

    Siegbahn, Per E M; Himo, Fahmi

    2009-06-01

    The quantum chemical cluster approach for modeling enzyme reactions is reviewed. Recent applications have used cluster models much larger than before which have given new modeling insights. One important and rather surprising feature is the fast convergence with cluster size of the energetics of the reactions. Even for reactions with significant charge separation it has in some cases been possible to obtain full convergence in the sense that dielectric cavity effects from outside the cluster do not contribute to any significant extent. Direct comparisons between quantum mechanics (QM)-only and QM/molecular mechanics (MM) calculations for quite large clusters in a case where the results differ significantly have shown that care has to be taken when using the QM/MM approach where there is strong charge polarization. Insights from the methods used, generally hybrid density functional methods, have also led to possibilities to give reasonable error limits for the results. Examples are finally given from the most extensive study using the cluster model, the one of oxygen formation at the oxygen-evolving complex in photosystem II.

  17. Acceleration of Intended Pozzolanic Reaction under Initial Thermal Treatment for Developing Cementless Fly Ash Based Mortar

    Directory of Open Access Journals (Sweden)

    Yang-Hee Kwon

    2017-02-01

    Full Text Available Without using strong alkaline solution or ordinary Portland cement, a new structural binder consisting of fly ash and hydrated lime was hardened through an intensified pozzolanic reaction. The main experimental variables are the addition of silica fume and initial thermal treatment (60 °C for 3 days. A series of experiments consisting of mechanical testing (compressive and flexural strength, modulus of elasticity, X-ray diffraction, and measurements of the heat of hydration, pore structure, and shrinkage were conducted. These tests show that this new fly ash-based mortar has a compressive strength of 15 MPa at 91 days without any silica fume addition or initial thermal treatment. The strength increased to over 50 MPa based on the acceleration of the intensified pozzolanic reaction from the silica fume addition and initial thermal treatment. This is explained by a significant synergistic effect induced by the silica fume. It intensifies the pozzolanic reaction under thermal treatment and provides a space filling effect. This improved material performance can open a new pathway to utilize the industrial by-product of fly ash in cementless construction materials.

  18. Emotions over time: synchronicity and development of subjective, physiological, and facial affective reactions to music.

    Science.gov (United States)

    Grewe, Oliver; Nagel, Frederik; Kopiez, Reinhard; Altenmüller, Eckart

    2007-11-01

    Most people are able to identify basic emotions expressed in music and experience affective reactions to music. But does music generally induce emotion? Does it elicit subjective feelings, physiological arousal, and motor reactions reliably in different individuals? In this interdisciplinary study, measurement of skin conductance, facial muscle activity, and self-monitoring were synchronized with musical stimuli. A group of 38 participants listened to classical, rock, and pop music and reported their feelings in a two-dimensional emotion space during listening. The first entrance of a solo voice or choir and the beginning of new sections were found to elicit interindividual changes in subjective feelings and physiological arousal. Quincy Jones' "Bossa Nova" motivated movement and laughing in more than half of the participants. Bodily reactions such as "goose bumps" and "shivers" could be stimulated by the "Tuba Mirum" from Mozart's Requiem in 7 of 38 participants. In addition, the authors repeated the experiment seven times with one participant to examine intraindividual stability of effects. This exploratory combination of approaches throws a new light on the astonishing complexity of affective music listening.

  19. Recent developments in fusion and direct reactions with weakly bound nuclei

    International Nuclear Information System (INIS)

    Canto, L.F.; Gomes, P.R.S.; Donangelo, R.; Lubian, J.; Hussein, M.S.

    2015-01-01

    In this Report we give a balanced account of the experimental and theoretical advances acquired over the last decade in the field of near-barrier fusion reactions induced by weakly bound stable and unstable nuclei. The elastic scattering and breakup reactions of these systems are also extensively reviewed as they play an important role in the fusion process. We review several theoretical tools used in the description of the data. The concepts of Complete Fusion (CF), Incomplete Fusion (ICF) and Total Fusion (TF), which is the sum of CF and ICF, are discussed and recent work on the calculation of these quantities is reviewed. The Continuum Discretized Coupled Channels (CDCC) method and its semiclassical version are described in detail and their limitations are pointed out. More importantly, we describe the salient features of the conclusions reached from the more than 40 measurements made, over a decade, of near-barrier fusion, elastic scattering and breakup reactions, and confront these data with the CDCC or other methods appropriate for these processes at the energy regime in question.

  20. Development of Functional Inorganic Materials by Soft Chemical Process Using Ion-Exchange Reactions

    Science.gov (United States)

    Feng, Qi

    Our study on soft chemical process using the metal oxide and metal hydroxide nanosheets obtained by exfoliation their layered compounds were reviewed. Ni(OH)2⁄MnO2 sandwich layered nanostructure can be prepared by layer by-layer stacking of exfoliated manganese oxide nanosheets and nickel hydroxide layers. Manganese oxide nanotubes can be obtained by curling the manganese oxide nanosheets using the cationic surfactants as the template. The layered titanate oriented thin film can be prepared by restacking the titanate nanosheets on a polycrystalline substrate, and transformed to the oriented BaTiO3 and TiO2 thin films by the topotactic structural transformation reactions, respectively. The titanate nanosheets can be transformed anatase-type TiO2 nanocrystals under hydrothermal conditions. The TiO2 nanocrystals are formed by a topotactic structural transformation reaction. The TiO2 nanocrystals prepared by this method expose specific crystal plane on their surfaces, and show high photocatalytic activity and high dye adsorption capacity for high performance dye-sensitized solar cell. A series of layered basic metal salt (LBMS) compounds were prepared by hydrothermal reactions of transition metal hydroxides and organic acids. We succeeded in the exfoliation of these LBMS compounds in alcohol solvents, and obtained the transition metal hydroxide nanosheets for the first time.

  1. Solid-state molecular organometallic chemistry. Single-crystal to single-crystal reactivity and catalysis with light hydrocarbon substrates.

    Science.gov (United States)

    Chadwick, F Mark; McKay, Alasdair I; Martinez-Martinez, Antonio J; Rees, Nicholas H; Krämer, Tobias; Macgregor, Stuart A; Weller, Andrew S

    2017-08-01

    Single-crystal to single-crystal solid/gas reactivity and catalysis starting from the precursor sigma-alkane complex [Rh(Cy 2 PCH 2 CH 2 PCy 2 )(η 2 η 2 -NBA)][BAr F 4 ] (NBA = norbornane; Ar F = 3,5-(CF 3 ) 2 C 6 H 3 ) is reported. By adding ethene, propene and 1-butene to this precursor in solid/gas reactions the resulting alkene complexes [Rh(Cy 2 PCH 2 CH 2 PCy 2 )(alkene) x ][BAr F 4 ] are formed. The ethene ( x = 2) complex, [Rh(Cy 2 PCH 2 CH 2 PCy 2 )(ethene) 2 ][BAr F 4 ]-Oct , has been characterized in the solid-state (single-crystal X-ray diffraction) and by solution and solid-state NMR spectroscopy. Rapid, low temperature recrystallization using solution methods results in a different crystalline modification, [Rh(Cy 2 PCH 2 CH 2 PCy 2 )(ethene) 2 ][BAr F 4 ]-Hex , that has a hexagonal microporous structure ( P 6 3 22). The propene complex ( x = 1) [Rh(Cy 2 PCH 2 CH 2 PCy 2 )(propene)][BAr F 4 ] is characterized as having a π-bound alkene with a supporting γ-agostic Rh···H 3 C interaction at low temperature by single-crystal X-ray diffraction, variable temperature solution and solid-state NMR spectroscopy, as well as periodic density functional theory (DFT) calculations. A fluxional process occurs in both the solid-state and solution that is proposed to proceed via a tautomeric allyl-hydride. Gas/solid catalytic isomerization of d 3 -propene, H 2 C 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111

  2. Organometallic synthesis of ZnO nanoparticles for gas sensing: towards selectivity through nanoparticles morphology

    Energy Technology Data Exchange (ETDEWEB)

    Ryzhikov, Andrey; Jońca, Justyna; Kahn, Myrtil; Fajerwerg, Katia [Laboratoire de Chimie de Coordination (LCC), CNRS (France); Chaudret, Bruno [Laboratoire de Physique et de Chimie de Nano-objets (LPCNO), INSA, UPS, CNRS (France); Chapelle, Audrey [Laboratoire d’Analyse et d’Architecture des Systèmes (LAAS), CNRS (France); Ménini, Philippe [Université Toulouse III, Paul Sabatier (France); Shim, Chang Hyun [Laboratoire d’Analyse et d’Architecture des Systèmes (LAAS), CNRS (France); Gaudon, Alain [Alpha M.O.S. SA (France); Fau, Pierre, E-mail: pierre.fau@lcc-toulouse.fr [Laboratoire de Chimie de Coordination (LCC), CNRS (France)

    2015-07-15

    ZnO nanoparticles (NP) with different morphologies such as nanorods (NR), isotropic NP, and cloud-like (CL) structures have been synthesized by an organometallic route. The prepared ZnO nanostructures have been deposited on miniaturized silicon gas sensor substrates by an inkjet method, and their responses to CO, C{sub 3}H{sub 8}, and NH{sub 3} gases have been studied at different operating temperatures (340–500 °C) and relative humidity of 50 %. It is noteworthy that the morphology of the nanostructure of the sensitive layer is maintained after thermal treatment. The morphology of ZnO NP significantly influences the sensor response level and their selectivity properties to reducing gases. Among the three different ZnO types, sensors prepared with NR show the highest response to both CO and C{sub 3}H{sub 8}. Sensors made of isotropic NP and CL structures show a lower but similar response to CO. From all investigated nanostructures, sensors made of CL structures show the weakest response to C{sub 3}H{sub 8}. With NH{sub 3} gas, no effect of the morphology of the ZnO sensitive layer has been evidenced. These different responses highlight the important role of the nanostructure of the ZnO sensitive layer and the nature of the target gas on the detection properties of the sensors. Graphical Abstract: Three different ZnO nanoparticles morphologies (cloud-like, dots, rods) have been employed as sensitive layers in chemoresistive sensors for the selective detection of CO, C{sub 3}H{sub 8} and NH{sub 3}.

  3. Probing the chemistry, electronic structure and redox energetics in pentavalent organometallic actinide complexes

    Energy Technology Data Exchange (ETDEWEB)

    Graves, Christopher R [Los Alamos National Laboratory; Vaughn, Anthony E [Los Alamos National Laboratory; Morris, David E [Los Alamos National Laboratory; Kiplinger, Jaqueline L [Los Alamos National Laboratory

    2008-01-01

    Complexes of the early actinides (Th-Pu) have gained considerable prominence in organometallic chemistry as they have been shown to undergo chemistries not observed with their transition- or lanthanide metal counterparts. Further, while bonding in f-element complexes has historically been considered to be ionic, the issue of covalence remains a subject of debate in the area of actinide science, and studies aimed at elucidating key bonding interactions with 5f-orbitals continue to garner attention. Towards this end, our interests have focused on the role that metal oxidation state plays in the structure, reactivity and spectral properties of organouranium complexes. We report our progress in the synthesis of substituted U{sup V}-imido complexes using various routes: (1) Direct oxidation of U{sup IV}-imido complexes with copper(I) salts; (2) Salt metathesis with U{sup V}-imido halides; (3) Protonolysis and insertion of an U{sup V}-imido alkyl or aryl complex with H-N{double_bond}CPh{sub 2} or N{triple_bond}C-Ph, respectively, to form a U{sup V}-imido ketimide complex. Further, we report and compare the crystallographic, electrochemical, spectroscopic and magnetic characterization of the pentavalent uranium (C{sub 5}Me{sub 5}){sub 2}U({double_bond}N-Ar)(Y) series (Y = OTf, SPh, C{triple_bond}C-Ph, NPh{sub 2}, OPh, N{double_bond}CPh{sub 2}) to further interrogate the molecular, electronic, and magnetic structures of this new class of uranium complexes.

  4. Optimization of the quantitative direct solid total-reflection X-ray fluorescence analysis of glass microspheres functionalized with Zr organometallic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Fernandez-Ruiz, Ramon, E-mail: ramon.fernandez@uam.e [Servicio Interdepartamental de Investigacion, Facultad de Ciencias, Universidad Autonoma de Madrid, Cantoblanco, E-28049, Madrid (Spain); Andres, Roman; Jesus, Ernesto de [Departamento de Quimica Inorganica, Universidad de Alcala, Campus Universitario, 28871, Alcala de Henares, Madrid (Spain); Terreros, Pilar [Instituto de Catalisis y Petroleo-Quimica, CSIC, Cantoblanco, 28049, Madrid (Spain)

    2010-06-15

    Quantitative determination of Zr in the system constituted by quartz microspheres functionalized with two kinds of organometallic compounds has been studied due to the importance of the correct quantization of the Zr from a catalytic point of view. Two parallel approximations were done, i.e. acid leaching and direct solid quantization. To validate the acid leaching TXRF measures, ICP-MS analysis were carried out. The results obtained by means of the optimization of the quantitative direct solid procedure show that, with a previous particle size distribution modification, TXRF obtain the same analytical results as ICP-MS and TXRF by acid leaching way but without previous chemical acid manipulation. This fact implies an important improvement for the analysis time, reagents costs and analysis facility and it proves again the versatility of TXRF to solve analytical problems in an easy, quick and accurate way. Additionally and for the direct solid TXRF measurements, a deeper study was done to evaluate the intrinsic analytical parameters of the Zr TXRF analysis of this material. So, the influence of the particle size distributions (modified by means of a high power ultrasound probe) with respect to uncertainty and detection limits for Zr were developed. The main analytical conclusion was the strong correlation between the average particle sizes and the TXRF analytical parameters of Zr measurements, i.e. concentration, accuracy, uncertainty and detection limits.

  5. Reaction of the hematopoietic system under long-term emotional stress developed after preliminary gamma-irradiation with low doses

    International Nuclear Information System (INIS)

    Moroz, B.B.; Deshevoj, Yu.B.; Lebedev, V.G.; Lyrshchikova, A.V.; Vorotnikova, T.V.

    1997-01-01

    In experiments on rats and mice it was shown that the preliminary protected gamma-irradiation with cumulative dose of 0.9 Gy (dose rate - 0.03 Gy/day) or single short-term gamma-irradiation with dose of 0.9 Gy (dose rate - 1.61 Gy/min) inhibited development of adaptive reactions and compensatory abilities of the hematopoietic system under long-term emotional stress

  6. Electro-oxidation of methanol in alkaline conditions using Pd–Ni nanoparticles prepared from organometallic precursors and supported on carbon vulcan

    Energy Technology Data Exchange (ETDEWEB)

    Manzo-Robledo, A., E-mail: amanzor@ipn.mx [UPALM, Laboratorio de Electroquímica y Corrosión, Escuela Superior de Ingeniería Química e Industrias Extractivas-IPN (Mexico); Costa, Natália J. S. [Universidade de São Paulo, Instituto de Química (Brazil); Philippot, K. [CNRS, LCC, Laboratoire de Chimie de Coordination (France); Rossi, Liane M. [Universidade de São Paulo, Instituto de Química (Brazil); Ramírez-Meneses, E. [Universidad Iberoamericana, Departamento de Ingeniería y Ciencias Químicas (Mexico); Guerrero-Ortega, L. P. A. [UPALM, Laboratorio de Electroquímica y Corrosión, Escuela Superior de Ingeniería Química e Industrias Extractivas-IPN (Mexico); Ezquerra-Quiroga, S. [Universidad Iberoamericana, Departamento de Ingeniería y Ciencias Químicas (Mexico)

    2015-12-15

    Oxidation of low-molecular weight alcohols as energy sources using metal nanoparticles has attracted considerable interest for use as a power source in portable electronic devices. In this work, a series of mono- and bimetallic nanoparticles based on palladium and nickel (Pd, Pd{sub 90}Ni{sub 10}, Pd{sub 50}Ni{sub 50}, Pd{sub 10}Ni{sub 90}, and Ni) have been synthesized from organometallic precursors, namely tris(dibenzylideneacetone) dipalladium(0), Pd{sub 2}(dba){sub 3}, and bis(1,5-cyclooctadiene)nickel(0), Ni(cod){sub 2}. Well-defined metal particles in the nanometric scale from 4.2 to 6.3 nm were observed by transmission electron microscopy. The as-prepared nanoparticles were mixed with a carbon Vulcan matrix (10 % wt. of the catalyst in turn) for investigation as electrocatalysts in methanol oxidation reaction (MOR) in alkaline conditions. The i–E profiles from cyclic voltammetry for the monometallic systems indicated a redox process attributed only to palladium or nickel, as expected. With the bimetallic nanomaterials, the redox process and the i–E characteristics are functions of the amount of nickel associated to palladium. From a fundamental point of view, it has been established that the OH ions’ interfacial interaction and the MOR kinetics are affected by the presence of nickel (decreasing the faradic current) as supported by the current versus potential profiles obtained as a function of methanol concentration and with temperature variation.

  7. Organometallic Pt precursor on graphite substrate: deposition from SC CO2, reduction and morphology transformation as revealed by SFM

    International Nuclear Information System (INIS)

    Elmanovich, Igor V.; Naumkin, Alexander V.; Gallyamov, Marat O.; Khokhlov, Alexei R.

    2012-01-01

    Organometallic Pt precursor was deposited on model highly oriented pyrolytic graphite substrate from solutions in supercritical carbon dioxide. Morphology transformations during reduction process including real-time observations were studied by scanning force microscopy (SFM). We confirmed that SC CO 2 is a promising mediator in deposition process even for rather hydrophobic supports. SFM data show that thermal decomposition of the PtMe 2 (COD) precursor with subsequent hydrogen post-treatment allows one to obtain rather pure and well-defined Pt nanoparticles with average height above a substrate level of 4.5 ± 0.6 nm.

  8. Development of melting temperature-based SYBR Green I polymerase chain reaction methods for multiplex genetically modified organism detection.

    Science.gov (United States)

    Hernández, Marta; Rodríguez-Lázaro, David; Esteve, Teresa; Prat, Salomé; Pla, Maria

    2003-12-15

    Commercialization of several genetically modified crops has been approved worldwide to date. Uniplex polymerase chain reaction (PCR)-based methods to identify these different insertion events have been developed, but their use in the analysis of all commercially available genetically modified organisms (GMOs) is becoming progressively insufficient. These methods require a large number of assays to detect all possible GMOs present in the sample and thereby the development of multiplex PCR systems using combined probes and primers targeted to sequences specific to various GMOs is needed for detection of this increasing number of GMOs. Here we report on the development of a multiplex real-time PCR suitable for multiple GMO identification, based on the intercalating dye SYBR Green I and the analysis of the melting curves of the amplified products. Using this method, different amplification products specific for Maximizer 176, Bt11, MON810, and GA21 maize and for GTS 40-3-2 soybean were obtained and identified by their specific Tm. We have combined amplification of these products in a number of multiplex reactions and show the suitability of the methods for identification of GMOs with a sensitivity of 0.1% in duplex reactions. The described methods offer an economic and simple alternative to real-time PCR systems based on sequence-specific probes (i.e., TaqMan chemistry). These methods can be used as selection tests and further optimized for uniplex GMO quantification.

  9. [Neurophysiological analysis of the development of endocrine and hypertensive reactions in long-term emotional stress].

    Science.gov (United States)

    Amiragova, M G; Arkhangel'skaia, M I; Polyntsev, Iu V; Vorontsov, V I

    1985-08-01

    A study was made of the effect of chronic emotional stress on the formation of hypertension in animals. This was shown to be related to dynamic changes in the function of the CNS, particularly in the hypothalamic apparatus of the neuroendocrine control. The above changes played a role in the formation of hypertensive vascular reactions accompanied by a high hormonal secretion of the adrenal cortex and thyroid. During stabilization of high arterial blood pressure at the late stages of the "after-effect", the hormonal secretion returns to normal.

  10. Glycerol carbonate in Ferrier reaction: Access to new enantiopure building blocks to develop glycoglycerolipid analogues.

    Science.gov (United States)

    da Costa, Pollyanna Leite Ferreira; Melo, Valentina Nascimento; Guimarães, Bruna Martins; Schuler, Marie; Pimenta, Vanessa; Rollin, Patrick; Tatibouët, Arnaud; de Oliveira, Ronaldo Nascimento

    2016-12-21

    Glycerol carbonate and tri-O-acetyl-D-glucal were used for the synthesis of glycero-functionalized carbohydrates. Ferrier reaction between the two partners afforded the O-glucoside in 84% yield. Spontaneous crystallization yielded 28% of a pure diastereoisomer with the S configuration as determined by X-ray crystallography. Then, the azido-glycerosugar was prepared in two steps: ring opening of the cyclic carbonate with sodium azide and per-acetylation with an excellent yield of 94%. A library of glycoconjugates were prepared using a 1,3-dipolar cycloaddition in yields ranging from 64 to 99%. Copyright © 2016 Elsevier Ltd. All rights reserved.

  11. Development of analysis model for mid and long-term effects of sodium water reaction event in LMR

    International Nuclear Information System (INIS)

    Eoh, Jae Hyuk; Sim, Yoon Sub; Kim, Seong O; Kim, Yeon Sik; Kim, Eui Kwang; Wi, Myung Hwan

    2002-04-01

    The Sodium-Water Reaction(SWR) is important in the design consideration of a LMR steam generator. To develop the analysis code for long-term effects of SWR, investigation on the characteristics of various SWR analysis code and the assessment of an analysis model for long term effects were performed. In an event of SWR, pressure spikes of wave propagation occur at its initial stage and last for a very short time, and then bulk motion of fluid and reaction products is progressed and lasts for a long time. In a case SWR occurs, a number of hydrogen bubbles produced and sodium is entrained into the bubbles through the gas-liquid bubble interfaces by evaporation or diffusion. The partial pressure of the sodium in a hydrogen bubble is determined as a function of the bubble size, temperature, and pressure, and is rapidly decreased as its size increased. From this, it can be considered that the bulk motion in the later phase of SWR is an axial motion caused by expansion of a single-phase hydrogen gas bubble produced by a reaction in the vicinity of the leak site. Through this investigation, a preliminary simple analysis model for long-term effects of SWR was set up and sensitivity study using the system design parameters such as pressure and temperature of IHTS for KALIMER was performed. Also, a simpler analysis model using the cover gas pressure change related to the production of a hydrogen bubble in a steam generator was developed from the analyses results. These simple analysis models of the reaction site and the pressure behavior with hydrogen production can be used to develop the mid and long-term analysis code for SWR in the KALIMER steam generator design

  12. Direct Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Austern, N. [University of Pittsburgh, Pittsburgh, PA (United States)

    1963-01-15

    In order to give a unified presentation of one point of view, these lectures are devoted only to a detailed development of the standard theories of direct reactions, starting from basic principles. Discussion is given of the present status of the theories, of the techniques used for practical calculation, and of possible future developments. The direct interaction (DI) aspects of a reaction are those which involve only a few of the many degrees of freedom of a nucleus. In fact the minimum number of degrees of freedom which must be involved in a reaction are those required to describe the initial and final channels, and DI studies typically consider these degrees of freedom and no others. Because of this simplicity DI theories may be worked out in painstaking detail. DI processes concern only part of the wave function for a problem. The other part involves complicated excitations of many degrees of freedom, and gives the compound nucleus (CN) effects. While it is extremely interesting to learn how to separate DI and CN effects in an orderly manner, if they are both present in a reaction, no suitable method has yet been found. Instead, current work stresses the kinds of reactions and the kinds of final states in which DI effects dominate and in which CN effects may almost be forgotten. The DI cross-sections which are studied are often extremely large, comparable to elastic scattering cross-sections. (author)

  13. Ion beam analysis - development and application of nuclear reaction analysis methods, in particular at a nuclear microprobe

    International Nuclear Information System (INIS)

    Sjoeland, K.A.

    1996-11-01

    This thesis treats the development of Ion Beam Analysis methods, principally for the analysis of light elements at a nuclear microprobe. The light elements in this context are defined as having an atomic number less than approx. 13. The work reported is to a large extent based on multiparameter methods. Several signals are recorded simultaneously, and the data can be effectively analyzed to reveal structures that can not be observed through one-parameter collection. The different techniques are combined in a new set-up at the Lund Nuclear Microprobe. The various detectors for reaction products are arranged in such a way that they can be used for the simultaneous analysis of hydrogen, lithium, boron and fluorine together with traditional PIXE analysis and Scanning Transmission Ion Microscopy as well as photon-tagged Nuclear Reaction Analysis. 48 refs

  14. Development of an apparatus to study chemical reactions at high temperature - a progress report

    Energy Technology Data Exchange (ETDEWEB)

    Sturzenegger, M; Schelling, Th; Steiner, E; Wuillemin, D [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1999-08-01

    TREMPER is an apparatus that was devised to study kinetic and thermodynamic aspects of high-temperature reactions under concentrated solar irradiation. The design allows investigations on solid or liquid samples under inert or reactive atmospheres. The working temperature is adjustable; the upper limit that has yet been reached is about 1900 K. TREMPER will facilitate chemical reactivity studies on a temperature level that is difficult to access by other means. First experiments were conducted to study the decomposition of manganese oxide MnO{sub 2}. Chemical analysis of exposed samples confirmed that the parent MnO{sub 2} was decomposed to mixtures of Mn O and Mn{sub 3}O{sub 4}. The amount of Mn O ranged from 60 mol-% in air to 86 mol-% under inert atmosphere. (author) 1 fig., 1 tab., 2 refs.

  15. Development of catalysts for chemical reactions driven by concentrated solar energy

    International Nuclear Information System (INIS)

    Berman, A.; Levitan, R.; Levy, M.

    1992-03-01

    The aim of this phase of the work is to study commercially available low priced catalysts, for the methanation and reforming processes in the closed-loop solar chemical heat pipe. This report summarized some long term tests of commercially available methanation catalysts and the measurement of their active surface before and after reaction. It was found that the 1%Ru on alumina stars catalysts (prepared by Englehard Company according to our request) is very active and stable at 350-750 C. The catalyst 'A' produced in Russia, is less active, however, did not lose the mechanical strength. The 50% Ni/SiO 2 catalyst is active as the 'A' catalyst but loses its activity after treatment at temperature > 600 C, its geometrical size shrinked. (authors). 25 refs., 25 figs., 36 tabs

  16. Quantum mechanical reactive scattering theory for simple chemical reactions: Recent developments in methodology and applications

    International Nuclear Information System (INIS)

    Miller, W.H.

    1989-08-01

    It has recently been discovered that the S-matrix version of the Kohn variational principle is free of the ''Kohn anomalies'' that have plagued other versions and prevented its general use. This has made a major contribution to heavy particle reactive (and also to electron-atom/molecule) scattering which involve non-local (i.e., exchange) interactions that prevent solution of the coupled channel equations by propagation methods. This paper reviews the methodology briefly and presents a sample of integral and differential cross sections that have been obtained for the H + H 2 → H 2 +H and D + H 2 → HD + H reactions in the high energy region (up to 1.2 eV translational energy) relevant to resonance structures reported in recent experiments. 35 refs., 11 figs

  17. Developments in the phenomenology of two-to-three particle reactions

    International Nuclear Information System (INIS)

    Berger, E.L.

    1975-07-01

    Recent progress in understanding data on two to three particle hadron reactions is described. The use of an s-channel azimuthal angle selection is advocated to identify and separate different exchange mechanisms which contribute to the same final state at low subenergy. Solutions to the neutral Q cross-over problem in the Deck model are discussed, and experimental tests are proposed. Methods are offered for enhancing resonance signals in the presence of a large Deck exchange background. The need for absorptive corrections to the usual Deck model is stressed in the light of new FNAL data on diffractive neutron dissociation and ISR data on proton dissociation. Results of an explicit absorbed pion exchange Deck model calculation are compared with data. (U.S.)

  18. Organometallic approach to polymer-protected antibacterial silver nanoparticles: optimal nanoparticle size-selection for bacteria interaction

    Energy Technology Data Exchange (ETDEWEB)

    Crespo, Julian; Garcia-Barrasa, Jorge; Lopez-de-Luzuriaga, Jose M.; Monge, Miguel, E-mail: miguel.monge@unirioja.es; Olmos, M. Elena [Universidad de La Rioja, Centro de Investigacion en Sintesis Quimica (CISQ), Departamento de Quimica (Spain); Saenz, Yolanda; Torres, Carmen [Centro de Investigacion Biomedica de La Rioja, Area de Microbiologia Molecular (Spain)

    2012-12-15

    The optimal size-specific affinity of silver nanoparticles (Ag NPs) towards E. coli bacteria has been studied. For this purpose, Ag NPs coated with polyvinylpyrrolidone (PVP) and cellulose acetate (CA) have been prepared using an organometallic approach. The complex NBu{sub 4}[Ag(C{sub 6}F{sub 5}){sub 2}] has been treated with AgClO{sub 4} in a 1:1 molar ratio giving rise to the nanoparticle precursor [Ag(C{sub 6}F{sub 5})] in solution. Addition of an excess of PVP (1) or CA (2) and 5 h of reflux in tetrahydrofuran (THF) at 66 Degree-Sign C leads to Ag NPs of small size (4.8 {+-} 3.0 nm for PVP-Ag NPs and 3.0 {+-} 1.2 nm for CA-Ag NPs) that coexist in both cases with larger nanoparticles between 7 and 25 nm. Both nanomaterials display a high antibacterial effectiveness against E. coli. The TEM analysis of the nanoparticle-bacterial cell membrane interaction shows an optimal size-specific affinity for PVP-Ag NPs of 5.4 {+-} 0.7 nm in the presence of larger size silver nanoparticles.Graphical AbstractAn organometallic approach permits the synthesis of small size silver nanoparticles (ca 5 nm) as a main population in the presence of larger size nanoparticles. Optimal silver nanoparticle size-selection (5.4 nm) for the interaction with the bacterial membrane is achieved.

  19. Heteroepitaxy of zinc-blende SiC nano-dots on Si substrate by organometallic ion beam

    International Nuclear Information System (INIS)

    Matsumoto, T.; Kiuchi, M.; Sugimoto, S.; Goto, S.

    2006-01-01

    The self-assembled SiC nano-dots were fabricated on Si(111) substrate at low-temperatures using the organometallic ion beam deposition technique. The single precursor of methylsilicenium ions (SiCH 3 + ) with the energy of 100 eV was deposited on Si(111) substrate at 500, 550 and 600 deg. C. The characteristics of the self-assembled SiC nano-dots were analyzed by reflection high-energy electron diffraction (RHEED), Raman spectroscopy and atomic force microscope (AFM). The RHEED patterns showed that the crystal structure of the SiC nano-dots formed on Si(111) substrate was zinc-blende SiC (3C-SiC) and it was heteroepitaxy. The self-assembled SiC nano-dots were like a dome in shape, and their sizes were the length of 200-300 nm and the height of 10-15 nm. Despite the low-temperature of 500 deg. C as SiC crystallization the heteroepitaxial SiC nano-dots were fabricated on Si(111) substrate using the organometallic ion beam

  20. Distribution of PCDD/Fs and organometallic compounds in sewage sludge of wastewater treatment plants in China

    International Nuclear Information System (INIS)

    Lu Mang; Wu Xuejiao; Zeng Decai; Liao Yong

    2012-01-01

    Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), organotin and organolead compounds were measured in sewage sludge samples collected from 24 wastewater treatment plants from 18 cities of 13 provinces in China. Total international toxicity equivalent (I-TEQ) values were evaluated for PCDD/Fs. The total concentration of PCDD/Fs ranged from 104.0 to 1661 pg/g dry weight (d.w.) and 2.51–75.21 pg I-TEQ/g d.w., indicating that all I-TEQs were below Chinese legislation limit value regulated for land application. The concentrations ranged from 258 to 3886, 126 to 1129, and 84–2133 ng/g as Sn d.w., for tributyltin (TBT), dibutyltin (DBT), and diphenyltin (DPhT), respectively. On the other side, organolead concentrations ranged from 85 to 668 with an average of 279 ng/g as lead. High concentrations of organolead compounds in sewage sludge indicated that the environmental impact of organolead compounds remains in China. - Highlights: ► The first study on PCDD/F distribution in sewage sludge in China on a national scale. ► The first study on organometallic compounds distribution in sewage sludge on a national scale. ► The persistence of tetraethyllead deserves attention. - This is the first study on the survey of the distributions of POPs and organometallic compounds in sewage sludge in China on a national scale.

  1. Electroluminescence Properties of IrQ(ppy)2 Dual-Emitter Organometallic Compound in Organic Light-Emitting Devices

    Science.gov (United States)

    Ciobotaru, Constantin Claudiu; Polosan, Silviu; Ciobotaru, Iulia Corina

    2018-02-01

    This paper reports the influence of the charge carrier mobility on the electroluminescent properties of a dual-emitter organometallic compound dispersed in two conjugated organic small-molecule host materials and embedded in organic light-emitting devices (OLEDs). The electroluminescent processes in OLEDs are strongly influenced by the host-guest interaction. The charge carrier mobility in the host material plays an important role in the electroluminescent processes but also depends on the triplet-triplet interaction with the organometallic compound. The low charge carrier mobility in 4,4'-bis( N-carbazolyl)-1,1'-biphenyl (CBP) host material reduces the electroluminescent processes, but they are slightly enhanced by the triplet-triplet exothermic charge transfer. The higher charge carrier mobility in the case of N, N'-bis(3-methylphenyl)- N, N'-diphenylbenzidine (TPD) host material influences the electroluminescent processes by the endothermic energy transfer at room temperature, which facilitates the triplet-triplet harvesting in the host-guest system. The excitation is transferred to the guest molecules by triplet-triplet interaction as a Dexter transfer, which occurs by endothermic transfer from the triplet exciton in the host to the triplet exciton in the guest.

  2. N-heterocyclic carbene metal complexes as bio-organometallic antimicrobial and anticancer drugs.

    Science.gov (United States)

    Patil, Siddappa A; Patil, Shivaputra A; Patil, Renukadevi; Keri, Rangappa S; Budagumpi, Srinivasa; Balakrishna, Geetha R; Tacke, Matthias

    2015-01-01

    Late transition metal complexes that bear N-heterocyclic carbene (NHC) ligands have seen a speedy growth in their use as both, metal-based drug candidates and potentially active homogeneous catalysts in a plethora of C-C and C-N bond forming reactions. This review article focuses on the recent developments and advances in preparation and characterization of NHC-metal complexes (metal: silver, gold, copper, palladium, nickel and ruthenium) and their biomedical applications. Their design, syntheses and characterization have been reviewed and correlated to their antimicrobial and anticancer efficacies. All these initial discoveries help validate the great potential of NHC-metal derivatives as a class of effective antimicrobial and anticancer agents.

  3. Copper-Catalyzed Oxidative Reaction of β-Keto Sulfones with Alcohols via C-S Bond Cleavage: Reaction Development and Mechanism Study.

    Science.gov (United States)

    Du, Bingnan; Wang, Wenmin; Wang, Yang; Qi, Zhenghang; Tian, Jiaqi; Zhou, Jie; Wang, Xiaochen; Han, Jianlin; Ma, Jing; Pan, Yi

    2018-02-16

    A Cu-catalyzed cascade oxidative radical process of β-keto sulfones with alcohols has been achieved by using oxygen as an oxidant. In this reaction, β-keto sulfones were converted into sulfinate esters under the oxidative conditions via cleavage of C-S bond. Experimental and computational studies demonstrate that a new pathway is involved in this reaction, which proceeds through the formation of the key four-coordinated Cu II intermediate, O-O bond homolysis induced C-S bond cleavage and Cu-catalyzed esterification to form the final products. This reaction provides a new strategy to sulfonate esters and enriches the research content of C-S bond cleavage and transformations. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Development of a model-independent evaluation of photon-deuteron reactions for the SAPHIR detector

    International Nuclear Information System (INIS)

    Wolf, A.

    1993-01-01

    The SAPHIR detector measures photon induced reactions with many particles in the final state. Thus a detailed investigation of those processes at photon energies between 0.4 and 3.3 GeV is possible. The interpretation of the distribution of the sample of events, which SAPHIR is able to reconstruct, has to be done after a correction of influences induced by the detector acceptance. In this work a model independent method of correcting and analysing the data is discussed. The implementation of the basic tools of this analysis is described and first tests with simulated and real events are performed. SAPHIR uses a time-of-flight system for the identification of particles. This work describes the structure of a program library, which supports an easy way of decoding the digitizations of this system (including calibration of the hardware) and obtaining the flight time for a particle in a event. The necessary step for calibrating the system are outlined, too. (orig.)

  5. Development of silver-gas diffusion electrodes for the oxygen reduction reaction by electrodeposition

    Energy Technology Data Exchange (ETDEWEB)

    Salomé, Sónia; Rego, Rosa; Oliveira, M. Cristina, E-mail: mcris@utad.pt

    2013-12-16

    Silver-gas diffusion electrodes (Ag-GDE) were prepared by direct deposition of the catalyst onto a carbon paper support by electrodeposition. This deposition technique, under potentiostatic and galvanostatic mode, allows the production of well dispersed ultra-low Ag loading levels. The catalytic activity of the prepared materials towards the oxygen reduction reaction (ORR) was investigated in the alkaline solution and its tolerance to methanol was evaluated. Based on an Ag-ink prepared from the electrodeposit material and RDE experiments, it was concluded that the ORR occurs via a four-electron pathway on the Ag electrodeposit. The combination of reasonably high catalytic activity, efficiency, low price, facile and green synthesis makes the electrodeposited Ag-GDE attractive for the ORR in alkaline fuel cells. - Highlights: • A facile and simple way to successfully prepare catalyzed gas diffusion electrodes. • Ultra-low loadings of Ag-GDEs can be achieved. • Good tolerance to methanol and a high mass activity (3.14 mA{sub Ag} mg{sup −1}). • ORR occurs via a four-electron pathway.

  6. Progress in Development of a Low Energy Reaction Cell for Distributed Power Applications

    International Nuclear Information System (INIS)

    Miley, G.H.; Castano, C.; Lipson, A.; Kim, S.O.; Luo, N.

    2002-01-01

    Power units using Low Energy Nuclear Reactions (LENRs) potentially offer a radical new approach to power units that could provide distributed power units in the 1-50 kW range. As described in prior ICONE papers [9, 23] these cells employ thin metallic film cathodes (order of 500 Angstrom, using variously Ni, Pd and Ti) with electrolytes such as 0.5-1 molar lithium sulfates in light water. Power densities exceeding 10 W/cc in the films have been achieved. An ultimate goal is to incorporate this thin-film technology into a 'tightly packed' cell design where the film material occupies ∼20% of the total volume. If this is achieved, power densities of ∼20 W/cm 3 appear feasible, opening the way to a number of potential applications involving distributed power. Recent studies reported here have concentrated on new electrode designs intended to maximize the proton loading in the films while maintaining the required proton and electron current densities. (authors)

  7. Rhodium-catalyzed [5 + 2 + 1] cycloaddition of ene-vinylcyclopropanes and CO: reaction design, development, application in natural product synthesis, and inspiration for developing new reactions for synthesis of eight-membered carbocycles.

    Science.gov (United States)

    Wang, Yi; Yu, Zhi-Xiang

    2015-08-18

    Practical syntheses of natural products and their analogues with eight-membered carbocyclic skeletons are important for medicinal and biological investigations. However, methods and strategies to construct the eight-membered carbocycles are limited. Therefore, developing new methods to synthesize the eight-membered carbocycles is highly desired. In this Account, we describe our development of three rhodium-catalyzed cycloadditions for the construction of the eight-membered carbocycles, which have great potential in addressing the challenges in the synthesis of medium-sized ring systems. The first reaction described in this Account is our computationally designed rhodium-catalyzed two-component [5 + 2 + 1] cycloaddition of ene-vinylcyclopropanes (ene-VCPs) and CO for the diastereoselective construction of bi- and tricyclic cyclooctenones. The design of this reaction is based on the hypothesis that the C(sp(3))-C(sp(3)) reductive elimination of the eight-membered rhodacycle intermediate generated from the rhodium-catalyzed cyclopropane cleavage and alkene insertion, giving Wender's [5 + 2] cycloadduct, is not easy. Under CO atmosphere, CO insertion may occur rapidly, converting the eight-membered rhodacycle into a nine-membered rhodacycle, which then undergoes an easy C(sp(2))-C(sp(3)) reductive elimination process and furnishes the [5 + 2 + 1] product. This hypothesis was supported by our preliminary DFT studies and also served as inspiration for the development of two [7 + 1] cycloadditions: the [7 + 1] cycloaddition of buta-1,3-dienylcyclopropanes (BDCPs) and CO for the construction of cyclooctadienones, and the benzo/[7 + 1] cycloaddition of cyclopropyl-benzocyclobutenes (CP-BCBs) and CO to synthesize the benzocyclooctenones. The efficiency of these rhodium-catalyzed cycloadditions can be revealed by the application in natural product synthesis. Two eight-membered ring-containing natural products, (±)-asterisca-3(15),6-diene and (+)-asteriscanolide, have been

  8. Development of a Knowledgebase (MetRxn) of Metabolites, Reactions and Atom Mappings to Accelerate Discovery and Redesign

    Energy Technology Data Exchange (ETDEWEB)

    Maranas, Costas D. [Pennsylvania State Univ., University Park, PA (United States)

    2017-12-11

    With advances in DNA sequencing and genome annotation techniques, the breadth of metabolic knowledge across all kingdoms of life is increasing. The construction of genome-scale models (GSMs) facilitates this distillation of knowledge by systematically accounting for reaction stoichiometry and directionality, gene to protein to reaction relationships, reaction localization among cellular organelles, metabolite transport costs and routes, transcriptional regulation, and biomass composition. Genome-scale reconstructions available now span across all kingdoms of life, from microbes to whole-plant models, and have become indispensable for driving informed metabolic designs and interventions. A key barrier to the pace of this development is our inability to utilize metabolite/reaction information from databases such as BRENDA [1], KEGG [2], MetaCyc [3], etc. due to incompatibilities of representation, duplications, and errors. Duplicate entries constitute a major impediment, where the same metabolite is found with multiple names across databases and models, which significantly slows downs the collating of information from multiple data sources. This can also lead to serious modeling errors such as charge/mass imbalances [4,5] which can thwart model predictive abilities such as identifying synthetic lethal gene pairs and quantifying metabolic flows. Hence, we created the MetRxn database [6] that takes the next step in integrating data from multiple sources and formats to automatically create a standardized knowledgebase. We subsequently deployed this resource to bring about new paradigms in genome-scale metabolic model reconstruction, metabolic flux elucidation through MFA, modeling of microbial communities, and pathway prospecting. This research has enabled the PI’s group to continue building upon research milestones and reach new ones (see list of MetRxn-related publications below).

  9. 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

  10. E-pharmacovigilance: development and implementation of a computable knowledge base to identify adverse drug reactions.

    Science.gov (United States)

    Neubert, Antje; Dormann, Harald; Prokosch, Hans-Ulrich; Bürkle, Thomas; Rascher, Wolfgang; Sojer, Reinhold; Brune, Kay; Criegee-Rieck, Manfred

    2013-09-01

    Computer-assisted signal generation is an important issue for the prevention of adverse drug reactions (ADRs). However, due to poor standardization of patients' medical data and a lack of computable medical drug knowledge the specificity of computerized decision support systems for early ADR detection is too low and thus those systems are not yet implemented in daily clinical practice. We report on a method to formalize knowledge about ADRs based on the Summary of Product Characteristics (SmPCs) and linking them with structured patient data to generate safety signals automatically and with high sensitivity and specificity. A computable ADR knowledge base (ADR-KB) that inherently contains standardized concepts for ADRs (WHO-ART), drugs (ATC) and laboratory test results (LOINC) was built. The system was evaluated in study populations of paediatric and internal medicine inpatients. A total of 262 different ADR concepts related to laboratory findings were linked to 212 LOINC terms. The ADR knowledge base was retrospectively applied to a study population of 970 admissions (474 internal and 496 paediatric patients), who underwent intensive ADR surveillance. The specificity increased from 7% without ADR-KB up to 73% in internal patients and from 19.6% up to 91% in paediatric inpatients, respectively. This study shows that contextual linkage of patients' medication data with laboratory test results is a useful and reasonable instrument for computer-assisted ADR detection and a valuable step towards a systematic drug safety process. The system enables automated detection of ADRs during clinical practice with a quality close to intensive chart review. © 2013 The Authors. British Journal of Clinical Pharmacology © 2013 The British Pharmacological Society.

  11. Boundary-layer development and transition due to free-stream exothermic reactions in shock-induced flows

    Science.gov (United States)

    Hall, J. L.

    1974-01-01

    A study of the effect of free-stream thermal-energy release from shock-induced exothermic reactions on boundary-layer development and transition is presented. The flow model is that of a boundary layer developing behind a moving shock wave in two-dimensional unsteady flow over a shock-tube wall. Matched sets of combustible hydrogen-oxygen-nitrogen mixtures and inert hydrogen-nitrogen mixtures were used to obtain transition data over a range of transition Reynolds numbers from 1,100,000 to 21,300,000. The heat-energy is shown to significantly stabilize the boundary layer without changing its development character. A method for application of this data to flat-plate steady flows is included.

  12. One- and two-dimensional infrared spectroscopic studies of solution-phase homogeneous catalysis and spin-forbidden reactions

    Energy Technology Data Exchange (ETDEWEB)

    Sawyer, Karma Rae [Univ. of California, Berkeley, CA (United States)

    2008-12-01

    Understanding chemical reactions requires the knowledge of the elementary steps of breaking and making bonds, and often a variety of experimental techniques are needed to achieve this goal. The initial steps occur on the femto- through picosecond time-scales, requiring the use of ultrafast spectroscopic methods, while the rate-limiting steps often occur more slowly, requiring alternative techniques. Ultrafast one and two-dimensional infrared and step-scan FTIR spectroscopies are used to investigate the photochemical reactions of four organometallic complexes. The analysis leads to a detailed understanding of mechanisms that are general in nature and may be applicable to a variety of reactions.

  13. Development of dose delivery verification by PET imaging of photonuclear reactions following high energy photon therapy

    International Nuclear Information System (INIS)

    Janek, S; Svensson, R; Jonsson, C; Brahme, A

    2006-01-01

    A method for dose delivery monitoring after high energy photon therapy has been investigated based on positron emission tomography (PET). The technique is based on the activation of body tissues by high energy bremsstrahlung beams, preferably with energies well above 20 MeV, resulting primarily in 11 C and 15 O but also 13 N, all positron-emitting radionuclides produced by photoneutron reactions in the nuclei of 12 C, 16 O and 14 N. A PMMA phantom and animal tissue, a frozen hind leg of a pig, were irradiated to 10 Gy and the induced positron activity distributions were measured off-line in a PET camera a couple of minutes after irradiation. The accelerator used was a Racetrack Microtron at the Karolinska University Hospital using 50 MV scanned photon beams. From photonuclear cross-section data integrated over the 50 MV photon fluence spectrum the predicted PET signal was calculated and compared with experimental measurements. Since measured PET images change with time post irradiation, as a result of the different decay times of the radionuclides, the signals from activated 12 C, 16 O and 14 N within the irradiated volume could be separated from each other. Most information is obtained from the carbon and oxygen radionuclides which are the most abundant elements in soft tissue. The predicted and measured overall positron activities are almost equal (-3%) while the predicted activity originating from nitrogen is overestimated by almost a factor of two, possibly due to experimental noise. Based on the results obtained in this first feasibility study the great value of a combined radiotherapy-PET-CT unit is indicated in order to fully exploit the high activity signal from oxygen immediately after treatment and to avoid patient repositioning. With an RT-PET-CT unit a high signal could be collected even at a dose level of 2 Gy and the acquisition time for the PET could be reduced considerably. Real patient dose delivery verification by means of PET imaging seems to be

  14. Development of an electron calorimeter to be used in high transverse momentum reaction studies

    International Nuclear Information System (INIS)

    Charpentier, Philippe.

    1977-01-01

    In order to select high transverse momentum particles, an electron calorimeter made of two super-units of 2x5 m 2 was developed. A new type of scintillator called Plexipop and having the following characteristics, was developed: the light produced equals only 20% of that produced by NE 110, it has a high attenuation length (about 3.80 m), and a short lifetime (5 nsec). Various calibration methods were defined for this apparatus. The resolution obtained was 5% at 10 GeV/c [fr

  15. Development of indirect spectrophotometric method for quantification of cephalexin in pure form and commercial formulation using complexation reaction

    International Nuclear Information System (INIS)

    Khan, M.N.; Hussain, R.; Kalsoom, S.; Saadiq, M.

    2016-01-01

    A simple, accurate and indirect spectrophotometric method was developed for the quantification of cephalexin in pure form and pharmaceutical products using complexation reaction. The developed method is based on the oxidation of the cephalexin with Fe/sup 3+/ in acidic medium. Then 1, 10- phenanthroline reacts with Fe/sup 2+/ and a red colored complex was formed. The absorbance of the complex was measured at 510 nm by spectrophotometer. Different experimental parameters affecting the complexation reactions were studied and optimized. Beer law was obeyed in the concentration range 0.4 -10 micro gmL/sup -1/ with a good correlation of 0.992. The limit of detection and limit of quantification were found to be 0.065 micro gmL/sup -1/ and 0.218 micro gmL/sup -1/ , respectively. The method have good reproducibility with a relative standard deviation of 6.26 percent (n = 6). The method was successfully applied for the determination of cephalexin in bulk powder and commercial formulation. Percent recoveries were found to range from 95.47 to 103.87 percent for the pure form and 98.62 to 103.35 percent for commercial formulations. (author)

  16. Development and interlaboratory validation of quantitative polymerase chain reaction method for screening analysis of genetically modified soybeans.

    Science.gov (United States)

    Takabatake, Reona; Onishi, Mari; Koiwa, Tomohiro; Futo, Satoshi; Minegishi, Yasutaka; Akiyama, Hiroshi; Teshima, Reiko; Kurashima, Takeyo; Mano, Junichi; Furui, Satoshi; Kitta, Kazumi

    2013-01-01

    A novel real-time polymerase chain reaction (PCR)-based quantitative screening method was developed for three genetically modified soybeans: RRS, A2704-12, and MON89788. The 35S promoter (P35S) of cauliflower mosaic virus is introduced into RRS and A2704-12 but not MON89788. We then designed a screening method comprised of the combination of the quantification of P35S and the event-specific quantification of MON89788. The conversion factor (Cf) required to convert the amount of a genetically modified organism (GMO) from a copy number ratio to a weight ratio was determined experimentally. The trueness and precision were evaluated as the bias and reproducibility of relative standard deviation (RSDR), respectively. The determined RSDR values for the method were less than 25% for both targets. We consider that the developed method would be suitable for the simple detection and approximate quantification of GMO.

  17. Caught in a Narrow Kantian Perception of Prosocial Development: Reactions to Campbell and Christopher's Critique of Moral Development Theory.

    Science.gov (United States)

    Eisenberg, Nancy

    1996-01-01

    Discusses the limitations of Campbell and Christopher's literature on moral development and altruism, claiming that the authors based some of their conclusions on questionable definitions, incorrect assumptions about others' assertions and beliefs, and reference to a limited portion of prosocial behavior. Suggests that Kantian presuppositions play…

  18. Analytic study of the chain dark decomposition reaction of iodides - atomic iodine donors - in the active medium of a pulsed chemical oxygen-iodine laser: 1. Criteria for the development of the branching chain dark decomposition reaction of iodides

    International Nuclear Information System (INIS)

    Andreeva, Tamara L; Kuznetsova, S V; Maslov, Aleksandr I; Sorokin, Vadim N

    2009-01-01

    The scheme of chemical processes proceeding in the active medium of a pulsed chemical oxygen-iodine laser (COIL) is analysed. Based on the analysis performed, the complete system of differential equations corresponding to this scheme is replaced by a simplified system of equations describing in dimensionless variables the chain dark decomposition of iodides - atomic iodine donors, in the COIL active medium. The procedure solving this system is described, the basic parameters determining the development of the chain reaction are found and its specific time intervals are determined. The initial stage of the reaction is analysed and criteria for the development of the branching chain decomposition reaction of iodide in the COIL active medium are determined. (active media)

  19. Diazo compounds and N-tosylhydrazones: novel cross-coupling partners in transition-metal-catalyzed reactions.

    Science.gov (United States)

    Xiao, Qing; Zhang, Yan; Wang, Jianbo

    2013-02-19

    Transition-metal-catalyzed carbene transformations and cross-couplings represent two major reaction types in organometallic chemistry and organic synthesis. However, for a long period of time, these two important areas have evolved separately, with essentially no overlap or integration. Thus, an intriguing question has emerged: can cross-coupling and metal carbene transformations be merged into a single reaction cycle? Such a combination could facilitate the development of novel carbon-carbon bond-forming methodologies. Although this concept was first explored about 10 years ago, rapid developments inthis area have been achieved recently. Palladium catalysts can be used to couple diazo compounds with a wide variety of organic halides. Under oxidative coupling conditions, diazo compounds can also react with arylboronic acids and terminal alkynes. Both of these coupling reactions form carbon-carbon double bonds. As the key step in these catalytic processes, Pd carbene migratory insertion plays a vital role in merging the elementary steps of Pd intermediates, leading to novel carbon-carbon bond formations. Because the diazo substrates can be generated in situ from N-tosylhydrazones in the presence of base, the N-tosylhydrazones can be used as reaction partners, making this type of cross-coupling reaction practical in organic synthesis. N-Tosylhydrazones are easily derived from the corresponding aldehydes or ketones. The Pd-catalyzed cross-coupling of N-tosylhydrazones is considered a complementary reaction to the classic Shapiro reaction for converting carbonyl functionalities into carbon-carbon double bonds. It can also serve as an alternative approach for the Pd-catalyzed cross-coupling of carbonyl compounds, which is usually achieved via triflates. The combination of carbene formation and cross-coupling in a single catalytic cycle is not limited to Pd-catalyzed reactions. Recent studies of Cu-, Rh-, Ni-, and Co-catalyzed cross-coupling reactions with diazo

  20. Development of catalytic materials for the synthesis of valuable chemical products via multifunctional and multisite reactions

    International Nuclear Information System (INIS)

    Apesteguia, C.R; Padro, C.L; Diez, V.K; Di Cosimo, J.I; Trasarti, A.F; Marchi, A.J

    2004-01-01

    This work reports on the successful development of solid catalytic materials carried out by our working group to obtain fine high yield chemical products. Specifically, a report is made of i) the development of metal/acid bi-functional catalysts to obtain racemic menthol from citral in a one step liquid phase process. This menthol is one of the most important chemical flavouring compounds in industry; ii) The use of acid zeolites containing a balanced concentration of Bronsted and Lewis heavy acid sites, which allow the selective synthesis of o-hydroxy acetophenone from the gas phase acylation of phenol with acetic acid. The o-hydroxy acetophenone is an intermediate compound in the production of 4-hydroxy coumarin and warfarin that are used as anticoagulants drugs; iii) The use of mixed MgAl x O y oxides containing dual acid-basic sites (Mg 2- O 2- and Al 3+ -O 2- ) to synthesize isoforone from acetone in gas phase. The isoforone is an intermediate key in the synthesis of vitamin E (CW)

  1. Protective Actions of 17β-Estradiol and Progesterone on Oxidative Neuronal Injury Induced by Organometallic Compounds

    Directory of Open Access Journals (Sweden)

    Yasuhiro Ishihara

    2015-01-01

    Full Text Available Steroid hormones synthesized in and secreted from peripheral endocrine glands pass through the blood-brain barrier and play a role in the central nervous system. In addition, the brain possesses an inherent endocrine system and synthesizes steroid hormones known as neurosteroids. Increasing evidence shows that neuroactive steroids protect the central nervous system from various harmful stimuli. Reports show that the neuroprotective actions of steroid hormones attenuate oxidative stress. In this review, we summarize the antioxidative effects of neuroactive steroids, especially 17β-estradiol and progesterone, on neuronal injury in the central nervous system under various pathological conditions, and then describe our recent findings concerning the neuroprotective actions of 17β-estradiol and progesterone on oxidative neuronal injury induced by organometallic compounds, tributyltin, and methylmercury.

  2. Size distribution of silver nanoclusters induced by ion, electron, laser beams and thermal treatments of an organometallic precursor

    International Nuclear Information System (INIS)

    D'Urso, L.; Nicolosi, V.; Compagnini, G.; Puglisi, O.

    2004-01-01

    Recently, a huge variety of physical and chemical synthetic processes have been reported to prepare nanostructured materials made of very small (diameter<50 nm) metallic clusters. Depending on the nature of clusters, this new kind of materials posses interesting properties (electronic, optical, magnetic, catalytic) that can be tailored as a function of the particles size and shape. Silver nanoparticles have been obtained by direct thermal treatment or by beam-enhanced decomposition (ion, electron and laser) of a silver organometallic compound (precursor) spinned onto suitable substrates. In this paper, we present the results of a study on the size distribution of such nanoparticles as a function of the different synthesis methods. It was found that the methods employed strongly affect the silver nanoparticles formation. Smaller silver nanoclusters were obtained after reduction by ion beam irradiation and thermal treatment, as observed by using different techniques (AFM, XRD and UV-Vis)

  3. Well-Defined Molybdenum Oxo Alkyl Complex Supported on Silica by Surface Organometallic Chemistry: A Highly Active Olefin Metathesis Precatalyst

    KAUST Repository

    Merle, Nicolas; Le Qué mé ner, Fré dé ric; Bouhoute, Yassine; Szeto, Kai C.; De Mallmann, Aimery; Barman, Samir; Samantaray, Manoja; Delevoye, Laurent; Gauvin, Ré gis M.; Taoufik, Mostafa; Basset, Jean-Marie

    2016-01-01

    The well-defined silica-supported molybdenum oxo alkyl species (SiO−)MoO(CH Bu) was selectively prepared by grafting of MoO(CH Bu)Cl onto partially dehydroxylated silica (silica) using the surface organometallic chemistry approach. This surface species was fully characterized by elemental analysis and DRIFT, solid-state NMR, and EXAFS spectroscopy. This new material is related to the active species of industrial supported MoO/SiO olefin metathesis catalysts. It displays very high activity in propene self-metathesis at mild (turnover number = 90 000 after 25 h). Remarkably, its catalytic performance outpaces those of the parent imido derivative and its tungsten oxo analogue.

  4. Well-Defined Molybdenum Oxo Alkyl Complex Supported on Silica by Surface Organometallic Chemistry: A Highly Active Olefin Metathesis Precatalyst

    KAUST Repository

    Merle, Nicolas

    2016-12-05

    The well-defined silica-supported molybdenum oxo alkyl species (SiO−)MoO(CH Bu) was selectively prepared by grafting of MoO(CH Bu)Cl onto partially dehydroxylated silica (silica) using the surface organometallic chemistry approach. This surface species was fully characterized by elemental analysis and DRIFT, solid-state NMR, and EXAFS spectroscopy. This new material is related to the active species of industrial supported MoO/SiO olefin metathesis catalysts. It displays very high activity in propene self-metathesis at mild (turnover number = 90 000 after 25 h). Remarkably, its catalytic performance outpaces those of the parent imido derivative and its tungsten oxo analogue.

  5. Development of an environmental high-voltage electron microscope for reaction science.

    Science.gov (United States)

    Tanaka, Nobuo; Usukura, Jiro; Kusunoki, Michiko; Saito, Yahachi; Sasaki, Katuhiro; Tanji, Takayoshi; Muto, Shunsuke; Arai, Shigeo

    2013-02-01

    Environmental transmission electron microscopy and ultra-high resolution electron microscopic observation using aberration correctors have recently emerged as topics of great interest. The former method is an extension of the so-called in situ electron microscopy that has been performed since the 1970s. Current research in this area has been focusing on dynamic observation with atomic resolution under gaseous atmospheres and in liquids. Since 2007, Nagoya University has been developing a new 1-MV high voltage (scanning) transmission electron microscope that can be used to observe nanomaterials under conditions that include the presence of gases, liquids and illuminating lights, and it can be also used to perform mechanical operations to nanometre-sized areas as well as electron tomography and elemental analysis by electron energy loss spectroscopy. The new instrument has been used to image and analyse various types of samples including biological ones.

  6. Colour and surface fluorescence development and their relationship with Maillard reaction markers as influenced by structural changes during cornflakes production.

    Science.gov (United States)

    Farroni, Abel; Buera, María Del Pilar

    2012-12-01

    The aim of this work was to study colour and surface fluorescence development in relation to the chemical markers for the Maillard reaction at the cooking, flaking and toasting stages of cornflake production process. Colour was measured by a calibrated computer vision system. Surface fluorescence was measured on compressed samples. Aqueous extracted Maillard reaction markers (hydroxymethylfurfural, carboxymethyl-lysine, absorbance at 420nm and total fluorescence) were measured on protease hydrolyzed samples. Sample microstructure was observed by scanning electron microscopy. During cooking the colour coordinates L(∗) and b(∗) decreased and a(∗) increased. After flaking, the samples appeared lighter, while the pigment concentration, fluorescence and hydroxymethylfurfural did not change. Toasting generated bubbles in the matrix and L(∗) apparently increased, although brown pigment concentration increased. Pigment concentration did not correlate with surface colour due to the destruction or generation of interfaces. Surface and microstructure effects can be avoided by milling and compressing the samples. Copyright © 2012 Elsevier Ltd. All rights reserved.

  7. Development of a polymerase chain reaction applicable to rapid and sensitive detection of Clonorchis sinensis eggs in human stool samples

    Science.gov (United States)

    Cho, Pyo Yun; Na, Byoung-Kuk; Mi Choi, Kyung; Kim, Jin Su; Cho, Shin-Hyeong; Lee, Won-Ja; Lim, Sung-Bin; Cha, Seok Ho; Park, Yun-Kyu; Pak, Jhang Ho; Lee, Hyeong-Woo; Hong, Sung-Jong; Kim, Tong-Soo

    2013-01-01

    Microscopic examination of eggs of parasitic helminths in stool samples has been the most widely used classical diagnostic method for infections, but tiny and low numbers of eggs in stool samples often hamper diagnosis of helminthic infections with classical microscopic examination. Moreover, it is also difficult to differentiate parasite eggs by the classical method, if they have similar morphological characteristics. In this study, we developed a rapid and sensitive polymerase chain reaction (PCR)-based molecular diagnostic method for detection of Clonorchis sinensis eggs in stool samples. Nine primers were designed based on the long-terminal repeat (LTR) of C. sinensis retrotransposon1 (CsRn1) gene, and seven PCR primer sets were paired. Polymerase chain reaction with each primer pair produced specific amplicons for C. sinensis, but not for other trematodes including Metagonimus yokogawai and Paragonimus westermani. Particularly, three primer sets were able to detect 10 C. sinensis eggs and were applicable to amplify specific amplicons from DNA samples purified from stool of C. sinensis-infected patients. This PCR method could be useful for diagnosis of C. sinensis infections in human stool samples with a high level of specificity and sensitivity. PMID:23916334

  8. Development of Real-Time Quantitative Polymerase Chain Reaction Assays to Track Treatment Response in Retinoid Resistant Acute Promyelocytic Leukemia

    Energy Technology Data Exchange (ETDEWEB)

    Jovanovic, Jelena V. [Cancer Genetics Laboratory, Department of Medical and Molecular Genetics, King’s College London School of Medicine, London (United Kingdom); Rennie, Kristian [GSTS Pathology, Guy’s Hospital, London (United Kingdom); Culligan, Dominic [Department of Haematology, Aberdeen Royal Infirmary, Aberdeen (United Kingdom); Peniket, Andrew [Department of Haematology, John Radcliffe Hospital, Oxford (United Kingdom); Lennard, Anne [Department of Haematology, Royal Victoria Infirmary, Newcastle (United Kingdom); Harrison, Justin [Department of Haematology, Hemel Hempstead Hospital, Hemel Hempstead (United Kingdom); Vyas, Paresh [Medical Research Council Molecular Haematology Unit, Weatherall Institute of Molecular Medicine, Oxford (United Kingdom); Grimwade, David, E-mail: david.grimwade@genetics.kcl.ac.uk [Cancer Genetics Laboratory, Department of Medical and Molecular Genetics, King’s College London School of Medicine, London (United Kingdom)

    2011-10-25

    Molecular detection of minimal residual disease (MRD) has become established to assess remission status and guide therapy in patients with ProMyelocytic Leukemia–RARA+ acute promyelocytic leukemia (APL). However, there are few data on tracking disease response in patients with rarer retinoid resistant subtypes of APL, characterized by PLZF–RARA and STAT5b–RARA. Despite their rarity (<1% of APL) we identified 6 cases (PLZF–RARA, n = 5; STAT5b–RARA, n = 1), established the respective breakpoint junction regions and designed reverse transcription-quantitative real-time polymerase chain reaction (RT-qPCR) assays to detect leukemic transcripts. The relative level of fusion gene expression in diagnostic samples was comparable to that observed in t(15;17) – associated APL, affording assay sensitivities of ∼1 in 10{sup 4}−10{sup 5}. Serial samples were available from two PLZF–RARA APL patients. One showed persistent polymerase chain reaction positivity, predicting subsequent relapse, and remains in CR2, ∼11 years post-autograft. The other, achieved molecular remission (CRm) with combination chemotherapy, remaining in CR1 at 6 years. The STAT5b–RARA patient failed to achieve CRm following frontline combination chemotherapy and ultimately proceeded to allogeneic transplant on the basis of a steadily rising fusion transcript level. These data highlight the potential of RT-qPCR detection of MRD to facilitate development of more individualized approaches to the management of rarer molecularly defined subsets of acute leukemia.

  9. Development of Real-Time Quantitative Polymerase Chain Reaction Assays to Track Treatment Response in Retinoid Resistant Acute Promyelocytic Leukemia

    International Nuclear Information System (INIS)

    Jovanovic, Jelena V.; Rennie, Kristian; Culligan, Dominic; Peniket, Andrew; Lennard, Anne; Harrison, Justin; Vyas, Paresh; Grimwade, David

    2011-01-01

    Molecular detection of minimal residual disease (MRD) has become established to assess remission status and guide therapy in patients with ProMyelocytic Leukemia–RARA+ acute promyelocytic leukemia (APL). However, there are few data on tracking disease response in patients with rarer retinoid resistant subtypes of APL, characterized by PLZF–RARA and STAT5b–RARA. Despite their rarity (<1% of APL) we identified 6 cases (PLZF–RARA, n = 5; STAT5b–RARA, n = 1), established the respective breakpoint junction regions and designed reverse transcription-quantitative real-time polymerase chain reaction (RT-qPCR) assays to detect leukemic transcripts. The relative level of fusion gene expression in diagnostic samples was comparable to that observed in t(15;17) – associated APL, affording assay sensitivities of ∼1 in 10 4 −10 5 . Serial samples were available from two PLZF–RARA APL patients. One showed persistent polymerase chain reaction positivity, predicting subsequent relapse, and remains in CR2, ∼11 years post-autograft. The other, achieved molecular remission (CRm) with combination chemotherapy, remaining in CR1 at 6 years. The STAT5b–RARA patient failed to achieve CRm following frontline combination chemotherapy and ultimately proceeded to allogeneic transplant on the basis of a steadily rising fusion transcript level. These data highlight the potential of RT-qPCR detection of MRD to facilitate development of more individualized approaches to the management of rarer molecularly defined subsets of acute leukemia.

  10. Investigation of Spectral Characteristics of Pulsed Xenon Lamps for Combined Photochemical Degradation of Organometallic Compounds in Liquid Radioactive Waste

    Directory of Open Access Journals (Sweden)

    M. A. Mishakov

    2017-01-01

    Full Text Available The paper considers the composition of liquid radioactive wastes from the nuclear plants. Using traditional ways to extract organometallic compounds formed, when using the deactivation solutions to clean the surfaces of nuclear plant rooms, are complicated. The paper studies the edge-cutting methods of solving this problem. Its proposal is to use a combined ultraviolet treatment for organometallic compounds degradation based on ethylenediaminetetraacetic acid (EDTA via pulsed xenon lamps. A potential use of the tubular and spherical geometry lamps is examined and advantages, disadvantages and features of these lamps are described. Instead of the pure EDTA the experiments used its disodium salt (Na2-EDTA. The hydrogen peroxide was used as an extra oxidizer. Absorption spectrums of solutions with various Na2-EDTA - hydrogen peroxide ratio were measured. It is found that the absorbance curve maximum is in the shortwave spectrum region (λ < 210 nm. The use of amalgam lamps of monochromatic radiation at wavelength λ = 254 nm will result only in formation of hydroxyl radicals but direct destruction processes of EDTA molecules due to radiation will be rare, and this decreases efficiency of their use.The spectral radiation characteristics of various continuum spectrum pulsed xenon lamps was measured. The experimental data expressed in relative units were compared with the emission spectrum of an absolutely black body. The paper shows that in spherical lamps high brightness temperature can be reached. Thus, in spherical lamps it is possible to obtain a spectrum, which is in maximum correlation with the absorption spectrum of the solutions under study, thereby making them a prospective radiation source for photo-degradation of EDTA compounds. For drawing a final conclusion it is necessary to conduct researches in order to compare Na2-EDTA degradation via tubular and spherical xenon lamps.

  11. Development of experimental method for self-wastage behavior in sodium-water reaction. Development of test rig (SWAT-2R) and study for experimental procedure

    International Nuclear Information System (INIS)

    Abe, Yuta; Shimoyama, Kazuhito; Kurihara, Akikazu

    2014-07-01

    In case of water leak from a penetrated crack on a tube of steam generator in the sodium cooled fast reactor (SFR), self-wastage, that increases the size of leak, may take place by corrosion related to chemical reaction between sodium and water. If the self-wastage continues in a certain period of time, the intact tube bundle may be damaged as a result of enlarged leak. For the safety evaluation of the accident, JAEA has been developing the analytical method of self-wastage using the multi-dimensional sodium-water reaction code. Experiments conducted so far used mainly crack-type test pieces. However, reproducibility was limited and it was difficult to evaluate individual effects of the phenomena in detail. This report describes the development of new experimental rig (SWAT-2R). SWAT-2R enables to examine corrosion effecting factors that were ambiguous in the previous studies. The report includes description of development of micro-leak test piece, examination of experimental procedure. The results will provide fundamental data for validation of the self-wastage analytical method. (author)

  12. Effects on the development of Dipylidium caninum and on the host reaction to this parasite in the adult flea (Ctenocephalides felis felis).

    Science.gov (United States)

    Pugh, R E

    1987-01-01

    Temperature was found to be a major factor affecting the development of Dipylidium caninum and the presence of a host reaction of adult Ctenocephalides felis felis to D. caninum. Adult fleas reared at 30-32 degrees C contained fully developed metacestodes when they emerged from their cocoons. However at lower temperatures, D. caninum could not complete development until the flea hosts had spent some time on their mammalian hosts. It was the surface temperature of the mammals (31-36 degrees C) and not the fleas' blood meals which resulted in the metacestodes completing their development. This development of D. caninum was therefore independent of the flea development. At 20 degrees C, a larger and more prolonged host reaction was mounted than at higher temperatures. The larval flea diet had a small effect on the subsequent cestode development and the adult fleas' reaction to it.

  13. Developing HIV-1 Protease Inhibitors through Stereospecific Reactions in Protein Crystals.

    Science.gov (United States)

    Olajuyigbe, Folasade M; Demitri, Nicola; De Zorzi, Rita; Geremia, Silvano

    2016-10-31

    Protease inhibitors are key components in the chemotherapy of HIV infection. However, the appearance of viral mutants routinely compromises their clinical efficacy, creating a constant need for new and more potent inhibitors. Recently, a new class of epoxide-based inhibitors of HIV-1 protease was investigated and the configuration of the epoxide carbons was demonstrated to play a crucial role in determining the binding affinity. Here we report the comparison between three crystal structures at near-atomic resolution of HIV-1 protease in complex with the epoxide-based inhibitor, revealing an in-situ epoxide ring opening triggered by a pH change in the mother solution of the crystal. Increased pH in the crystal allows a stereospecific nucleophile attack of an ammonia molecule onto an epoxide carbon, with formation of a new inhibitor containing amino-alcohol functions. The described experiments open a pathway for the development of new stereospecific protease inhibitors from a reactive lead compound.

  14. Developing HIV-1 Protease Inhibitors through Stereospecific Reactions in Protein Crystals

    Directory of Open Access Journals (Sweden)

    Folasade M. Olajuyigbe

    2016-10-01

    Full Text Available Protease inhibitors are key components in the chemotherapy of HIV infection. However, the appearance of viral mutants routinely compromises their clinical efficacy, creating a constant need for new and more potent inhibitors. Recently, a new class of epoxide-based inhibitors of HIV-1 protease was investigated and the configuration of the epoxide carbons was demonstrated to play a crucial role in determining the binding affinity. Here we report the comparison between three crystal structures at near-atomic resolution of HIV-1 protease in complex with the epoxide-based inhibitor, revealing an in-situ epoxide ring opening triggered by a pH change in the mother solution of the crystal. Increased pH in the crystal allows a stereospecific nucleophile attack of an ammonia molecule onto an epoxide carbon, with formation of a new inhibitor containing amino-alcohol functions. The described experiments open a pathway for the development of new stereospecific protease inhibitors from a reactive lead compound.

  15. Preparative and mechanistic studies toward the rational development of catalytic, enantioselective selenoetherification reactions.

    Science.gov (United States)

    Denmark, Scott E; Kalyani, Dipannita; Collins, William R

    2010-11-10

    A systematic investigation into the Lewis base catalyzed, asymmetric, intramolecular selenoetherification of olefins is described. A critical challenge for the development of this process was the identification and suppression of racemization pathways available to arylseleniranium ion intermediates. This report details a thorough study of the influences of the steric and electronic modulation of the arylselenenyl group on the configurational stability of enantioenriched seleniranium ions. These studies show that the 2-nitrophenyl group attached to the selenium atom significantly attenuates the racemization of seleniranium ions. A variety of achiral Lewis bases catalyze the intramolecular selenoetherification of alkenes using N-(2-nitrophenylselenenyl)succinimide as the electrophile along with a Brønsted acid. Preliminary mechanistic studies suggest the intermediacy of ionic Lewis base-selenium(II) adducts. Most importantly, a broad survey of chiral Lewis bases revealed that 1,1'-binaphthalene-2,2'-diamine (BINAM)-derived thiophosphoramides catalyze the cyclization of unsaturated alcohols in the presence of N-(2-nitrophenylselenenyl)succinimide and methanesulfonic acid. A variety of cyclic seleno ethers were produced in good chemical yields and in moderate to good enantioselectivities, which constitutes the first catalytic, enantioselective selenofunctionalization of unactivated olefins.

  16. Mechanism of Doping Gallium Arsenide with Carbon Tetrachloride During Organometallic Vapor-Phase Epitaxy

    National Research Council Canada - National Science Library

    Warddrip, Michael

    1997-01-01

    .... In addition, the reaction of CC14 with the GaAs(001) surface was monitored in ultrahigh vacuum using infrared spectroscopy, temperature programmed desorption, and scanning tunneling microscopy...

  17. Detection of human herpesvirus 8 by quantitative polymerase chain reaction: development and standardisation of methods.

    Science.gov (United States)

    Speicher, David J; Johnson, Newell W

    2012-09-11

    Human herpesvirus 8 (HHV-8), the aetiological agent of Kaposi's sarcoma (KS), multicentric Castleman's disease (MCD), and primary effusion lymphoma (PEL) is rare in Australia, but endemic in Sub-Saharan Africa, parts of South-east Asia and Oceania. While the treatment of external KS lesions can be monitored by clinical observation, the internal lesions of KS, MCD and PEL require extensive and expensive internal imaging, or autopsy. In patients with MCD and PEL, if HHV-8 viraemia is not reduced quickly, ~50% die within 24 months. HHV-8 qPCR is a valuable tool for monitoring HHV-8 viraemia, but is not available in many parts of the world, including those with high prevalence of KS and HHV-8. A new molecular facility with stringent three-phase workflow was established, adhering to NPAAC and CLSI guidelines. Three fully validated quantitative assays were developed: two for detection and quantification of HHV-8; one for GAPDH, necessary for normalisation of viral loads in tissue and peripheral blood. The HHV-8 ORF73 and ORF26 qPCR assays were 100% specific. All qPCR assays, displayed a broad dynamic range (102 to 1010 copies/μL TE Buffer) with a limit of detection of 4.85x103, 5.61x102, and 2.59x102 copies/μL TE Buffer and a limit of quantification of 4.85x103, 3.01x102, and 1.38x102 copies/μL TE Buffer for HHV-8 ORF73, HHV-8 ORF26, and GAPDH respectively.The assays were tested on a panel of 35 KS biopsies from Queensland. All were HHV-8 qPCR positive with average viral load of 2.96x105 HHV-8 copies/μL DNA extract (range: 4.37x103 to 1.47x106 copies/μL DNA extract): When normalised these equate to an average viral load of 2.44x104 HHV-8 copies/103 cells (range: 2.20x102 to 7.38x105 HHV-8 copies/103 cells). These are the first fully optimised, validated and MIQE compliant HHV-8 qPCR assays established in Australia. They worked well for qualitative detection of HHV-8 in archival tissue, and are well-suited for quantitative detection in whole blood. They are now

  18. Detection of human herpesvirus 8 by quantitative polymerase chain reaction: development and standardisation of methods

    Directory of Open Access Journals (Sweden)

    Speicher David J

    2012-09-01

    Full Text Available Abstract Background Human herpesvirus 8 (HHV-8, the aetiological agent of Kaposi’s sarcoma (KS, multicentric Castleman’s disease (MCD, and primary effusion lymphoma (PEL is rare in Australia, but endemic in Sub-Saharan Africa, parts of South-east Asia and Oceania. While the treatment of external KS lesions can be monitored by clinical observation, the internal lesions of KS, MCD and PEL require extensive and expensive internal imaging, or autopsy. In patients with MCD and PEL, if HHV-8 viraemia is not reduced quickly, ~50% die within 24 months. HHV-8 qPCR is a valuable tool for monitoring HHV-8 viraemia, but is not available in many parts of the world, including those with high prevalence of KS and HHV-8. Methods A new molecular facility with stringent three-phase workflow was established, adhering to NPAAC and CLSI guidelines. Three fully validated quantitative assays were developed: two for detection and quantification of HHV-8; one for GAPDH, necessary for normalisation of viral loads in tissue and peripheral blood. Results The HHV-8 ORF73 and ORF26 qPCR assays were 100% specific. All qPCR assays, displayed a broad dynamic range (102 to 1010 copies/μL TE Buffer with a limit of detection of 4.85x103, 5.61x102, and 2.59x102 copies/μL TE Buffer and a limit of quantification of 4.85x103, 3.01x102, and 1.38x102 copies/μL TE Buffer for HHV-8 ORF73, HHV-8 ORF26, and GAPDH respectively. The assays were tested on a panel of 35 KS biopsies from Queensland. All were HHV-8 qPCR positive with average viral load of 2.96x105 HHV-8 copies/μL DNA extract (range: 4.37x103 to 1.47x106 copies/μL DNA extract: When normalised these equate to an average viral load of 2.44x104 HHV-8 copies/103 cells (range: 2.20x102 to 7.38x105 HHV-8 copies/103 cells. Conclusions These are the first fully optimised, validated and MIQE compliant HHV-8 qPCR assays established in Australia. They worked well for qualitative detection of HHV-8 in archival tissue, and are well

  19. Click and Release: A Chemical Strategy toward Developing Gasotransmitter Prodrugs by Using an Intramolecular Diels-Alder Reaction.

    Science.gov (United States)

    Ji, Xingyue; Zhou, Cheng; Ji, Kaili; Aghoghovbia, Robert E; Pan, Zhixiang; Chittavong, Vayou; Ke, Bowen; Wang, Binghe

    2016-12-19

    Prodrug strategies have been proven to be a very effective way of addressing delivery problems. Much of the chemistry in prodrug development relies on the ability to mask an appropriate functional group, which can be removed under appropriate conditions. However, developing organic prodrugs of gasotransmitters represent unique challenges. This is especially true with carbon monoxide, which does not have an easy "handle" for bioreversible derivatization. By taking advantage of an intramolecular Diels-Alder reaction, we have developed a prodrug strategy for preparations of organic CO prodrugs that are stable during synthesis and storage, and yet readily release CO with tunable release rates under near physiological conditions. The effectiveness of the CO prodrug system in delivering a sufficient quantity of CO for possible therapeutic applications has been studied using a cell culture anti-inflammatory assay and a colitis animal model. These studies fully demonstrate the proof of concept, and lay a strong foundation for further medicinal chemistry work in developing organic CO prodrugs. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Development of a Tandem Repeat-Based Polymerase Chain Displacement Reaction Method for Highly Sensitive Detection of 'Candidatus Liberibacter asiaticus'.

    Science.gov (United States)

    Lou, Binghai; Song, Yaqin; RoyChowdhury, Moytri; Deng, Chongling; Niu, Ying; Fan, Qijun; Tang, Yan; Zhou, Changyong

    2018-02-01

    Huanglongbing (HLB) is one of the most destructive diseases in citrus production worldwide. Early detection of HLB pathogens can facilitate timely removal of infected citrus trees in the field. However, low titer and uneven distribution of HLB pathogens in host plants make reliable detection challenging. Therefore, the development of effective detection methods with high sensitivity is imperative. This study reports the development of a novel method, tandem repeat-based polymerase chain displacement reaction (TR-PCDR), for the detection of 'Candidatus Liberibacter asiaticus', a widely distributed HLB-associated bacterium. A uniquely designed primer set (TR2-PCDR-F/TR2-PCDR-1R) and a thermostable Taq DNA polymerase mutant with strand displacement activity were used for TR-PCDR amplification. Performed in a regular thermal cycler, TR-PCDR could produce more than two amplicons after each amplification cycle. Sensitivity of the developed TR-PCDR was 10 copies of target DNA fragment. The sensitive level was proven to be 100× higher than conventional PCR and similar to real-time PCR. Data from the detection of 'Ca. L. asiaticus' with filed samples using the above three methods also showed similar results. No false-positive TR-PCDR amplification was observed from healthy citrus samples and water controls. These results thereby illustrated that the developed TR-PCDR method can be applied to the reliable, highly sensitive, and cost-effective detection of 'Ca. L. asiaticus'.

  1. Development of Portable Pulsed Neutron Generators Utilizing a D-T or D-D Fusion Reaction

    International Nuclear Information System (INIS)

    Nishimura, Kazuya; Miake, Yoshinobu; Kato, Michio; Rintsu, Yukou

    2001-01-01

    Prototypes of sealed neutron tubes in a D-T or D-D fusion reaction for logging while drilling (LWD) were developed; then operational tests were performed to check their functional properties. One of the prototypes passed most of the specified conditions for using LWD. Further studies were needed to put a sealed neutron tube into practical use. For applications to other fields, such as an in situ calibration source for neutron detector efficiencies and an in situ calibration source for fusion systems, a sealed neutron tube is needed to have higher-intensity neutron output and a long life. Thus, the performance of the ion source used in the neutron tube is improved to obtain high gas utilization efficiencies or low-pressure operation with high ionization efficiencies. The characteristics of the new ion sources used in the foregoing sealed neutron tube are discussed in terms of preliminary tests. The aforementioned performances are obtained

  2. Development of the work function approach to the underpotential deposition of metals. Application to the hydrogen evolution reaction

    International Nuclear Information System (INIS)

    Trasatti, S.

    1975-01-01

    A theory is developed for the underpotential deposition of metals. Concepts are then extended to oxygen and hydrogen adsorption. Analysis of results shows that, unlike oxygen adsorption, hydrogen adsorption in solution probably follows a different pattern with respect to the gas phase situation. The hydrogen evolution reaction is discussed in the light of the above findings and it is shown that usual concepts regarding the reactivity scale of metals towards hydrogen should be reconsidered taking into account solvent and entropy effects. The latters can account for the behaviour of sp-metals. The formers are important with transition metals. The final picture is consistent with the idea that M-H 2 O interactions are much stronger on transition than on sp-metals. (orig.) [de

  3. Development of a screening method for genetically modified soybean by plasmid-based quantitative competitive polymerase chain reaction.

    Science.gov (United States)

    Shimizu, Eri; Kato, Hisashi; Nakagawa, Yuki; Kodama, Takashi; Futo, Satoshi; Minegishi, Yasutaka; Watanabe, Takahiro; Akiyama, Hiroshi; Teshima, Reiko; Furui, Satoshi; Hino, Akihiro; Kitta, Kazumi

    2008-07-23

    A novel type of quantitative competitive polymerase chain reaction (QC-PCR) system for the detection and quantification of the Roundup Ready soybean (RRS) was developed. This system was designed based on the advantage of a fully validated real-time PCR method used for the quantification of RRS in Japan. A plasmid was constructed as a competitor plasmid for the detection and quantification of genetically modified soy, RRS. The plasmid contained the construct-specific sequence of RRS and the taxon-specific sequence of lectin1 (Le1), and both had 21 bp oligonucleotide insertion in the sequences. The plasmid DNA was used as a reference molecule instead of ground seeds, which enabled us to precisely and stably adjust the copy number of targets. The present study demonstrated that the novel plasmid-based QC-PCR method could be a simple and feasible alternative to the real-time PCR method used for the quantification of genetically modified organism contents.

  4. Identification of nickel response genes in abnormal early developments of sea urchin by differential display polymerase chain reaction.

    Science.gov (United States)

    Ryu, Tae Kwon; Lee, Gunsup; Rhee, Yong; Park, Heung-Sik; Chang, Man; Lee, Sukchan; Lee, Jaean; Lee, Taek-Kyun

    2012-10-01

    Bioassays and biomarkers have been previously developed to assess the effects of heavy metal contaminants on the early life stages of the sea urchin. In this study, malformation in the early developmental processes was observed in sea urchin (Strongylocentrotus intermedius) larvae exposed to 10 ppm Ni for over 30 h. The most critical stage at which the triggering of nickel effects takes place is thought to be the blastula stage, which occurs after fertilization in larval development. To investigate the molecular-level responses of sea urchin exposed to heavy metal stress and to explore the differentially expressed genes that are induced or repressed by nickel, differential display polymerase chain reaction (DD-PCR) was used with sea urchin mRNAs. The malformation-related genes expressed in the early life stages of the sea urchin were cloned from larvae exposed to 10 ppm of nickel for 15 h, and accessed via DD-PCR. Sequence analysis results revealed that each of the genes evidenced high homology with EGF2, PCSK9, serine/threonine protein kinase, apolipophorin precursor protein, and MGC80921 protein/transcript variant 2. This result may prove useful in the development of novel biomarkers for the assessment of heavy metal stresses on sea urchin embryos. Copyright © 2012 Elsevier Inc. All rights reserved.

  5. 2013 Gordon Research Conference, Inorganic reaction mechanisms, Galveston, TX, March 3-8 2013

    Energy Technology Data Exchange (ETDEWEB)

    Abu-Omar, Mahdi M. [Purdue Univ., West Lafayette, IN (United States)

    2012-12-08

    The 2013 Gordon Conference on Inorganic Reaction Mechanisms will present cutting-edge research on the molecular aspects of inorganic reactions involving elements from throughout the periodic table and state-of-the art techniques that are used in the elucidation of reaction mechanisms. The Conference will feature a wide range of topics, such as homogeneous and heterogeneous catalysis, metallobiochemistry, electron-transfer in energy reactions, polymerization, nitrogen fixation, green chemistry, oxidation, solar conversion, alkane functionalization, organotransition metal chemistry, and computational chemistry. The talks will cover themes of current interest including energy, materials, and bioinorganic chemistry. Sections cover: Electron-Transfer in Energy Reactions; Catalytic Polymerization and Oxidation Chemistry; Kinetics and Spectroscopy of Heterogeneous Catalysts; Metal-Organic Chemistry and its Application in Synthesis; Green Energy Conversion;Organometallic Chemistry and Activation of Small Molecules; Advances in Kinetics Modeling and Green Chemistry; Metals in Biology and Disease; Frontiers in Catalytic Bond Activation and Cleavage.

  6. Temperatures during flower bud development affect pollen germination, self-incompatibility reaction and early fruit development of clementine (Citrus clementina Hort. ex Tan.).

    Science.gov (United States)

    Distefano, G; Gentile, A; Hedhly, A; La Malfa, S

    2018-03-01

    One of the key environmental factors affecting plant reproductive systems is temperature. Characterising such effects is especially relevant for some commercially important genera such as Citrus. In this genus, failure of fertilisation results in parthenocarpic fruit development and seedlessness, which is a much-prized character. Here, we characterise the effects of temperature on flower and ovary development, and on pollen-pistil interactions in 'Comune' clementine (Citrus clementina Hort. ex Tan.). We examine flower bud development, in vitro pollen germination and pollen-pistil interaction at different temperatures (15, 20, 25 or 30 °C). These temperatures span the range from 'cold' to 'hot' weather during the flowering season in many citrus-growing regions. Temperature had a strong effect on flower and ovary development, pollen germination, and pollen tube growth kinetics. In particular, parthenocarpic fruit development (indicated by juice vesicle growth) was initiated early if flowers were exposed to warmer temperatures during anthesis. Exposure to different temperatures during flower bud development also alters expression of the self-incompatibility reaction. This affects the point in the pistil at which pollen tube growth is arrested and confirms the role of sub- and supra-optimal temperatures in determining the numbers of pollen tubes reaching the ovary. © 2017 German Society for Plant Sciences and The Royal Botanical Society of the Netherlands.

  7. Factors affecting the development of adverse drug reactions to β-blockers in hospitalized cardiac patient population

    Directory of Open Access Journals (Sweden)

    Mugoša S

    2016-08-01

    Full Text Available Snežana Mugoša,1,2 Nataša Djordjević,3 Nina Djukanović,4 Dragana Protić,5 Zoran Bukumirić,6 Ivan Radosavljević,7 Aneta Bošković,8 Zoran Todorović5,9 1Department of Pharmacotherapy, Faculty of Pharmacy, University of Montenegro, 2Clinical Trial Department, Agency for Medicines and Medical Devices of Montenegro, Podgorica, Montenegro; 3Department of Pharmacology and Toxicology, Faculty of Medical Sciences, University of Kragujevac, Kragujevac, 4High Medical School “Milutin Milanković”, Belgrade, 5Department of Pharmacology, Clinical Pharmacology and Toxicology, 6Institute for Medical Statistics and Informatics, Faculty of Medicine, University of Belgrade, Belgrade, 7Department of Surgery, Faculty of Medical Sciences, University of Kragujevac, Kragujevac, Serbia; 8Clinic for Heart Diseases, Clinical Centre of Montenegro, Podgorica, Montenegro; 9Department of Clinical Immunology and Allergy, Medical Center “Bežanijska kosa”, Belgrade, Serbia Abstract: The aim of the present study was to undertake a study on the prevalence of cytochrome P450 2D6 (CYP2D6 poor metabolizer alleles (*3, *4, *5, and *6 on a Montenegrin population and its impact on developing adverse drug reactions (ADRs of β-blockers in a hospitalized cardiac patient population. A prospective study was conducted in the Cardiology Center of the Clinical Center of Montenegro and included 138 patients who had received any β-blocker in their therapy. ADRs were collected using a specially designed questionnaire, based on the symptom list and any signs that could point to eventual ADRs. Data from patients’ medical charts, laboratory tests, and other available parameters were observed and combined with the data from the questionnaire. ADRs to β-blockers were observed in 15 (10.9% patients. There was a statistically significant difference in the frequency of ADRs in relation to genetically determined enzymatic activity (P<0.001, with ADRs’ occurrence significantly

  8. Phase Transition Enthalpy Measurements of Organic and Organometallic Compounds. Sublimation, Vaporization and Fusion Enthalpies From 1880 to 2015. Part 1. C1 - C10

    Science.gov (United States)

    Acree, William; Chickos, James S.

    2016-09-01

    A compendium of phase change enthalpies published in 2010 is updated to include the period 1880-2015. Phase change enthalpies including fusion, vaporization, and sublimation enthalpies are included for organic, organometallic, and a few inorganic compounds. Part 1 of this compendium includes organic compounds from C1 to C10. Part 2 of this compendium, to be published separately, will include organic and organometallic compounds from C11 to C192. Sufficient data are presently available to permit thermodynamic cycles to be constructed as an independent means of evaluating the reliability of the data. Temperature adjustments of phase change enthalpies from the temperature of measurement to the standard reference temperature, T = 298.15 K, and a protocol for doing so are briefly discussed.

  9. Molecule-Level g-C3N4 Coordinated Transition Metals as a New Class of Electrocatalysts for Oxygen Electrode Reactions

    KAUST Repository

    Zheng, Yao

    2017-02-21

    Organometallic complexes with metal-nitrogen/carbon (M-N/C) coordination are the most important alternatives to precious metal catalysts for oxygen reduction and evolution reactions (ORR and OER) in energy conversion devices. Here, we designed and developed a range of molecule-level graphitic carbon nitride (g-C3N4) coordinated transition metals (M-C3N4) as a new generation of M-N/C catalysts for these oxygen electrode reactions. As a proof-of-concept example, we conducted theoretical evaluation and experimental validation on a cobalt-C3N4 catalyst with a desired molecular configuration, which possesses comparable electrocatalytic activity to that of precious metal benchmarks for the ORR and OER in alkaline media. The correlation of experimental and computational results confirms that this high activity originates from the precise M-N2 coordination in the g-C3N4 matrix. Moreover, the reversible ORR/OER activity trend for a wide variety of M-C3N4 complexes has been constructed to provide guidance for the molecular design of this promising class of catalysts.

  10. Developing a 3-choice serial reaction time task for examining neural and cognitive function in an equine model.

    Science.gov (United States)

    Roberts, Kirsty; Hemmings, Andrew J; McBride, Sebastian D; Parker, Matthew O

    2017-12-01

    Large animal models of human neurological disorders are advantageous compared to rodent models due to their neuroanatomical complexity, longevity and their ability to be maintained in naturalised environments. Some large animal models spontaneously develop behaviours that closely resemble the symptoms of neural and psychiatric disorders. The horse is an example of this; the domestic form of this species consistently develops spontaneous stereotypic behaviours akin to the compulsive and impulsive behaviours observed in human neurological disorders such as Tourette's syndrome. The ability to non-invasively probe normal and abnormal equine brain function through cognitive testing may provide an extremely useful methodological tool to assess brain changes associated with certain human neurological and psychiatric conditions. An automated operant system with the ability to present visual and auditory stimuli as well as dispense salient food reward was developed. To validate the system, ten horses were trained and tested using a standard cognitive task (three choice serial reaction time task (3-CSRTT)). All animals achieved total learning criterion and performed six probe sessions. Learning criterion was met within 16.30±0.79 sessions over a three day period. During six probe sessions, level of performance was maintained at 80.67±0.57% (mean±SEM) accuracy. This is the first mobile fully automated system developed to examine cognitive function in the horse. A fully-automated operant system for mobile cognitive function of a large animal model has been designed and validated. Horses pose an interesting complementary model to rodents for the examination of human neurological dysfunction. Copyright © 2017 Elsevier B.V. All rights reserved.

  11. Mechanistic studies on reactivities of organometallic macrocyclic complexes of chromium and cobalt

    International Nuclear Information System (INIS)

    Shi, Shu.

    1990-01-01

    Reaction pathways leading to the formation and cleavage of a transition metal-carbon bond at various oxidation states of the metal occupy a central position in understanding many enzymatic reactions and designing catalysts. The report is divided into six parts that (1) focus on the homolysis vs heterolysis of a C-Cr(III) bond, (2) describes a unique chain reaction and a S E 2 reaction I 2 and RCrL 2+ , (3) concerns the oxidation of organochromium(III) complexes by dihalide and pseudo-dihalide radical anions generated by pulse radiolysis, (4) concentrates on the oxidation mechanism of RCr(H 2 O) 2+ and the fate of RCr(H 2 O) 3+ as well as the corresponding reduction potentials, (5) extends study of organocobalt complexes with attention to reduction induced cleavages of a transition metal-carbon bond, and (6) describes the crystallization of [(CH 3 ) 4 N][Co(dmgBF 2 ) 2 py] and reports its molecular structure as determined by x-ray diffraction. 182 refs., 25 figs., 16 tabs. (BM)

  12. Mechanistic studies on reactivities of organometallic macrocyclic complexes of chromium and cobalt

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Shu.

    1990-12-10

    Reaction pathways leading to the formation and cleavage of a transition metal-carbon bond at various oxidation states of the metal occupy a central position in understanding many enzymatic reactions and designing catalysts. The report is divided into six parts that (1) focus on the homolysis vs heterolysis of a C-Cr(III) bond, (2) describes a unique chain reaction and a S{sub E}2 reaction I{sub 2} and RCrL{sup 2+}, (3) concerns the oxidation of organochromium(III) complexes by dihalide and pseudo-dihalide radical anions generated by pulse radiolysis, (4) concentrates on the oxidation mechanism of RCr(H{sub 2}O){sup 2+} and the fate of RCr(H{sub 2}O){sup 3+} as well as the corresponding reduction potentials, (5) extends study of organocobalt complexes with attention to reduction induced cleavages of a transition metal-carbon bond, and (6) describes the crystallization of ((CH{sub 3}){sub 4}N)(Co(dmgBF{sub 2}){sub 2}py) and reports its molecular structure as determined by x-ray diffraction. 182 refs., 25 figs., 16 tabs. (BM)

  13. Microfluidic technology platforms for synthesizing, labeling and measuring the kinetics of transport and biochemical reactions for developing molecular imaging probes

    Energy Technology Data Exchange (ETDEWEB)

    Phelps, Michael E. [Univ. of California, Los Angeles, CA (United States)

    2009-09-01

    Radiotracer techniques are used in environmental sciences, geology, biology and medicine. Radiotracers with Positron Emission Tomography (PET) provided biological examinations of ~3 million patients 2008. Despite the success of positron labeled tracers in many sciences, there is limited access in an affordable and convenient manner to develop and use new tracers. Integrated microfluidic chips are a new technology well matched to the concentrations of tracers. Our goal is to develop microfluidic chips and new synthesis approaches to enable wide dissemination of diverse types of tracers at low cost, and to produce new generations of radiochemists for which there are many unfilled jobs. The program objectives are to: 1. Develop an integrated microfluidic platform technology for synthesizing and 18F-labeling diverse arrays of different classes of molecules. 2. Incorporate microfluidic chips into small PC controlled devices (“Synthesizer”) with a platform interfaced to PC for electronic and fluid input/out control. 3. Establish a de-centralized model with Synthesizers for discovering and producing molecular imaging probes, only requiring delivery of inexpensive [18F]fluoride ion from commercial PET radiopharmacies vs the centralized approach of cyclotron facilities synthesizing and shipping a few different types of 18F-probes. 4. Develop a position sensitive avalanche photo diode (PSAPD) camera for beta particles embedded in a microfluidic chip for imaging and measuring transport and biochemical reaction rates to valid new 18F-labeled probes in an array of cell cultures. These objectives are met within a research and educational program integrating radio-chemistry, synthetic chemistry, biochemistry, engineering and biology in the Crump Institute for Molecular Imaging. The Radiochemistry Training Program exposes PhD and post doctoral students to molecular imaging in vitro in cells and microorganisms in microfluidic chips and in vivo with PET, from new technologies

  14. The reaction π-p → π-π-π+p: Development of the analysis methods and selected results

    Science.gov (United States)

    Ryabchikov, D.

    2016-01-01

    We present the description of the analysis methods and results of applying them to the exclusive diffractive reaction π-p → π-π-π+p of 50 . 106 events measured with COMPASS detector. The large statistics of π-π-π+ events enables the two-dimensional partial-wave analysis independently in 100 bins of m(3π) with 0.5 < m(3π) < 2.5 GeV/c2 and in 11 intervals of squared momentum transfer with 0.1 < t' < 1 GeV2/c2. The partial-wave analysis sub-density matrix is the subject to further mass-dependent fits describing the data in terms of resonances in 3π system and coherent background contributions. The novel approach of extracting JPC = 0++(π+π-)S isobar amplitudes as model-free functions, different for several JPC 3π states, is used. It demonstrates the presence of processes π(1800) → f0(980)π and π(1800) → f0(1500)π as well as π2(1880) → f0(980)π and new narrow signal a1(1420) → f0(980)π, without any established shapes used for (π+π-)S isobars. The presented analysis is subject to further development and refinements which currently take place.

  15. Development of real-time quantitative polymerase chain reaction assays to track treatment response in retinoid resistant acute promyelocytic leukemia

    Directory of Open Access Journals (Sweden)

    Jelena V Jovanovic

    2011-10-01

    Full Text Available Molecular detection of minimal residual disease (MRD has become established to assess remission status and guide therapy in patients with PML-RARA+ acute promyelocytic leukemia (APL. However, there are few data on tracking disease response in patients with rarer retinoid resistant subtypes of APL, characterized by PLZF-RARA and STAT5b-RARA. Despite their relative rarity (<1% of APL we identified 6 cases (PLZF-RARA, n=5; STAT5b-RARA, n=1, established the respective breakpoint junction regions and designed real-time quantitative polymerase chain reaction (RQ-PCR assays to detect leukemic transcripts. The relative level of fusion gene expression in diagnostic samples was comparable to that observed in t(15;17-associated APL, affording assay sensitivities of ~1 in 104-105. Serial samples were available from 2 PLZF-RARA APL patients. One showed persistent PCR positivity, predicting subsequent relapse, and remains in CR2, ~11 years post-autograft. The other, achieved molecular remission (CRm with combination chemotherapy, remaining in CR1 at 6 years. The STAT5b-RARA patient failed to achieve CRm following frontline combination chemotherapy and ultimately proceeded to allogeneic transplant on the basis of a steadily rising fusion transcript level. These data highlight the potential of RQ-PCR detection of MRD to facilitate development of more individualized approaches to the management of rarer molecularly-defined subsets of acute leukemia.

  16. Development of Chemistry Triangle Oriented Module on Topic of Reaction Rate for Senior High School Level Grade XI Chemistry Learning.

    Science.gov (United States)

    Sari, D. R.; Hardeli; Bayharti

    2018-04-01

    This study aims to produce chemistry triangle oriented module on topic of reaction rate, and to reveal the validity and practicality level of the generated module. The type of research used is EducationalDesign Research (EDR) with development model is Plompmodel. This model consists of three phases, which are preliminary research, prototyping phase, and assessment phase. The instrument used in this research is questionnaire validity and practicality. The data of the research were analyzed by using Kappa Cohen formula. The chemistry triangle oriented module validation sheet was given to 5 validators consisting of 3 chemistry lecturers and 2 high school chemistry teachers, while the practicality sheet was given to 2 chemistry teachers, 6 students of SMAN 10 Padang grade XII MIA 5 on the small groupevaluation and 25 students of SMAN 10 Padang grade XII MIA 6 on the field test. Based on the questionnaire validity analysis, the validity level of the module is very high with the value of kappa moment 0.87. The level of practicality based on teacher questionnaire response is very high category with a kappa moment value 0.96. Based on the questionnaire of student responses on small group evaluation, the level of practicality is very high category with a kappa moment 0.81, and the practicality is very high category with kappa moment value 0.83 based on questionnaire of student response on field test.

  17. Catalysts prepared by interaction of transition metal organometallic compounds with the surface of supporters

    International Nuclear Information System (INIS)

    Ryndin, Yu.A.; Kuznetsov, B.N.; Moroz, Eh.M.; Tripol'skij, A.A.; Ermakov, Yu.I.

    1977-01-01

    The phase composition and dispersion of the catalyst (W + Pt)/SiO 2 , subjected to oxidation and reduction at an elevated temperature was investigated by roentgenographic methods (radial distribution of atoms and broadening of X-ray lines). The X-ray data are compared with the results of chemisorption measurements of platinum dispersion in the specimens and their activity in reactions of benzene hydration and ethane hydrogenolysis. It has been established that catalysts reduced at 600 deg C and not subjected to oxidation, as well as catalysts oxidized at 200 deg C and then reduced at 600 deg C are characterized by a high platinum dispersion. The dispersion catalysts are noted for their activity in the reaction of benzene hydration and ethane hydrogenolysis. On the other hand, the activity of catalysts oxidized and reduced in rigid conditions (600 deg C, air) is much lower and is close to the activity of the coarsely dispersed PtSiO 2 catalyst

  18. The processing of CdSe/Polymer nanocomposites via solution organometallic chemistry

    International Nuclear Information System (INIS)

    Khanna, P.K.; Singh, Narendra; Charan, Shobhit; Lonkar, Sunil P.; Reddy, A. Satyanarayana; Patil, Yogesh; Viswanath, A. Kasi

    2006-01-01

    This paper presents in situ preparation of CdSe nanoparticles using poly(vinyl alcohol) [PVA] and polymethylmethacrylate [PMMA] as matrices by use of organoselenium compound. Reaction of cadmium metal salt and 1,2,3-selenadiazole (the source of selenium) enabled formation of CdSe nanoparticles. Use of selenadiazole in the present work with polymer is first of its kind. The radical polymerization of methycrylate monomer with benzoyl peroxide followed by reaction of respective reagents have been successfully employed to synthesize CdSe/PMMA nanocomposite. Similarly, reaction between selenadiazole and cadmium metal salt in aq. PVA yielded polymer coated or mixed CdSe nanoparticles. The UV-vis absorption spectra showed blue shift of about 200 nm with respect to band-gap energy of bulk CdSe, due to size quantization effect in CdSe particles. An emission band was observed at 530 nm in photoluminescence spectrum (PL) of CdSe/PMMA. IR spectra indicated shifts in the values of the polymer functional group due to nanoparticles. X-ray measurement of CdSe/Polymer nano-composites showed broad pattern for cubic CdSe and particle size of CdSe was estimated to be <10 nm. TGA revealed gradual weight loss between 200 and 400 deg. C indicating increased thermal stability of the polymer

  19. Development of a General Aza-Cope Reaction Trigger Applied to Fluorescence Imaging of Formaldehyde in Living Cells.

    Science.gov (United States)

    Bruemmer, Kevin J; Walvoord, Ryan R; Brewer, Thomas F; Burgos-Barragan, Guillermo; Wit, Niek; Pontel, Lucas B; Patel, Ketan J; Chang, Christopher J

    2017-04-19

    Formaldehyde (FA) is a reactive signaling molecule that is continuously produced through a number of central biological pathways spanning epigenetics to one-carbon metabolism. On the other hand, aberrant, elevated levels of FA are implicated in disease states ranging from asthma to neurodegenerative disorders. In this context, fluorescence-based probes for FA imaging are emerging as potentially powerful chemical tools to help disentangle the complexities of FA homeostasis and its physiological and pathological contributions. Currently available FA indicators require direct modification of the fluorophore backbone through complex synthetic considerations to enable FA detection, often limiting the generalization of designs to other fluorophore classes. To address this challenge, we now present the rational, iterative development of a general reaction-based trigger utilizing 2-aza-Cope reactivity for selective and sensitive detection of FA in living systems. Specifically, we developed a homoallylamine functionality that can undergo a subsequent self-immolative β-elimination, creating a FA-responsive trigger that is capable of masking a phenol on a fluorophore or any other potential chemical scaffold for related imaging and/or therapeutic applications. We demonstrate the utility of this trigger by creating a series of fluorescent probes for FA with excitation and emission wavelengths that span the UV to visible spectral regions through caging of a variety of dye units. In particular, Formaldehyde Probe 573 (FAP573), based on a resorufin scaffold, is the most red-shifted and FA sensitive in this series in terms of signal-to-noise responses and enables identification of alcohol dehydrogenase 5 (ADH5) as an enzyme that regulates FA metabolism in living cells. The results provide a starting point for the broader use of 2-aza-Cope reactivity for probing and manipulating FA biology.

  20. Development of species-specific DNA probes for Campylobacter jejuni, Campylobacter coli, and Campylobacter lari by polymerase chain reaction fingerprinting

    NARCIS (Netherlands)

    Giesendorf, B A; van Belkum, A; Koeken, A; Stegeman, H; Henkens, M H; van der Plas, J; Goossens, H; Niesters, H G; Quint, W G

    The application of polymerase chain reaction (PCR) fingerprinting assays enables discrimination between species and strains of microorganisms. PCR primers aiming at arbitrary sequences in combination with primers directed against the repetitive extragenic palindrome (REP) or enterobacterial

  1. Nuclear reactions

    International Nuclear Information System (INIS)

    Corner, J.; Richardson, K.; Fenton, N.

    1990-01-01

    Nuclear reactions' marks a new development in the study of television as an agency of public policy debate. During the Eighties, nuclear energy became a major international issue. The disasters at Three-mile Island and Chernobyl created a global anxiety about its risks and a new sensitivity to it among politicians and journalists. This book is a case-study into documentary depictions of nuclear energy in television and video programmes and into the interpretations and responses of viewers drawn from many different occupational groupings. How are the complex and specialist arguments about benefit, risk and proof conveyed through the different conventions of commentary, interview and film sequence? What symbolic associations does the visual language of television bring to portrayals of the issue? And how do viewers make sense of various and conflicting accounts, connecting what they see and hear on the screen with their pre-existing knowledge, experience and 'civic' expectations. The authors examine some of the contrasting forms and themes which have been used by programme makers to explain and persuade, and then give a sustained analysis of the nature and sources of viewers' own accounts. 'Nuclear Reactions' inquires into the public meanings surrounding energy and the environment, spelling out in its conclusion some of the implications for future media treatments of this issue. It is also a key contribution to the international literature on 'television knowledge' and the processes of active viewing. (author)

  2. Iron selenide films by aerosol assisted chemical vapor deposition from single source organometallic precursor in the presence of surfactants

    Energy Technology Data Exchange (ETDEWEB)

    Hussain, Raja Azadar [Department of Chemistry, Quaid-i-Azam University, 45320 Islamabad (Pakistan); Badshah, Amin, E-mail: aminbadshah@yahoo.com [Department of Chemistry, Quaid-i-Azam University, 45320 Islamabad (Pakistan); Younis, Adnan [School of Materials Science and Engineering, University of New South Wales, Sydney 2052, NSW (Australia); Khan, Malik Dilshad [Department of Chemistry, Quaid-i-Azam University, 45320 Islamabad (Pakistan); Akhtar, Javeed [Department of Physics, COMSATS Institute of Information Technology, Park Road, Chak Shahzad, Islamabad (Pakistan)

    2014-09-30

    This article presents the synthesis and characterization (multinuclear nuclear magnetic resonance, Fourier transform infrared spectroscopy, carbon–hydrogen–nitrogen–sulfur analyzer, atomic absorption spectrometry and thermogravimetric analysis) of a single source organometallic precursor namely 1-acetyl-3-(4-ferrocenylphenyl)selenourea for the fabrication of iron selenide (FeSe) films on glass substrates using aerosol assisted chemical vapor deposition (AACVD). The changes in the morphologies of the films have been monitored by the use of two different surfactants i.e. triton X-100 and tetraoctylphosphonium bromide during AACVD. The role of surfactant has been evaluated by examining the interaction of the surfactants with the precursor by using UV–vis spectroscopy and cyclic voltammetry. The fabricated FeSe films have been characterized with powder X-ray diffraction, scanning electron microscopy and energy dispersive spectroscopy. - Highlights: • Ferrocene incorporated selenourea (FIS) has been synthesized and characterized. • FeSe thin films have been fabricated from FIS. • Mechanism of film growth was studied with cyclic voltammetry and UV–vis spectroscopy.

  3. Growth and physicochemical properties of organometallic (DL)-trithioureatartrato-O1,O2,O3-cadmium(II) single crystals

    Science.gov (United States)

    Sathyamoorthy, K.; Vinothkumar, P.; Irshad Ahamed, J.; Murali Manohar, P.; Priya, M.; Liu, Jinghe

    2018-04-01

    Single crystals of organometallic (DL)-trithioureatartrato-O1,O2,O3-cadmium(II) (TUDLC) have been grown from methanol solution by using the slow evaporation of solvent growth technique. The lattice structure and crystalline perfection have been determined by carrying out single crystal X-ray diffraction and high resolution X-ray diffraction measurements. The grown crystal was characterized thermally and mechanically by carrying out thermo-gravimetric and micro hardness measurements. The linear and nonlinear optical characterizations were made by carrying out optical transmittance, surface laser damage threshold, particle size-dependent second harmonic generation (SHG) efficiency and photo conductivity measurements. The grown crystal was electrically characterized by carrying out frequency-dependent dielectric measurements. Chemical etching study was also carried out and the dislocation density was estimated. Results obtained in the present study indicate that the grown TUDLC crystal is optically transparent with lower cut-off wavelength 304 nm, mechanically soft, thermally stable up to 101 °C and NLO active with SHG efficiency 2.13 (in KDP unit). The grown crystal is found to have considerably large size, good crystalline perfection, large specific heat capacity, higher surface laser damage threshold and negative photoconductivity.

  4. Growth and optical characteristics of Tm-doped AlGaN layer grown by organometallic vapor phase epitaxy

    Science.gov (United States)

    Takatsu, J.; Fuji, R.; Tatebayashi, J.; Timmerman, D.; Lesage, A.; Gregorkiewicz, T.; Fujiwara, Y.

    2018-04-01

    We report on the growth and optical properties of Tm-doped AlGaN layers by organometallic vapor phase epitaxy (OMVPE). The morphological and optical properties of Tm-doped GaN (GaN:Tm) and Tm-doped AlGaN (AlGaN:Tm) were investigated by Nomarski differential interference contrast microscopy and photoluminescence (PL) characterization. Nomarski images reveal an increase of surface roughness upon doping Tm into both GaN and AlGaN layers. The PL characterization of GaN:Tm shows emission in the near-infrared range originating from intra-4f shell transitions of Tm3+ ions. In contrast, AlGaN:Tm also exhibits blue light emission from Tm3+ ions. In that case, the wider band gap of the AlGaN host allows energy transfer to higher states of the Tm3+ ions. With time-resolved PL measurements, we could distinguish three types of luminescent sites of Tm3+ in the AlGaN:Tm layer, having different decay times. Our results confirm that Tm ions can be doped into GaN and AlGaN by OMVPE, and show potential for the fabrication of novel high-color-purity blue light emitting diodes.

  5. Mechanisms of chemical vapor generation by aqueous tetrahydridoborate. Recent developments toward the definition of a more general reaction model

    Science.gov (United States)

    D'Ulivo, Alessandro

    2016-05-01

    A reaction model describing the reactivity of metal and semimetal species with aqueous tetrahydridoborate (THB) has been drawn taking into account the mechanism of chemical vapor generation (CVG) of hydrides, recent evidences on the mechanism of interference and formation of byproducts in arsane generation, and other evidences in the field of the synthesis of nanoparticles and catalytic hydrolysis of THB by metal nanoparticles. The new "non-analytical" reaction model is of more general validity than the previously described "analytical" reaction model for CVG. The non-analytical model is valid for reaction of a single analyte with THB and for conditions approaching those typically encountered in the synthesis of nanoparticles and macroprecipitates. It reduces to the previously proposed analytical model under conditions typically employed in CVG for trace analysis (analyte below the μM level, borane/analyte ≫ 103 mol/mol, no interference). The non-analytical reaction model is not able to explain all the interference effects observed in CVG, which can be achieved only by assuming the interaction among the species of reaction pathways of different analytical substrates. The reunification of CVG, the synthesis of nanoparticles by aqueous THB and the catalytic hydrolysis of THB inside a common frame contribute to rationalization of the complex reactivity of aqueous THB with metal and semimetal species.

  6. Development of a new molecular dynamics method for tribochemical reaction and its application to formation dynamics of MoS2 tribofilm

    International Nuclear Information System (INIS)

    Morita, Yusuke; Onodera, Tasuku; Suzuki, Ai; Sahnoun, Riadh; Koyama, Michihisa; Tsuboi, Hideyuki; Hatakeyama, Nozomu; Endou, Akira; Takaba, Hiromitsu; Kubo, Momoji; Del Carpio, Carlos A.; Shin-yoshi, Takatoshi; Nishino, Noriaki; Suzuki, Atsushi; Miyamoto, Akira

    2008-01-01

    Recently we have developed a novel molecular dynamics program NEW-RYUDO-CR, which can deal with chemical reactions. The developed method has been applied to the study of tribochemical reaction dynamics of MoS 2 tribofilm on iron surface. The initially amorphous MoS 2 layer self-organized its structure as result of the tribochemical reactions and formed layered MoS 2 tribofilm. The friction coefficient significantly decreased as the MoS 2 tribofilm was formed. Besides, sliding was observed between sulfur layers of MoS 2 tribofilms which occurred due to repulsive Coulombic interaction forces between sulfur atoms. This indicates that the formation of the layered MoS 2 tribofilm is important to achieve better lubrication properties

  7. 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.

  8. Kinetics of evaporation of barium THD precursors used for organometallic chemical vapor deposition (OMCVD) thin films

    Science.gov (United States)

    Burtman, V.; Schieber, M.; Yitzchaik, S.; Yaroslavsky, Y.

    1997-04-01

    Various methods have been used to synthesize Ba(THD) 2 and its molecular structure has been studied using nuclear magnetic resonance. Compared with Raman and infrared spectroscopy it was found that NMR is very useful to determine quantitatively the decomposition through aging of Ba(THD) 2. The transport kinetics of Ba(THD) 2 has been studied under experimental conditions of a OMCVD reactor. It has been found that the freshly prepared Ba(THD) 2 by the reaction of Ba metal with THD ligand in anhydrous conditions with subsequent crystallization from methanol transported quantitatively without decomposition. A simple model shows that the transport kinetics corresponds to a diffusion controlled process.

  9. Fundamental understanding of oxygen reduction and reaction behavior and developing high performance and stable hetero-structured cathodes

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Xingbo [West Virginia Univ., Morgantown, WV (United States)

    2016-11-14

    New unique hetero-structured cathode has been developed in this project. La2NiO4+δ (LNO) as a surface catalyst with interstitial oxygen defects was introduced onto the state-of-the-art (La0.6Sr0.4)0.95Co0.2Fe0.8O3-δ (LSCF) cathode to enhance the surface-limited ORR kinetics on SOFC cathode. Furthermore, the hetero-structured cathode surface maintains high activity under electrode polarization with much less negative effects from surface cation segregation of Sr, which is known to cause degradation issues for conventional LSCF and LSC cathodes, thus improving the cathode long-term stability. The interface chemistry distribution and oxygen transport properties have been studied to prove the enhancement of power out and stability of LNO-infiltrated LSCF cathode. The further investigation demonstrates that CeO2 & La2-xNiO4+δ (x=0-0.2) co-infiltration is a simple and cost-effective method to improve both performance and stability of LSCF cathode by limiting nano-particles growth/delamination and further improve the surface stability. For the first time, a physical model is proposed to illustrate how unique interstitial species on hetero-structured cathode surface work to regulate the exchange rate of the incorporation reaction. Meanwhile, fundamental investigation of the surface oxygen exchange and bulk oxygen transport properties under over-potential conditions across cathode materials have been carried out in this project, which were discussed and compared to the Nernst equation that is generally applied to treat any oxide electrodes under equilibrium.

  10. CLM4-BeTR, a generic biogeochemical transport and reaction module for CLM4: model development, evaluation, and application

    Directory of Open Access Journals (Sweden)

    J. Y. Tang

    2013-01-01

    Full Text Available To improve regional and global biogeochemistry modeling and climate predictability, we have developed a generic reactive transport module for the land model CLM4 (called CLM4-BeTR (Biogeochemical Transport and Reactions. CLM4-BeTR represents the transport, interactions, and biotic and abiotic transformations of an arbitrary number of tracers (aka chemical species in an arbitrary number of phases (e.g., dissolved, gaseous, sorbed, aggregate. An operator splitting approach was employed and consistent boundary conditions were derived for each modeled sub-process. Aqueous tracer fluxes, associated with hydrological processes such as surface run-on and run-off, belowground drainage, and ice to liquid conversion were also computed consistently with the bulk water fluxes calculated by the soil physics module in CLM4. The transport code was evaluated and found in good agreement with several analytical test cases using a time step of 30 min. The model was then applied at the Harvard Forest site with a representation of depth-dependent belowground biogeochemistry. The results indicated that, at this site, (1 CLM4-BeTR was able to simulate soil–surface CO2 effluxes and soil CO2 profiles accurately; (2 the transient surface CO2 effluxes calculated based on the tracer transport mechanism were in general not equal to the belowground CO2 production rates with the magnitude of the difference being a function of averaging timescale and site conditions: differences were large (−20 ~ 20% on hourly, smaller (−5 ~ 5% at daily timescales, and persisted to the monthly timescales with a smaller magnitude (<4%; (3 losses of CO2 through processes other than surface gas efflux were less than 1% of the overall soil respiration; and (4 the contributions of root respiration and heterotrophic respiration have distinct temporal signals in surface CO2 effluxes and soil CO2 concentrations. The

  11. Summary remarks and recommended reactions for an international data file for dosimetry applications for LWR, FBR, and MFR reactor research, development and testing programs

    International Nuclear Information System (INIS)

    McElroy, W.N.; Lippincott, E.P.; Grundl, J.A.; Fabry, A.; Dierckx, R.; Farinelli, U.

    1979-01-01

    The need for the use of an internationally accepted data file for dosimetry applications for light water reactor (LWR), fast breeder reactor (FBR), and magnetic fusion reactor (MFR) research, development, and testing programs continues to exist for the Nuclear Industry. The work of this IAEA meeting, therefore, will be another important step in achieving consensus agreement on an internationally recommended file and its purpose, content, structure, selected reactions, and associated uncertainy files. Summary remarks and a listing of recommended reactions for consideration in the formulation of an ''International Data File for Dosimetry Applications'' are presented in subsequent sections of this report

  12. Investigation of coulomb and pairing effects using new developed empirical formulas for proton-induced reaction cross sections

    International Nuclear Information System (INIS)

    Tel, E.; Aydin, E. G.; Aydin, A.; Kaplan, A.; Boeluekdemir, M. H.; Okuducu, S.

    2010-01-01

    We have investigated Coulomb and pairing effects by using new empirical formulas including the new coefficients for (p, α) at 17.9 MeV, (p, np) at 22.3 MeV, and (p, nα) at 24.8 and 28.5 MeV energies. A new formula is obtained by adjusting Levkovskii's original asymmetry parameter formula and also Tel et al. formula for proton-induced reactions. The new coefficients by using least-squares fitting method for the reactions are determined. In addition, the findings of the present study are compared with the available experimental data.

  13. Development of a test for recording both visual and auditory reaction times, potentially useful for future studies in patients on opioids therapy

    Directory of Open Access Journals (Sweden)

    Miceli L

    2015-02-01

    Full Text Available Luca Miceli,1 Rym Bednarova,2 Alessandro Rizzardo,1 Valentina Samogin,1 Giorgio Della Rocca1 1Department of Anesthesia and Intensive Care Medicine, University of Udine, 2Department of Pain Medicine and Palliative Care, Hospital of Latisana, Latisana, Udine, Italy Objective: Italian Road Law limits driving while undergoing treatment with certain kinds of medication. Here, we report the results of a test, run as a smartphone application (app, assessing auditory and visual reflexes in a sample of 300 drivers. The scope of the test is to provide both the police force and medication-taking drivers with a tool that can evaluate the individual’s capacity to drive safely. Methods: The test is run as an app for Apple iOS and Android mobile operating systems and facilitates four different reaction times to be assessed: simple visual and auditory reaction times and complex visual and auditory reaction times. Reference deciles were created for the test results obtained from a sample of 300 Italian subjects. Results lying within the first three deciles were considered as incompatible with safe driving capabilities. Results: Performance is both age-related (r>0.5 and sex-related (female reaction times were significantly slower than those recorded for male subjects, P<0.05. Only 21% of the subjects were able to perform all four tests correctly. Conclusion: We developed and fine-tuned a test called Safedrive that measures visual and auditory reaction times through a smartphone mobile device; the scope of the test is two-fold: to provide a clinical tool for the assessment of the driving capacity of individuals taking pain relief medication; to promote the sense of social responsibility in drivers who are on medication and provide these individuals with a means of testing their own capacity to drive safely. Keywords: visual reaction time, auditory reaction time, opioids, Safedrive

  14. Development of Refractory Ceramics for The Oxygen Evolution Reaction (OER) Electrocatalyst Support for Water Electrolysis at elevated temperatures

    DEFF Research Database (Denmark)

    Nikiforov, Aleksey; Prag, Carsten Brorson; Polonsky, J.

    2012-01-01

    Commercial TaC and Si3N4 powders were tested as possible electrocatalyst support materials for the Oxygen Evolution Reaction (OER) for PEM water electrolysers, operating at elevated temperatures. TaC and Si3N4 were characterised by thermogravimmetric and differential thermal analysis...

  15. The development of reactions of the public to warning and emergency situations in France, Greece and The Netherlands

    NARCIS (Netherlands)

    Wiegman, O.; Boer, Hendrik; Gutteling, Jan M.; Komilis, E.; Cadet, B.

    1992-01-01

    This article describes the different reactions to emergency warning messages among residents living within a 3-km radius of a hazardous chemical complex and by people living at least 10 km from an industrial site in France, Greece, and the Netherlands. Belief in warning, primary and secondary

  16. Development of Novel Electrode Materials for the Electrocatalysis of Oxygen-Transfer and Hydrogen-Transfer Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Simpson, Brett Kimball [Iowa State Univ., Ames, IA (United States)

    2002-01-01

    Throughout this thesis, the fundamental aspects involved in the electrocatalysis of anodic O-transfer reactions and cathodic H-transfer reactions have been studied. The investigation into anodic O-transfer reactions at undoped and Fe(III)[doped MnO2 films] revealed that MnO2 film electrodes prepared by a cycling voltammetry deposition show improved response for DMSO oxidation at the film electrodes vs. the Au substrate. Doping of the MnO2 films with Fe(III) further enhanced electrode activity. Reasons for this increase are believed to involve the adsorption of DMSO by the Fe(III) sites. The investigation into anodic O-transfer reactions at undoped and Fe(III)-doped RuO2 films showed that the Fe(III)-doped RuO2-film electrodes are applicable for anodic detection of sulfur compounds. The Fe(III) sites in the Fe-RuO2 films are speculated to act as adsorption sites for the sulfur species while the Ru(IV) sites function for anodic discharge of H2O to generate the adsorbed OH species. The investigation into cathodic H-transfer reactions, specifically nitrate reduction, at various pure metals and their alloys demonstrated that the incorporation of metals into alloy materials can create a material that exhibits bifunctional properties for the various steps involved in the overall nitrate reduction reaction. The Sb10Sn20Ti70, Cu63Ni37 and Cu25Ni75 alloy electrodes exhibited improved activity for nitrate reduction as compared to their pure component metals. The Cu63Ni37 alloy displayed the highest activity for nitrate reduction. The final investigation was a detailed study of the electrocatalytic activity of cathodic H-transfer reactions (nitrate reduction) at various compositions of Cu-Ni alloy electrodes. Voltammetric response for NO3- at the Cu-Ni alloy electrode is superior to

  17. Reaction heats and bond strengths based on a series of lectures given to postgraduate students at the University of Keele, 1960

    CERN Document Server

    Mortimer, C T

    1962-01-01

    Reaction Heats and Bond Strengths presents the variations in the heats of particular types of reaction. This book covers a variety of topics, including the hydrogenation and polymerization of olefinic compounds, the dissociation of organic and organo-metallic compounds, and the molecular-addition compounds. Organized into 10 chapters, this book begins with an overview of the concept of bond energy that can be very useful where a comparison is being made between two dissimilar molecules. This text then examines the strain in cyclopropane and cyclobutane, which is largely a result of angular str

  18. Reactions of radioactive 18F with alkenes, alkynes, and other substrates

    International Nuclear Information System (INIS)

    Rowland, F.S.; Rust, F.; Frank, J.P.

    1978-01-01

    The technique of using thermalized 18 F atoms for the study of fluorine atom reactions has proven very useful with unsaturated hydrocarbons and halocarbons, providing data on mechanisms, relative rate constants and factors controlling such reactions. The characteristic difficulties of macroscopic 19 F chemistry are often avoided at tracer levels, and analysis by radio gas chromatography can be quite straightforward. However, experiments at pressures below 0.1 atm are relatively difficult, and most of the usual analytical methods are inapplicable at product mole fractions -10 . Many other classes of compounds can be readily substituted for alkenes and alkynes with little variation in equipment and technique. The extension to study 18 F atom reactions with organometallic compounds is one example of the broad applicability of tracer 18 F studies. 57 references, 5 figures, 10 tables

  19. Ionic Liquids as Solvents for Rhodium and Platinum Catalysts Used in Hydrosilylation Reaction

    Directory of Open Access Journals (Sweden)

    Witold Zielinski

    2016-08-01

    Full Text Available A group of imidazolium and pyridinium based ionic liquids has been synthetized, and their ability to dissolve and activate the catalysts used in hydrosilylation reaction of 1-octane and 1,1,1,3,5,5,5-heptamethyltrisiloxane was investigated. An organometallic catalyst as well as inorganic complexes of platinum and rhodium dissolved in ionic liquids were used, forming liquid solutions not miscible with the substrates or with the products of the reaction. The results show that application of such a simple biphasic catalytic system enables reuse of ionic liquid phase with catalysts in multiple reaction cycles reducing the costs and decreasing the amount of catalyst needed per mole of product.

  20. Advances in the catalysts development in base of mixed oxides for control reactions of N2O

    International Nuclear Information System (INIS)

    Garcia, M.A.; Perez, R.; Gomez, A.; Diaz, G.

    2000-01-01

    The catalytic supports Al 2 O 3 , La 2 O 3 and Al 2 O 3 -La 2 O 3 were prepared by the precipitation and coprecipitation techniques. The catalytic supports Al 2 O 3 , La 2 O 3 and Al 2 O 3 -La 2 O 3 were characterized by several techniques for to determine texture (BET), crystallinity (XRD), chemical composition (SEM), FTIR and it was evaluated their total acidity by the reaction with 2-propanol. It was continued with the cobalt addition by Impregnation and coprecipitation and it was evaluated its catalytic activity in the N 2 O decomposition reaction. Also it was realized the N 2 O reduction with Co using these catalysts. (Author)

  1. Development of methods of transport of nuclear reaction products by helium jet, in connection with the ALICE accelerator

    International Nuclear Information System (INIS)

    Deprun, C.; Gauvin, H.; Le Beyec, Y.

    1976-01-01

    The He-jet transport systems for use with the heavy-ion accelerator ALICE at Orsay are described in detail. The dependence of the gas flow rate on various parameters (pressure, length and diameter of the capillary) was investigated. Off-line measurements were carried out with a 252 Cf source. Effect on collection yield of UV radiation and additives to the helium was checked. The influence of the distance between the target and the capillary on the collection efficiency for short-lived isotopes of Yb was investigated. Some other useful details are also discussed (collector, volume of the reaction chamber, etc.). Various applications of the He-jet method are described: particle identification, angular distribution of reaction products, mass identification of radioactive nuclei. (Auth.)

  2. Kinetics analysis for development of a rate constant estimation model for ultrasonic degradation reaction of methylene blue.

    Science.gov (United States)

    Kobayashi, Daisuke; Honma, Chiemi; Matsumoto, Hideyuki; Takahashi, Tomoki; Kuroda, Chiaki; Otake, Katsuto; Shono, Atsushi

    2014-07-01

    Ultrasound has been used as an advanced oxidation method for wastewater treatment. Sonochemical degradation of organic compounds in aqueous solution occurs by pyrolysis and/or reaction with hydroxyl radicals. Moreover, kinetics of sonochemical degradation has been proposed. However, the effect of ultrasonic frequency on degradation rate has not been investigated. In our previous study, a simple model for estimating the apparent degradation rate of methylene blue was proposed. In this study, sonochemical degradation of methylene blue was performed at various frequencies. Apparent degradation rate constant was evaluated assuming that sonochemical degradation of methylene blue was a first-order reaction. Specifically, we focused on effects of ultrasonic frequency and power on rate constant, and the applicability of our proposed model was demonstrated. Using this approach, maximum sonochemical degradation rate was observed at 490 kHz, which agrees with a previous investigation into the effect of frequency on the sonochemical efficiency value evaluated by KI oxidation dosimetry. Degradation rate increased with ultrasonic power at every frequency. It was also observed that threshold power must be reached for the degradation reaction to progress. The initial methylene blue concentration and the apparent degradation rate constant have a relation of an inverse proportion. Our proposed model for estimating the apparent degradation rate constant using ultrasonic power and sonochemical efficiency value can apply to this study which extended the frequency and initial concentration range. Copyright © 2013 Elsevier B.V. All rights reserved.

  3. Molecular mechanism of cell damage and protection against ionizing radiation. Communication 3. Correlation between the protective effect and development of a non-specific reaction

    International Nuclear Information System (INIS)

    Veksler, A.M.; Ermekova, V.M.; Kozlovich, L.I.

    1975-01-01

    The dynamics of reversible unspecific reaction (UR) of chinese hamster fibroblast cell culture to hypothermia and cysteamine addition has been studied. A correlation between UR development and radioresistance has been established. The post-irradiation protection has been shown to grow undulatorilly o cysteamine addition at different times after irradiation. This is explained by superimposition of two processes: realization of latent lesions which is delayed by UR development, and repair of these lesions by the enzymatic system the activity of which changes periodicallY, also as a result of UR development

  4. Development of a high-density gas-jet target for nuclear astrophysics and reaction studies with rare isotope beams. Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Uwe, Greife [Colorado School of Mines, Golden, CO (United States)

    2014-08-12

    The purpose of this project was to develop a high-density gas jet target that will enable a new program of transfer reaction studies with rare isotope beams and targets of hydrogen and helium that is not currently possible and will have an important impact on our understanding of stellar explosions and of the evolution of nuclear shell structure away from stability. This is the final closeout report for the project.

  5. Development of a high-density gas-jet target for nuclear astrophysics and reaction studies with rare isotope beams. Final Report

    International Nuclear Information System (INIS)

    Uwe, Greife

    2014-01-01

    The purpose of this project was to develop a high-density gas jet target that will enable a new program of transfer reaction studies with rare isotope beams and targets of hydrogen and helium that is not currently possible and will have an important impact on our understanding of stellar explosions and of the evolution of nuclear shell structure away from stability. This is the final closeout report for the project.

  6. Quasielastic reactions

    International Nuclear Information System (INIS)

    Henning, W.

    1979-01-01

    Quasielastic reaction studies, because of their capability to microscopically probe nuclear structure, are still of considerable interest in heavy-ion reactions. The recent progress in understanding various aspects of the reaction mechanism make this aim appear closer. The relation between microscopic and macroscopic behavior, as suggested, for example, by the single proton transfer data to individual final states or averaged excitation energy intervals, needs to be explored. It seems particularly useful to extend measurements to higher incident energies, to explore and understand nuclear structure aspects up to the limit of the energy range where they are important

  7. Utility of Hantzsch reaction for development of highly sensitive spectrofluorimetric method for determination of alfuzosin and terazosin in bulk, dosage forms and human plasma.

    Science.gov (United States)

    Hammad, Mohamed A; Omar, Mahmoud A; Salman, Baher I

    2017-09-01

    A highly sensitive, cheap, simple and accurate spectrofluorimetric method has been developed and validated for the determination of alfuzosin hydrochloride and terazosin hydrochloride in their pharmaceutical dosage forms and in human plasma. The developed method is based on the reaction of the primary amine moiety in the studied drugs with acetylacetone and formaldehyde according to the Hantzsch reaction, producing yellow fluorescent products that can be measured spectrofluorimetrically at 480 nm after excitation at 415 nm. Different experimental parameters affecting the development and stability of the reaction products were carefully studied and optimized. The fluorescence-concentration plots of alfuzosin and terazosin were rectilinear over a concentration range of 70-900 ng ml -1 , with quantitation limits 27.1 and 32.2 ng ml -1 for alfuzosin and terazosin, respectively. The proposed method was validated according to ICH guidelines and successfully applied to the analysis of the investigated drugs in dosage forms, content uniformity test and spiked human plasma with high accuracy. Copyright © 2017 John Wiley & Sons, Ltd.

  8. How low does iron go? Chasing the active species in fe-catalyzed cross-coupling reactions.

    Science.gov (United States)

    Bedford, Robin B

    2015-05-19

    The catalytic cross-coupling reactions of organic halides or related substrates with organometallic nucleophiles form the cornerstone of many carbon-carbon bond-forming processes. While palladium-based catalysts typically mediate such reactions, there are increasing concerns about the long-term sustainability of palladium in synthesis. This is due to the high cost of palladium, coupled with its low natural abundance, environmentally deleterious extraction (∼6 g of metal are produced per ton of ore), toxicity, and competition for its use from the automotive and consumer electronics sectors. Therefore, there is a growing interest in replacing palladium-based catalysts with those incorporating more earth-abundant elements. With its low cost, high natural abundance, and low toxicity, iron makes a particularly appealing alternative, and accordingly, the development of iron-catalyzed cross-coupling is undergoing explosive growth. However, our understanding of the mechanisms that underpin the iron-based catalytic cycles is still very much in its infancy. Mechanistic insight into catalytic reactions is not only academically important but also allows us to maximize the efficiency of processes or even to develop entirely new transformations. Key to the development of robust mechanistic models for cross-coupling is knowing the lowest oxidation state in the cycle. Once this is established, we can explore subsequent redox processes and build the catalytic manifold. Until we know with confidence what the lowest oxidation state is, any cycles proposed are largely just guesswork. To date, Fe(-II), Fe(-I), Fe(0), Fe(I), and Fe(II) have been proposed as contenders for the lowest-oxidation-state species in the cycle in iron-catalyzed cross-coupling; the aim of this Account is to pull together the various pieces of evidence in support, or otherwise, of each of these suggestions in turn. There currently exists no direct evidence that oxidation states below Fe(0) are active in the

  9. Free and Protein-Bound Maillard Reaction Products in Beer: Method Development and a Survey of Different Beer Types.

    Science.gov (United States)

    Hellwig, Michael; Witte, Sophia; Henle, Thomas

    2016-09-28

    The Maillard reaction is important for beer color and flavor, but little is known about the occurrence of individual glycated amino acids in beer. Therefore, seven Maillard reaction products (MRPs), namely, fructosyllysine, maltulosyllysine, pyrraline, formyline, maltosine, MG-H1, and argpyrimidine, were synthesized and quantitated in different types of beer (Pilsner, dark, bock, wheat, and nonalcoholic beers) by HPLC-ESI-MS/MS in the multiple reaction monitoring mode through application of the standard addition method. Free MRPs were analyzed directly. A high molecular weight fraction was isolated by dialysis and hydrolyzed enzymatically prior to analysis. Maltulosyllysine was quantitated for the first time in food. The most important free MRPs in beer are fructosyllysine (6.8-27.0 mg/L) and maltulosyllysine (3.7-21.8 mg/L). Beer contains comparatively high amounts of late-stage free MRPs such as pyrraline (0.2-1.6 mg/L) and MG-H1 (0.3-2.5 mg/L). Minor amounts of formyline (4-230 μg/L), maltosine (6-56 μg/L), and argpyrimidine (0.1-4.1 μg/L) were quantitated. Maltulosyllysine was the most significant protein-bound MRP, but both maltulosyllysine and fructosyllysine represent only 15-60% of the total protein-bound lysine-derived Amadori products. Differences in the patterns of protein-bound and free individual MRPs and the ratios between them were identified, which indicate differences in their chemical, biochemical, and microbiological stabilities during the brewing process.

  10. Development of time-resolved electron momentum spectroscopy. Toward real-time imaging of frontier electrons in molecular reactions

    International Nuclear Information System (INIS)

    Yamazaki, M.; Takahashi, M.

    2016-01-01

    This report will introduce a new experimental technique to readers, which we would like to propose towards advances in the field of molecular reaction dynamics. It is time-resolved electron momentum spectroscopy and aims to take in momentum space snapshots of the rapid change of molecular orbitals, which is the driving force behind any structural changes occurring in transient molecules. Following a description of the working principle of the technique, some preliminary result will be presented in order to illustrate the current performance of the apparatus. (author)

  11. cycloaddition reactions

    Indian Academy of Sciences (India)

    Unknown

    Molecular Modeling Group, Organic Chemical Sciences, Indian Institute of Chemical Technology,. Hyderabad ... thus obtained are helpful to model the regioselectivity ... compromise to model Diels–Alder reactions involving ...... acceptance.

  12. Low-voltage organic field-effect transistors based on novel high-κ organometallic lanthanide complex for gate insulating materials

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Qi; Li, Yi; Zhang, Yang; Song, You, E-mail: wangxzh@nju.edu.cn, E-mail: yli@nju.edu.cn, E-mail: yousong@nju.edu.cn; Wang, Xizhang, E-mail: wangxzh@nju.edu.cn, E-mail: yli@nju.edu.cn, E-mail: yousong@nju.edu.cn; Hu, Zheng [Key Laboratory of Mesoscopic Chemistry of MOE, Jiangsu Provincial Lab for Nanotechnology, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China. High-Tech Research Institute of Nanjing University (Suzhou), Suzhou 215123 (China); Sun, Huabin; Li, Yun, E-mail: wangxzh@nju.edu.cn, E-mail: yli@nju.edu.cn, E-mail: yousong@nju.edu.cn; Shi, Yi [School of Electronic Science and Engineering and Jiangsu Provincial Key Laboratory of Photonic and Electronic Materials, Nanjing University, Nanjing 210093 (China)

    2014-08-15

    A novel high-κ organometallic lanthanide complex, Eu(tta){sub 3}L (tta=2-thenoyltrifluoroacetonate, L = 4,5-pinene bipyridine), is used as gate insulating material to fabricate low-voltage pentacene field-effect transistors (FETs). The optimized gate insulator exhibits the excellent properties such as low leakage current density, low surface roughness, and high dielectric constant. When operated under a low voltage of −5 V, the pentacene FET devices show the attractive electrical performance, e.g. carrier mobility (μ{sub FET}) of 0.17 cm{sup 2} V{sup −1} s{sup −1}, threshold voltage (V{sub th}) of −0.9 V, on/off current ratio of 5 × 10{sup 3}, and subthreshold slope (SS) of 1.0 V dec{sup −1}, which is much better than that of devices obtained on conventional 300 nm SiO{sub 2} substrate (0.13 cm{sup 2} V{sup −1} s{sup −1}, −7.3 V and 3.1 V dec{sup −1} for μ{sub FET}, V{sub th} and SS value when operated at −30 V). These results indicate that this kind of high-κ organometallic lanthanide complex becomes a promising candidate as gate insulator for low-voltage organic FETs.

  13. Low-voltage organic field-effect transistors based on novel high-κ organometallic lanthanide complex for gate insulating materials

    Directory of Open Access Journals (Sweden)

    Qi Liu

    2014-08-01

    Full Text Available A novel high-κ organometallic lanthanide complex, Eu(tta3L (tta=2-thenoyltrifluoroacetonate, L = 4,5-pinene bipyridine, is used as gate insulating material to fabricate low-voltage pentacene field-effect transistors (FETs. The optimized gate insulator exhibits the excellent properties such as low leakage current density, low surface roughness, and high dielectric constant. When operated under a low voltage of −5 V, the pentacene FET devices show the attractive electrical performance, e.g. carrier mobility (μFET of 0.17 cm2 V−1 s−1, threshold voltage (Vth of −0.9 V, on/off current ratio of 5 × 103, and subthreshold slope (SS of 1.0 V dec−1, which is much better than that of devices obtained on conventional 300 nm SiO2 substrate (0.13 cm2 V−1 s−1, −7.3 V and 3.1 V dec−1 for μFET, Vth and SS value when operated at −30 V. These results indicate that this kind of high-κ organometallic lanthanide complex becomes a promising candidate as gate insulator for low-voltage organic FETs.

  14. Highly Functionalized and Potent Antiviral Cyclopentane Derivatives Formed by a Tandem Process Consisting of Organometallic, Transition-Metal-Catalyzed, and Radical Reaction Steps

    Czech Academy of Sciences Publication Activity Database

    Jagtap, Pratap; Ford, Leigh Robert; Deister, E.; Pohl, Radek; Císařová, I.; Hodek, Jan; Weber, Jan; Mackman, R.; Bahador, G.; Jahn, Ullrich

    2014-01-01

    Roč. 20, č. 33 (2014), s. 10298-10304 ISSN 0947-6539 R&D Projects: GA ČR GA203/09/1936 Institutional support: RVO:61388963 Keywords : antiviral activity * cyclopentanes * isomerization * organic synthesis * radicals Subject RIV: CC - Organic Chemistry Impact factor: 5.731, year: 2014

  15. Development of an enzymatic microreactor based on microencapsulated laccase with off-line capillary electrophoresis for measurement of oxidation reactions.

    Science.gov (United States)

    Roman-Gusetu, Georgiana; Waldron, Karen C; Rochefort, Dominic

    2009-11-20

    Microencapsulation is used here as a new technique to immobilize enzymes in a microreactor coupled off-line to capillary electrophoresis (CE), allowing the determination of enzymatic reaction products. The redox enzyme laccase was encapsulated using the method of interfacial cross-linking of poly(ethyleneimine) (PEI). The 50 microm diameter capsules were slurry packed from a suspension into a capillary-sized reactor made easily and quickly from a short length of 530 microm diameter fused-silica tubing. The volume of the bed of laccase microcapsules in the microreactor was in the order of 1.1 microL through which 50 microL of the substrate o-phenylenediamine (OPD) was flowed. The oxidation product 2,3-diaminophenazine (DAP) and the remaining OPD were quantified by CE in a pH 2.5 phosphate buffer. Peak migration time reproducibility was in the order of 0.4% RSD and peak area reproducibility was less than 1.7% RSD within the same day. Using the OPD peak area calibration curve, a conversion efficiency of 48% was achieved for a 2-min oxidation reaction in the microreactor.

  16. A New Epoxy-Based Layered Silicate Nanocomposite Using a Hyperbranched Polymer: Study of the Curing Reaction and Nanostructure Development.

    Science.gov (United States)

    Cortés, Pilar; Fraga, Iria; Calventus, Yolanda; Román, Frida; Hutchinson, John M; Ferrando, Francesc

    2014-03-04

    Polymer layered silicate (PLS) nanocomposites have been prepared with diglycidyl ether of bisphenol-A (DGEBA) epoxy resin as the matrix and organically modified montmorillonite (MMT) as the clay nanofiller. Resin-clay mixtures with different clay contents (zero, two, five and 10 wt%) were cured, both isothermally and non-isothermally, using a poly(ethyleneimine) hyperbranched polymer (HBP), the cure kinetics being monitored by differential scanning calorimetry (DSC). The nanostructure of the cured nanocomposites was characterized by small angle X-ray scattering (SAXS) and transmission electron microscopy (TEM), and their mechanical properties were determined by dynamic mechanical analysis (DMA) and impact testing. The results are compared with an earlier study of the structure and properties of the same DGEBA-MMT system cured with a polyoxypropylene diamine, Jeffamine. There are very few examples of the use of HBP as a curing agent in epoxy PLS nanocomposites; here, it is found to enhance significantly the degree of exfoliation of these nanocomposites compared with those cured with Jeffamine, with a corresponding enhancement in the impact energy for nanocomposites with the low clay content of 2 wt%. These changes are attributed to the different cure kinetics with the HBP, in which the intra-gallery homopolymerization reaction is accelerated, such that it occurs before the bulk cross-linking reaction.

  17. A New Epoxy-Based Layered Silicate Nanocomposite Using a Hyperbranched Polymer: Study of the Curing Reaction and Nanostructure Development

    Directory of Open Access Journals (Sweden)

    Pilar Cortés

    2014-03-01

    Full Text Available Polymer layered silicate (PLS nanocomposites have been prepared with diglycidyl ether of bisphenol-A (DGEBA epoxy resin as the matrix and organically modified montmorillonite (MMT as the clay nanofiller. Resin-clay mixtures with different clay contents (zero, two, five and 10 wt% were cured, both isothermally and non-isothermally, using a poly(ethyleneimine hyperbranched polymer (HBP, the cure kinetics being monitored by differential scanning calorimetry (DSC. The nanostructure of the cured nanocomposites was characterized by small angle X-ray scattering (SAXS and transmission electron microscopy (TEM, and their mechanical properties were determined by dynamic mechanical analysis (DMA and impact testing. The results are compared with an earlier study of the structure and properties of the same DGEBA-MMT system cured with a polyoxypropylene diamine, Jeffamine. There are very few examples of the use of HBP as a curing agent in epoxy PLS nanocomposites; here, it is found to enhance significantly the degree of exfoliation of these nanocomposites compared with those cured with Jeffamine, with a corresponding enhancement in the impact energy for nanocomposites with the low clay content of 2 wt%. These changes are attributed to the different cure kinetics with the HBP, in which the intra-gallery homopolymerization reaction is accelerated, such that it occurs before the bulk cross-linking reaction.

  18. Aspects of transmetallation reactions of 2-Me2NCH2C6H4- and 2,6-(Me2NCH2)-C6H3-metal (Pd,Pt,Hg,Tl) complexes with metal carboxylates and low-valent metal (Pd,Pt) complexes

    NARCIS (Netherlands)

    Koten, G. van; Ploeg, A.F.M.J. van der; Vrieze, K.

    1981-01-01

    A study has been made of reactions involving organometallic compounds containing ortho-Me{2}NCH{2} substituted aryl ligands. The single step syntheses of the new compounds [(2-Me{2}NCH{2}C{6}H{4}){2}TlCl], [ [{(S)-2-Me{2}NCH(Me)C{6}H{4}}{2}TlCl], [{(S)-2-Me{2}NCH(Me)C{6}H{4}}TlCl{2}], [{2,

  19. Preparation of Conductive Organometallic Complexes and Their Pastes or Inks Using the Electron Beam Apparatus

    International Nuclear Information System (INIS)

    Gu, Ja Min; Lee, Hyosun; Lee, Byung Cheol; Park, Ji Hyun

    2011-01-01

    We have synthesized the silver and copper complexes using the ligands, amine derivatives Ν-methylhydantoin amine, Ν-triethanol amine, the copper complexes are prepared depending on the equivalents of starting materials, however the silver complexes failed. In case of terephthalic acid, glutaric acid, we have synthesized silver and copper complexes successfully. We have measured conductivity of silver and copper complexes paste and ink themselves by thermal reduction using PULSE UV method. A couple of synthesized copper complex's paste have shown some resistance which is not enough for the conductive materials. Commercially silver pastes composed of silver oxide and silver salt of carboxylic acid, applied to the printed transistor circuits with suitable process, i. e. thermal reduction. This process substituted for electron beam brings a simplification of process, economical, environmental friendly process and a development of in the application of flexible substrate

  20. DEVELOPMENT OF REACTION-DRIVEN IONIC TRANSPORT MEMBRANES (ITMs) TECHNOLOGY: PHASE IV/BUDGET PERIOD 6 “Development of ITM Oxygen Technology for Integration in IGCC and Other Advanced Power Generation Systems”

    Energy Technology Data Exchange (ETDEWEB)

    David, Studer

    2012-03-01

    Air Products and Chemicals, along with development participants and in association with the U.S. Department of Energy, has made substantial progress in developing a novel air separation technology. Unlike conventional cryogenic processes, this method uses high-temperature ceramic membranes to produce high-purity oxygen. The membranes selectively transport oxygen ions with high flux and infinite theoretical selectivity. Reaction-driven ceramic membranes are fabricated from non-porous, multi-component metallic oxides, operate at temperatures typically over 700°C, and have exceptionally high oxygen flux and selectivity. Oxygen from low-pressure air permeates as oxygen ions through the ceramic membrane and is consumed through chemical reactions, thus creating a chemical driving force that pulls oxygen ions across the membrane at high rates. The oxygen reacts with a hydrocarbon fuel in a partial oxidation process to produce a hydrogen and carbon monoxide mixture – synthesis gas. This project expands the partial-oxidation scope of ITM technology beyond natural gas feed and investigates the potential for ITM reaction-driven technology to be used in conjunction with gasification and pyrolysis technologies to provide more economical routes for producing hydrogen and synthesis gas. This report presents an overview of the ITM reaction-driven development effort, including ceramic materials development, fabrication and testing of small-scale ceramic modules, ceramic modeling, and the investigation of gasifier integration schemes

  1. Redox and Lewis acid relay catalysis: a titanocene/zinc catalytic platform in the development of multicomponent coupling reactions.

    Science.gov (United States)

    Gianino, Joseph B; Campos, Catherine A; Lepore, Antonio J; Pinkerton, David M; Ashfeld, Brandon L

    2014-12-19

    A titanocene-catalyzed multicomponent coupling is described herein. Using catalytic titanocene, phosphine, and zinc dust, zinc acetylides can be generated from the corresponding iodoalkynes to affect sequential nucleophilic additions to aromatic aldehydes. The intermediate propargylic alkoxides are trapped in situ with acetic anhydride, which are susceptible to a second nucleophilic displacement upon treatment with a variety of electron-rich species, including acetylides, allyl silanes, electron-rich aromatics, silyl enol ethers, and silyl ketene acetals. Additionally, employing cyclopropane carboxaldehydes led to ring-opened products resulting from iodine incorporation. Taken together, these results form the basis for a new mode of three-component coupling reactions, which allows for rapid access to value added products in a single synthetic operation.

  2. Real-time detection of sub-monolayer desorption phenomena during electrochemical reactions: Instrument development and applications

    DEFF Research Database (Denmark)

    Trimarco, Daniel Bøndergaard

    , making it highly suitable for electrochemistry studies. Incorporating the membrane chip into a stagnant thin-layer electrochemistry cell, 100% collection efficiency is ensured, which makes it possible to utilize the full dynamic range of a standard MS, and thereby analyze desorption phenomena during...... are made possible by the transient and steady-state introduction CO reactant gas, respectively, through the membrane. A mass transport model is used to describe the analytetransport from the surface of an electrode, through the stagnant thin-layer cell, through the membrane chip and into the mass...... reaction pathway towards methane production is temporarily established. The phenomenon is shown only to affect the formation of methane, leaving ethylene and hydrogen formation unaffected. Using density functional theory (DFT) it is demonstrated that adsorbed oxygen on surface sites adjacent...

  3. Development of a propidium monoazide-polymerase chain reaction assay for detection of viable Lactobacillus brevis in beer.

    Science.gov (United States)

    Ma, Yanlin; Deng, Yang; Xu, Zhenbo; Liu, Junyan; Dong, Jianjun; Yin, Hua; Yu, Junhong; Chang, Zongming; Wang, Dongfeng

    The spoilage of beer by bacteria is of great concern to the brewer as this can lead to turbidity and abnormal flavors. The polymerase chain reaction (PCR) method for detection of beer-spoilage bacteria is highly specific and provides results much faster than traditional microbiology techniques. However, one of the drawbacks is the inability to differentiate between live and dead cells. In this paper, the combination of propidium monoazide (PMA) pretreatment and conventional PCR had been described. The established PMA-PCR identified beer spoilage Lactobacillus brevis based not on their identity, but on the presence of horA gene which we show to be highly correlated with the ability of beer spoilage LAB to grow in beer. The results suggested that the use of 30μg/mL or less of PMA did not inhibit the PCR amplification of DNA derived from viable L. brevis cells. The minimum amount of PMA to completely inhibit the PCR amplification of DNA derived from dead L. brevis cells was 2.0μg/mL. The detection limit of PMA-PCR assay described here was found to be 10 colony forming units (CFU)/reaction for the horA gene. Moreover, the horA-specific PMA-PCR assays were subjected to 18 reference isolates, representing 100% specificity with no false positive amplification observed. Overall the use of horA-specific PMA-PCR allows for a substantial reduction in the time required for detection of potential beer spoilage L. brevis and efficiently differentiates between viable and nonviable cells. Copyright © 2017 Sociedade Brasileira de Microbiologia. Published by Elsevier Editora Ltda. All rights reserved.

  4. New Therapeutic Agent against Arterial Thrombosis: An Iridium(III-Derived Organometallic Compound

    Directory of Open Access Journals (Sweden)

    Chih-Wei Hsia

    2017-12-01

    Full Text Available Platelet activation plays a major role in cardio and cerebrovascular diseases, and cancer progression. Disruption of platelet activation represents an attractive therapeutic target for reducing the bidirectional cross talk between platelets and tumor cells. Platinum (Pt compounds have been used for treating cancer. Hence, replacing Pt with iridium (Ir is considered a potential alternative. We recently developed an Ir(III-derived complex, [Ir(Cp*1-(2-pyridyl-3-(2-hydroxyphenylimidazo[1,5-a]pyridine Cl]BF4 (Ir-11, which exhibited strong antiplatelet activity; hence, we assessed the therapeutic potential of Ir-11 against arterial thrombosis. In collagen-activated platelets, Ir-11 inhibited platelet aggregation, adenosine triphosphate (ATP release, intracellular Ca2+ mobilization, P-selectin expression, and OH· formation, as well as the phosphorylation of phospholipase Cγ2 (PLCγ2, protein kinase C (PKC, mitogen-activated protein kinases (MAPKs, and Akt. Neither the adenylate cyclase inhibitor nor the guanylate cyclase inhibitor reversed the Ir-11-mediated antiplatelet effects. In experimental mice, Ir-11 prolonged the bleeding time and reduced mortality associated with acute pulmonary thromboembolism. Ir-11 plays a crucial role by inhibiting platelet activation through the inhibition of the PLCγ2–PKC cascade, and the subsequent suppression of Akt and MAPK activation, ultimately inhibiting platelet aggregation. Therefore, Ir-11 can be considered a new therapeutic agent against either arterial thrombosis or the bidirectional cross talk between platelets and tumor cells.

  5. Electrochemistry of Simple Organometallic Models of Iron-Iron Hydrogenases in Organic Solvent and Water.

    Science.gov (United States)

    Gloaguen, Frederic

    2016-01-19

    Synthetic models of the active site of iron-iron hydrogenases are currently the subjects of numerous studies aimed at developing H2-production catalysts based on cheap and abundant materials. In this context, the present report offers an electrochemist's view of the catalysis of proton reduction by simple binuclear iron(I) thiolate complexes. Although these complexes probably do not follow a biocatalytic pathway, we analyze and discuss the interplay between the reduction potential and basicity and how these antagonist properties impact the mechanisms of proton-coupled electron transfer to the metal centers. This question is central to any consideration of the activity at the molecular level of hydrogenases and related enzymes. In a second part, special attention is paid to iron thiolate complexes holding rigid and unsaturated bridging ligands. The complexes that enjoy mild reduction potentials and stabilized reduced forms are promising iron-based catalysts for the photodriven evolution of H2 in organic solvents and, more importantly, in water.

  6. Air-tolerant C–C bond formation via organometallic ruthenium catalysis: diverse catalytic pathways involving (C5Me5)Ru or (C5H5)Ru are robust to molecular oxygen

    Czech Academy of Sciences Publication Activity Database

    Severa, Lukáš; Vávra, Jan; Kohoutová, Anna; Čížková, Martina; Šálová, Tereza; Hývl, Jakub; Šaman, David; Pohl, Radek; Adriaenssens, Louis; Teplý, Filip

    2009-01-01

    Roč. 50, č. 31 (2009), s. 4526-4528 ISSN 0040-4039 Institutional research plan: CEZ:AV0Z40550506 Keywords : ruthenium * organometallic catalysis * [2+2+2] cycloaddition * terminal alkynes Subject RIV: CC - Organic Chemistry Impact factor: 2.660, year: 2009

  7. The use of a well-defined surface organometallic complex as a probe molecule: [(≡SiO)TaVCl2Me2] shows different isolated silanol sites on the silica surface

    KAUST Repository

    Chen, Yin

    2014-01-01

    TaVCl2Me3 reacts with silica(700) and produces two different [(≡SiO)TaVCl2Me2] surface organometallic species, suggesting a heterogeneity of the highly dehydroxylated silica surface, which was studied with a combined experimental and theoretical approach. This journal is © the Partner Organisations 2014.

  8. The use of a well-defined surface organometallic complex as a probe molecule: [(≡SiO)TaVCl2Me2] shows different isolated silanol sites on the silica surface

    KAUST Repository

    Chen, Yin; Zheng, Bin; Abou-Hamad, Edy; Hamieh, Ali Imad Ali; Hamzaoui, Bilel; Huang, Kuo-Wei; Basset, Jean-Marie

    2014-01-01

    TaVCl2Me3 reacts with silica(700) and produces two different [(≡SiO)TaVCl2Me2] surface organometallic species, suggesting a heterogeneity of the highly dehydroxylated silica surface, which was studied with a combined experimental and theoretical approach. This journal is © the Partner Organisations 2014.

  9. Reaction mechanisms

    International Nuclear Information System (INIS)

    Nguyen Trong Anh

    1988-01-01

    The 1988 progress report of the Reaction Mechanisms laboratory (Polytechnic School, France), is presented. The research topics are: the valence bond methods, the radical chemistry, the modelling of the transition states by applying geometric constraints, the long range interactions (ion - molecule) in gaseous phase, the reaction sites in gaseous phase and the mass spectroscopy applications. The points of convergence between the investigations of the mass spectroscopy and the theoretical chemistry teams, as well as the purposes guiding the research programs, are discussed. The published papers, the conferences, the congress communications and the thesis, are also reported [fr

  10. The Reaction Wheel Pendulum

    CERN Document Server

    Block, Daniel J; Spong, Mark W

    2007-01-01

    This monograph describes the Reaction Wheel Pendulum, the newest inverted-pendulum-like device for control education and research. We discuss the history and background of the reaction wheel pendulum and other similar experimental devices. We develop mathematical models of the reaction wheel pendulum in depth, including linear and nonlinear models, and models of the sensors and actuators that are used for feedback control. We treat various aspects of the control problem, from linear control of themotor, to stabilization of the pendulum about an equilibrium configuration using linear control, t

  11. The study on the pH behavior of the HFSC leached solution. The development of model considering the pozzolanic reaction

    International Nuclear Information System (INIS)

    Yoshida, Yasushi; Mihara, Morihiro

    2005-09-01

    The development of low alkalinity cement (high fly-ash contained silica-fume cement, HFSC) has been carried out in JNC. Low alkalinity for this cement is achieved by adding pozzolan materials to ordinary portland cement and Ca ion attributed to high alkalinity is consumed by forming CHS gel. This report shows the calculation model to predict the composition for HFSC reacted solution which considers cement mineral dissolution/precipitation as equilibrium reactions and dissolution for pozzolan material as a kinetic reaction. The dissolution kinetic equation for pozzolan material is also derived from leaching experiment. This calculation model is applied to the leaching experiment where powdered HFSC was reacted with distilled water. As a result of comparison between calculation and experimental measurement at the early stage for leaching the tendency for pH, pH decrease from 12.5 to 11.5 drastically, could be interpreted by this calculation model, however, after this drastic pH decreasing pH predicted by calculation model also shows drastic decrease whereas pH for experiment decreased mildly around pH 11.5. It could be thought that this difference between experiment and calculation is caused by inappropriate modelling for CSH gel dissolution/precipitation of C/S value lower than 1.0. For this C/S range thermodynamic data for intermediate and end member for solid solution for CSH gel and in addition the reaction kinetic for CSH gel should be examined in detail. (author)

  12. Development of [18F]halofluorination and [18F]fluoride ion displacement reactions for the synthesis of F-18 labelled radiopharmaceuticals

    International Nuclear Information System (INIS)

    Chi, D.Y.

    1986-01-01

    Two fluorine-18 labeling methods, [ 18 F]halofluorination and [ 18 F]fluoride ion displacement reactions, have been developed to assess their potential for labeling molecules with the positron-emitting radionuclide fluorine-18 at the no-carrier-added level. Olefin halofluorination involves the in situ generation of a halogen-fluoride reagent and subsequent addition to an olefin. The characteristics of this reaction were investigated with three model olefins (allylbenzene, 1-hexene, and propene). A two-step method for the preparation of fluoroalkyl substituted amines and amides has been achieved. The sequence involves fluoride ion displacement of trifluoromethanesulfonates (triflates) from short-chain haloalkyl triflates, followed by fluoroalkylation of the amine or amide. Alternatively, short-chain fluoroalkyl halides can be prepared by halofluorination of a terminal olefin. These reactions have been used to prepare various fluoroalkyl derivatives of 1-phenylpiperazine and N-fluoroalkyl derivatives of the neuroleptic agent spiperone. A series of fluorine-18 labeled N-fluoroalkylated spiperone derivatives were synthesized by N-alkylation of spiperone with fluoroalkyl halides

  13. Low Speed Technology for Small Turbine Development Reaction Injection Molded 7.5 Meter Wind Turbine Blade

    Energy Technology Data Exchange (ETDEWEB)

    David M. Wright; DOE Project Officer - Keith Bennett

    2007-07-31

    An optimized small turbine blade (7.5m radius) was designed and a partial section molded with the RIM (reaction-injection molded polymer) process for mass production. The intended market is for generic three-bladed wind turbines, 100 kilowatts or less, for grid-assist end users with rural and semi-rural sites, such as the farm/ranch market, having low to moderate IEC Class 3-4 wind regimes. This blade will have substantial performance improvements over, and be cheaper than, present-day 7.5m blades. This is made possible by the injection-molding process, which yields high repeatability, accurate geometry and weights, and low cost in production quantities. No wind turbine blade in the 7.5m or greater size has used this process. The blade design chosen uses a RIM skin bonded to a braided infused carbon fiber/epoxy spar. This approach is attractive to present users of wind turbine blades in the 5-10m sizes. These include rebladeing California wind farms, refurbishing used turbines for the Midwest farm market, and other manufacturers introducing new turbines in this size range.

  14. Picosecond dynamics of reactions in the liquid phase: studies of iodine photodissociation and development of new laser techniques

    International Nuclear Information System (INIS)

    Berg, M.A.

    1985-09-01

    Iodine photodissociation and recombination was studied as a model for processes common to chemical reaction in the liquid phase. Picosecond transient absorption measurements from 1000 to 295 nm were used to monitor the dynamics in a variety of solvents. Most of the atoms which undergo geminate recombination were found to do so in less than or equal to 15 ps, in agreement with the results of existing molecular dynamics simulations. Vibrational relaxation times vary from approx.15 ps near the middle of the ground state well to approx.150 ps for complete relaxation to v = 0. The prediction of strong resonant vibrational energy transfer to chlorinated methane solvents was not supported, but some evidence for this mechanism was found for alkane solvents. Current theory is unable to explain the large variation (65 to 2700 ps) of the excited A'-state lifetime in various solvents. The 10-Hz amplified, synchronously-pumped dye laser which was used in these studies is described and characterized. SERS (Stimulated Electronic Raman Scattering) and difference frequency mixing were used in the generation of the infrared and far-infrared, respectively. 54 refs., 38 figs., 3 tabs

  15. Developing effective campaign messages to prevent neural tube defects: a qualitative assessment of women's reactions to advertising concepts.

    Science.gov (United States)

    Massi Lindsey, Lisa L; Silk, Kami J; Von Friederichs-Fitzwater, Marlene M; Hamner, Heather C; Prue, Christine E; Boster, Franklin J

    2009-03-01

    The incidence of neural tube defects (NTDs), serious birth defects of the brain and spine that affect approximately 3,000 pregnancies in the United States each year, can be reduced by 50-70% with daily periconceptional consumption of the B vitamin folic acid. Two studies were designed to assess college women's reactions to and perceptions of potential campaign advertising concepts derived from preproduction formative research to increase folic acid consumption through the use of a daily multivitamin. Study one assessed draft advertising concepts in eight focus groups (N = 71) composed of college-enrolled women in four cities geographically dispersed across the United States. Based on study one results, the concepts were revised and reassessed in study two with a different sample (eight focus groups; N = 73) of college women in the same four cities. Results indicated that participants generally responded favorably to concepts in each of the two studies, and provided insight into individual concepts to increase their overall appeal and effectiveness. The specific findings and implications of these results are discussed.

  16. Development of a quantitative competitive reverse transcriptase polymerase chain reaction for the quantification of growth hormone gene expression in pigs

    Directory of Open Access Journals (Sweden)

    Maurício Machaim Franco

    2003-01-01

    Full Text Available After the advent of the genome projects, followed by the discovery of DNA polymorphisms, basic understanding of gene expression is the next focus to explain the association between polymorphisms and the level of gene expression, as well as to demonstrate the interaction among genes. Among the various techniques for the investigation of transcriptional profiling involving patterns of gene expression, quantitative PCR is the simplest analytical laboratory technique. The objective of this work was to analyze two strategies of a competitive PCR technique for the quantification of the pig growth hormone (GH gene expression. A pair of primers was designed targeting exons 3 and 5, and two competitive PCR strategies were performed, one utilizing a specific amplicon as a competitor, and the other utilizing a low-stringency PCR amplicon as a competitor. The latter strategy proved to be easier and more efficient, offering an accessible tool that can be used in any kind of competitive reaction, facilitating the study of gene expression patterns for both genetics and diagnostics of infectious diseases.

  17. Development of a novel algorithm and production of new nuclear data libraries for the treatment of sequential (x,n) reactions in fusion material activation calculations

    International Nuclear Information System (INIS)

    Cierjacks, S.W.; Oblozinsky, P.; Kelzenberg, S.; Rzehorz, B.

    1993-01-01

    A new algorithm and three major nuclear data libraries were developed for the kinematically complete treatment of sequential (x,n) reactions in fusion material activation calculations. The new libraries include data for virtually all isotopes with Z ≤ 84 (A ≤ 210) and half-lives exceeding 1 day; primary neutron energies E n 3 He, and α with energies E x < 24 MeV. While production cross sections of charged particles for primary (n,x) reactions can be deduced from the European activation file, the KFKSPEC data file was created for the corresponding normalized charged-particle spectra. The second data file, KFKXN, contains cross sections for secondary (x,n) reactions. The third data file, KFKSTOP, has a complete set of differential ranges for all five aforementioned light charged particles and all elements from hydrogen to uranium. The KFKSPEC and KFKXN libraries are based essentially on nuclear model calculations using the statistical evaporation model superimposed with the pre-equilibrium contribution as implemented in the Lawrence Livermore National Laboratory ALICE code. The KFKSPEC library includes 633 isotopes, of which 55 are in their isomeric states, and contains 63,300 spectra of the (n,x) type with almost 1.5 million data points. The KFKXN library also includes 633 isotopes and contains all (x,n) and partly (x,2n) cross sections for 4431 reactions with ∼ 106,000 data points. The KFKSTOP library is considered complete and has 11,040 data points. 42 refs., 2 figs., 4 tabs

  18. Allergic reactions

    Science.gov (United States)

    ... that don't bother most people (such as venom from bee stings and certain foods, medicines, and pollens) can ... person. If the allergic reaction is from a bee sting, scrape the ... more venom. If the person has emergency allergy medicine on ...

  19. Expedient multi-step synthesis of organometallic complexes of Tc and Re in high effective specific activity. A new platform for the production of molecular imaging and therapy agents.

    Science.gov (United States)

    Causey, Patrick W; Besanger, Travis R; Schaffer, Paul; Valliant, John F

    2008-09-15

    For over thirty years, instant labeling kits which involve no purification steps have been the only method used to prepare (99m)Tc radiopharmaceuticals for clinical studies. To address the limitations imposed by instant kits, which is hindering the development of molecularly targeted Tc- and Re-based imaging and therapy agents, a new strategy for the rapid multistep synthesis and purification of organometallic technetium-based molecular probes and corresponding rhenium-based therapeutic analogues was developed. Beginning with MO4(-) (M = (99m)Tc, (186/188)Re), the carbonyl precursor [M(CO)3(H2O)3](+) was synthesized in 3 min in quantitative yield in a microwave reactor. A dipicolyl ligand was added and the chelate complex was formed in high yield in 2 min using microwave heating at 150 degrees C. This was followed by a new purification strategy to remove unlabeled ligand which entailed using a copper resin/C18 solid phase extraction protocol giving the desired product in greater than 78% decay corrected yield (dcy). Conversion to the corresponding succinimidyl active ester was achieved following a 5 min microwave irradiation at 120 degrees C and C18 solid phase extraction purification in 60% dcy. A series of amides were prepared subsequently by microwave heating at 120 degrees C for 5 min producing the desired targets in greater than 86% dcy. The reported method represents a move away from traditional instant kits toward more versatile platform synthesis and purification technologies that are better suited for producing modern molecular imaging and therapy agents.

  20. Sodium-water wastage and reactions program performed by general electric in support of the US. AEC LMFBR steam generator development

    International Nuclear Information System (INIS)

    Greene, D.A.

    1975-01-01

    This paper constitutes an interim report on the sodium-water reaction programs performed, using the GE-SOWAT, GE-SMALL LEAK BEHAVIOR RIG, and GE-PTTR facilities in support of LMFBR steam generator development and its application to the Clinch River Breeder Reactor Plant. Test data from these rigs are presented, including wastage data as a function of water injection rate, sodium temperature, and orifice geometry. Initial results for self-wastage of defects under prototypical conditions, and from proof-of-principle tests of a protected heat transfer tube concept are also presented. An analytical basis for wastage phenomena is suggested. (author)

  1. Sodium-water wastage and reactions program performed by general electric in support of the US. AEC LMFBR steam generator development

    Energy Technology Data Exchange (ETDEWEB)

    Greene, D A

    1975-07-01

    This paper constitutes an interim report on the sodium-water reaction programs performed, using the GE-SOWAT, GE-SMALL LEAK BEHAVIOR RIG, and GE-PTTR facilities in support of LMFBR steam generator development and its application to the Clinch River Breeder Reactor Plant. Test data from these rigs are presented, including wastage data as a function of water injection rate, sodium temperature, and orifice geometry. Initial results for self-wastage of defects under prototypical conditions, and from proof-of-principle tests of a protected heat transfer tube concept are also presented. An analytical basis for wastage phenomena is suggested. (author)

  2. Guiding gate-etch process development using 3D surface reaction modeling for 7nm and beyond

    Science.gov (United States)

    Dunn, Derren; Sporre, John R.; Deshpande, Vaibhav; Oulmane, Mohamed; Gull, Ronald; Ventzek, Peter; Ranjan, Alok

    2017-03-01

    Increasingly, advanced process nodes such as 7nm (N7) are fundamentally 3D and require stringent control of critical dimensions over high aspect ratio features. Process integration in these nodes requires a deep understanding of complex physical mechanisms to control critical dimensions from lithography through final etch. Polysilicon gate etch processes are critical steps in several device architectures for advanced nodes that rely on self-aligned patterning approaches to gate definition. These processes are required to meet several key metrics: (a) vertical etch profiles over high aspect ratios; (b) clean gate sidewalls free of etch process residue; (c) minimal erosion of liner oxide films protecting key architectural elements such as fins; and (e) residue free corners at gate interfaces with critical device elements. In this study, we explore how hybrid modeling approaches can be used to model a multi-step finFET polysilicon gate etch process. Initial parts of the patterning process through hardmask assembly are modeled using process emulation. Important aspects of gate definition are then modeled using a particle Monte Carlo (PMC) feature scale model that incorporates surface chemical reactions.1 When necessary, species and energy flux inputs to the PMC model are derived from simulations of the etch chamber. The modeled polysilicon gate etch process consists of several steps including a hard mask breakthrough step (BT), main feature etch steps (ME), and over-etch steps (OE) that control gate profiles at the gate fin interface. An additional constraint on this etch flow is that fin spacer oxides are left intact after final profile tuning steps. A natural optimization required from these processes is to maximize vertical gate profiles while minimizing erosion of fin spacer films.2

  3. Organometallic Polymeric Conductors

    Science.gov (United States)

    Youngs, Wiley J.

    1997-01-01

    For aerospace applications, the use of polymers can result in tremendous weight savings over metals. Suitable polymeric materials for some applications like EMI shielding, spacecraft grounding, and charge dissipation must combine high electrical conductivity with long-term environmental stability, good processability, and good mechanical properties. Recently, other investigators have reported hybrid films made from an electrically conductive polymer combined with insulating polymers. In all of these instances, the films were prepared by infiltrating an insulating polymer with a precursor for a conductive polymer (either polypyrrole or polythiophene), and oxidatively polymerizing the precursor in situ. The resulting composite films have good electrical conductivity, while overcoming the brittleness inherent in most conductive polymers. Many aerospace applications require a combination of properties. Thus, hybrid films made from polyimides or other engineering resins are of primary interest, but only if conductivities on the same order as those obtained with a polystyrene base could be obtained. Hence, a series of experiments was performed to optimize the conductivity of polyimide-based composite films. The polyimide base chosen for this study was Kapton. 3-MethylThiophene (3MT) was used for the conductive phase. Three processing variables were identified for producing these composite films, namely time, temperature, and oxidant concentration for the in situ oxidation. Statistically designed experiments were used to examine the effects of these variables and synergistic/interactive effects among variables on the electrical conductivity and mechanical strength of the films. Multiple linear regression analysis of the tensile data revealed that temperature and time have the greatest effect on maximum stress. The response surface of maximum stress vs. temperature and time (for oxidant concentration at 1.2 M) is shown. Conductivity of the composite films was measured for over 150 days in air at ambient temperature. The conductivity of the films dropped only half an order of magnitude in that time. Films aged under vacuum at ambient temperature diminished slightly in conductivity in the first day, but did not change thereafter. An experimental design approach will be applied to maximize the efficiency of the laboratory effort. The material properties (initial and long term) will also be monitored and assessed. The experimental results will add to the existing database for electrically conductive polymer materials. Attachments: 1) Synthesis Crystal Structure, and Polymerization of 1,2:5,6:9,10-Tribenzo-3,7,11,13-tetradehydro(14) annulene. 2) Reinvestigation of the Photocyclization of 1,4-Phenylene Bis(phenylmaleic anhydride): Preparation and Structure of (5)Helicene 5,6:9,10-Dianhydride. 3) Preparation and Structure Charecterization of a Platinum Catecholate Complex Containing Two 3-Ethynyltheophone Groups. and 4) Rigid-Rod Polymers Based on Noncoplanar 4,4'-Biphenyldiamines: A Review of Polymer Properties vs Configuration of Diamines.

  4. Tailored Organometallic Polymers

    Science.gov (United States)

    1993-01-31

    Webster, W. R. Herder, D. Y. Sogah, W. B. Farnham, T. V. ajan Babu, J. Am. Chem. soL • J105~. 5706-5708. [101 A. Boudin, (. Cerveau , C. Chuit, R.J. P...mngli,. 7., 237. [12] A. Boudin, G. Cerveau , C. Chuit, R. J. P. Corriu, C. Reyd, . o isj=, 7, 1165. [13] C. Brelire, R. J. P. Corriu, G. Royo, W. W. C...M.aa, J. Zwecker, Qrgg.omtaffic_ 9M 2, 2633-2635. [14] R. Tacke, J. Sperlich, C. Strohman, G. MatternU Ch 4 3.B=r 1 , 124., 1491-1496. [15] G. Cerveau

  5. Bridging ligands in organometallic chemistry. II. Synthesis and reactivity of the green dimer of molybdenocene containing a bridging fulvalene ligand

    Energy Technology Data Exchange (ETDEWEB)

    Smart, J.C.; Curtis, C.J.

    1978-11-01

    Synthesis, precipitation, and isolation of dicyclopentadienyl(fulvalene)dihydridomolybdenum are described. The compound was used in reaction studies involving the addition of carbon monoxide and deprotonation with n-butyllithium. Data for elemental analysis, ir spectral and NMR(in toluene-d) spectral analysis are reported for the title compound and its reaction products.

  6. Development of absorption fiber optic sensor for distributed measurement of ammonia gas

    Science.gov (United States)

    Aubrecht, J.; Kalvoda, L.

    2013-05-01

    Polymer-clad silica optical fibers are employed for development of different absorption optic fiber sensors of gaseous analytes. In our case, the physical principles of the detection are combined with a chemical reaction between analyte and suitable opto-chemical absorption reagents. Selected organometallic complex reagents with different lengths of lateral aliphatic chains are studied with respect to the type of central ions and their coordinative conditions to surrounding ligands. The effect of solvent type on solubility and the long-term stability of the prepared reagents in solid matrix are presented and discussed. Various methods are also tested in order to achieve an effective reagent immobilization into the polymer matrix, which creates optical fiber cladding. The chemical reaction of the reagents with ammonia based on ligand exchange process is accompanied by changes of visible-near-infrared optical absorption influencing via evanescent field on the guided light intensity. Experimental results suggest that the selected reagents provide optical properties suitable for practical sensing applications and that the sensitized PCS optical fibers could be used for detection of ammonia gas.

  7. Development of field-based real-time reverse transcription-polymerase chain reaction assays for detection of Chikungunya and O'nyong-nyong viruses in mosquitoes.

    Science.gov (United States)

    Smith, Darci R; Lee, John S; Jahrling, Jordan; Kulesh, David A; Turell, Michael J; Groebner, Jennifer L; O'Guinn, Monica L

    2009-10-01

    Chikungunya (CHIK) and O'nyong-nyong (ONN) are important emerging arthropod-borne diseases. Molecular diagnosis of these two viruses in mosquitoes has not been evaluated, and the effects of extraneous mosquito tissue on assay performance have not been tested. Additionally, no real-time reverse transcription-polymerase chain reaction (RT-PCR) assay exists for detecting ONN virus (ONNV) RNA. We describe the development of sensitive and specific real-time RT-PCR assays for detecting CHIK and ONN viral RNA in mosquitoes, which have application for field use. In addition, we compared three methods for primer/probe design for assay development by evaluating their sensitivity and specificity. This comparison resulted in development of virus-specific assays that could detect less than one plaque-forming unit equivalent of each of the viruses in mosquitoes. The use of these assays will aid in arthropod-borne disease surveillance and in the control of the associated diseases.

  8. Involvement of ethylene in lesion development and systemic acquired resistance in tobacco during the hypersensitive reaction to tobacco mosaic virus

    NARCIS (Netherlands)

    Knoester, M.; Linthorst, H.J.M.; Bol, J.F.; Loon, L.C. van

    2001-01-01

    Different approaches were taken to investigate the significance of ethylene in lesion development and systemic acquired resistance (SAR) in tobacco (Nicotiana tabacum) reacting hypersensitively to tobacco mosaic virus (TMV). Gaseous ethylene, the ethylene precursor 1-aminocyclopropane-1-carboxylic

  9. Well-Defined Silica Grafted Molybdenum Bis(imido) Catalysts for Imine Metathesis Reactions

    KAUST Repository

    Barman, Samir

    2017-04-06

    Novel site-isolated tetracoordinated molybdenum complexes possessing bis(imido) ligands, [(≡Si–O)2Mo(═NR)2] (R = t-Bu, 2,6-C6H3-i-Pr2), were immobilized on partially dehydroxylated silica (SiO2-200) by a rigorous surface organometallic chemistry protocol. The newly developed materials adorned with bis(imido) functional units, which were previously exploited mainly as spectator ligands on silica-supported olefin metathesis molybdenum catalysts, are found to be efficient heterogeneous catalytic systems for imine cross metathesis under mild conditions.

  10. Well-Defined Silica Grafted Molybdenum Bis(imido) Catalysts for Imine Metathesis Reactions

    KAUST Repository

    Barman, Samir; Merle, Nicolas; Minenkov, Yury; De Mallmann, Aimery; Samantaray, Manoja; Le Qué mé ner, Fré dé ric; Szeto, Kai C.; Abou-Hamad, Edy; Cavallo, Luigi; Taoufik, Mostafa; Basset, Jean-Marie

    2017-01-01

    Novel site-isolated tetracoordinated molybdenum complexes possessing bis(imido) ligands, [(≡Si–O)2Mo(═NR)2] (R = t-Bu, 2,6-C6H3-i-Pr2), were immobilized on partially dehydroxylated silica (SiO2-200) by a rigorous surface organometallic chemistry protocol. The newly developed materials adorned with bis(imido) functional units, which were previously exploited mainly as spectator ligands on silica-supported olefin metathesis molybdenum catalysts, are found to be efficient heterogeneous catalytic systems for imine cross metathesis under mild conditions.

  11. Development of a Monte Carlo code for the data analysis of the {sup 18}F(p,α){sup 15}O reaction at astrophysical energies

    Energy Technology Data Exchange (ETDEWEB)

    Caruso, A.; Cherubini, S.; Spitaleri, C.; La Cognata, M.; Lamia, L.; Rapisarda, G.; Romano, S.; Sergi, ML. [Dipartimento di Fisica e Astronomia, Catania, Italy and INFN-Laboratori Nazionali del Sud, Catania (Italy); Crucillà, V. [INFN-Laboratori Nazionali del Sud, Catania (Italy); Gulino, M. [Universitá di Enna KORE, Enna, Italy and INFN-Laboratori Nazionali del Sud, Catania (Italy); Kubono, S. [Riken, Wako, Tokyo, Japan and Center for Nuclear Study, The University of Tokyo (Japan); Yamaguchi, H.; Hayakawa, S.; Wakabayashi, Y. [Center for Nuclear Study, The University of Tokyo (Japan); Iwasa, N. [Department of Physics, Tohoku University, Sendai (Japan); Kato, S. [Department of Physics, Yamagata University, Yamagata (Japan); Komatsubara, T. [Rare Isotope Science Project, Institute for Basic Science, Yuseong-daero, Yuseong-gu, Daejeon 305-811 (Korea, Republic of); Teranishi, T. [Department of Physics, Kyushu University, Fukuoka (Japan); Coc, A. [Centre de Spectrométrie Nucléaire et de Spectrométrie de Masse, Orsay (France); Hammache, F. [Institut de Physique Nucléaire, IN2P3, Orsay (France); and others

    2015-02-24

    Novae are astrophysical events (violent explosion) occurring in close binary systems consisting of a white dwarf and a main-sequence star or a star in a more advanced stage of evolution. They are called 'narrow systems' because the two components interact with each other: there is a process of mass exchange with resulting in the transfer of matter from the companion star to the white dwarf, leading to the formation of this last of the so-called accretion disk, rich mainly of hydrogen. Over time, more and more material accumulates until the pressure and the temperature reached are sufficient to trigger nuclear fusion reactions, rapidly converting a large part of the hydrogen into heavier elements. The products of 'hot hydrogen burning' are then placed in the interstellar medium as a result of violent explosions. Studies on the element abundances observed in these events can provide important information about the stages of evolution stellar. During the outbursts of novae some radioactive isotopes are synthesized: in particular, the decay of short-lived nuclei such as {sup 13}N and {sup 18}F with subsequent emission of gamma radiation energy below 511 keV. The gamma rays from products electron-positron annihilation of positrons emitted in the decay of {sup 18}F are the most abundant and the first observable as soon as the atmosphere of the nova starts to become transparent to gamma radiation. Hence the importance of the study of nuclear reactions that lead both to the formation and to the destruction of {sup 18}F. Among these, the {sup 18}F(p,α){sup 15}O reaction is one of the main channels of destruction. This reaction was then studied at energies of astrophysical interest. The experiment done at Riken, Japan, has as its objective the study of the {sup 18}F(p,α){sup 15}O reaction, using a beam of {sup 18}F produced at CRIB, to derive important information about the phenomenon of novae. In this paper we present the experimental technique and the

  12. Risk factors in the development of adverse reactions to N-acetylcysteine in patients with paracetamol poisoning

    DEFF Research Database (Denmark)

    Schmidt, L E; Dalhoff, K

    2001-01-01

    AIMS: To identify risk factors in the development of side-effects to N-acetylcysteine (NAC) in patients with paracetamol poisoning. METHODS: A retrospective study was carried out based upon the hospital charts of 529 consecutive patients admitted with paracetamol poisoning, all treated with NAC...... 2.9 times (95% CI 2.1, 4.7) more likely to develop side-effects (Chi-square: P = 0.004). Side-effects were of similar severity in asthmatics and nonasthmatics. A history of medical allergy was not a risk factor. Serum paracetamol was lower in patients with side-effects than in those without (Mann......-Whitney: P = 0.00006). CONCLUSIONS: Asthma must be considered a risk factor in the development of side-effects to NAC. However, the side-effects are easily managed and there is no reason to withhold NAC from any patient with paracetamol poisoning. Paracetamol itself seems to offer some protection against...

  13. Lattice site location of optical centers in GaN:Eu light emitting diode material grown by organometallic vapor phase epitaxy

    KAUST Repository

    Lorenz, K.; Alves, E.; Roqan, Iman S.; O’ Donnell, K. P.; Nishikawa, A.; Fujiwara, Y.; Boćkowski, M.

    2010-01-01

    Eu-doped GaN was grown by organometallic vapor phase epitaxy at temperatures from 900 to 1100 °C. Eu incorporation is influenced by temperature with the highest concentration found for growth at 1000 °C. In all samples, Eu is incorporated entirely on substitutional Ga sites with a slight displacement which is highest (∼0.2 Å) in the sample grown at 900 °C and mainly directed along the c-axis. The major optical Eu3+ centers are identical for in situdoped and ion-implanted samples after high temperature and pressure annealing. The dominant Eu3+luminescence lines are attributed to isolated, substitutional Eu.

  14. Phase Transition Enthalpy Measurements of Organic and Organometallic Compounds and Ionic Liquids. Sublimation, Vaporization, and Fusion Enthalpies from 1880 to 2015. Part 2. C11-C192

    Science.gov (United States)

    Acree, William; Chickos, James S.

    2017-03-01

    The second part of this compendium concludes with a collection of phase change enthalpies of organic molecules inclusive of C11-C192 reported over the period 1880-2015. Also included are phase change enthalpies including fusion, vaporization, and sublimation enthalpies for organometallic, ionic liquids, and a few inorganic compounds. Paper I of this compendium, published separately, includes organic compounds from C1 to C10 and describes a group additivity method for evaluating solid, liquid, and gas phase heat capacities as well as temperature adjustments of phase changes. Paper II of this compendium also includes an updated version of a group additivity method for evaluating total phase change entropies which together with the fusion temperature can be useful in estimating total phase change enthalpies. Other uses include application in identifying potential substances that either form liquid or plastic crystals or exhibit additional phase changes such as undetected solid-solid transitions or behave anisotropically in the liquid state.

  15. Lattice site location of optical centers in GaN:Eu light emitting diode material grown by organometallic vapor phase epitaxy

    KAUST Repository

    Lorenz, K.

    2010-09-16

    Eu-doped GaN was grown by organometallic vapor phase epitaxy at temperatures from 900 to 1100 °C. Eu incorporation is influenced by temperature with the highest concentration found for growth at 1000 °C. In all samples, Eu is incorporated entirely on substitutional Ga sites with a slight displacement which is highest (∼0.2 Å) in the sample grown at 900 °C and mainly directed along the c-axis. The major optical Eu3+ centers are identical for in situdoped and ion-implanted samples after high temperature and pressure annealing. The dominant Eu3+luminescence lines are attributed to isolated, substitutional Eu.

  16. Development of models to follow vapour-aerosol reactions and iodine chemistry, technical progress report, 1 January - 31 August 1991

    International Nuclear Information System (INIS)

    Deane, A.M.; Henshaw, J.; Sims, H.E.; Ellicott, P.; Morton, D.A.V.; Newland, M.S.; Roberts, G.J.; Smith, P.N.

    1991-12-01

    Iodine chemistry and vapour-aerosol interactions have been identified as key uncertainties in modelling severe accidents in nuclear plant. The objectives of this work programme are to develop a better understanding of such behaviour and to incorporate the findings into a model. This report describes work conducted during the first eight months of the contract. (author)

  17. The Development, Implementation and Application of Accurate Quantum Chemical Methods for Molecular Structure, Spectra and Reaction Paths

    Science.gov (United States)

    2016-02-02

    Bartlett, Nigel G. J. Richards, Robert W. Molt, Alison M. Lecher. Facile Csp2 Csp2 bond cleavage in oxalic acid-derived radicals: Implications for...Transfer The ACES III program system being developed un this grant is in wide use at the DOD HPCC. Active users at ARL include de Carlos Taylor , Betsy Rice

  18. Development and validation of a SYBR Green I-based real-time polymerase chain reaction method for detection of haptoglobin gene deletion in clinical materials.

    Science.gov (United States)

    Soejima, Mikiko; Tsuchiya, Yuji; Egashira, Kouichi; Kawano, Hiroyuki; Sagawa, Kimitaka; Koda, Yoshiro

    2010-06-01

    Anhaptoglobinemic patients run the risk of severe anaphylactic transfusion reaction because they produce serum haptoglobin (Hp) antibodies. Being homozygous for the Hp gene deletion (HP(del)) is the only known cause of congenital anhaptoglobinemia, and clinical diagnosis of HP(del) before transfusion is important to prevent anaphylactic shock. We recently developed a 5'-nuclease (TaqMan) real-time polymerase chain reaction (PCR) method. A SYBR Green I-based duplex real-time PCR assay using two forward primers and a common reverse primer followed by melting curve analysis was developed to determine HP(del) zygosity in a single tube. In addition, to obviate initial DNA extraction, we examined serially diluted blood samples as PCR templates. Allelic discrimination of HP(del) yielded optimal results at blood sample dilutions of 1:64 to 1:1024. The results from 2231 blood samples were fully concordant with those obtained by the TaqMan-based real-time PCR method. The detection rate of the HP(del) allele by the SYBR Green I-based method is comparable with that using the TaqMan-based method. This method is readily applicable due to its low initial cost and analyzability using economical real-time PCR machines and is suitable for high-throughput analysis as an alternative method for allelic discrimination of HP(del).

  19. Synthesis of a sugar-organometallic compound 1,1 Prime -difurfurylferrocene and its microwave preparation of carbon/iron oxide nanocomposite

    Energy Technology Data Exchange (ETDEWEB)

    Zhao Shanyu, E-mail: syzhao65@gmail.com [School of Environmental and Safty Engineering, Changzhou University, Changzhou, Jiangsu 213164 (China); Department of Chemistry, Brown University, Providence, RI 02912-9108 (United States); Cooper, Daniel C. [Department of Chemistry, Brown University, Providence, RI 02912-9108 (United States); Xu, Haixun [Institute of Building Materials, Dalian University of Technology, Dalian, Liaoning 116024 (China); Zhu Pinghua [School of Environmental and Safty Engineering, Changzhou University, Changzhou, Jiangsu 213164 (China); Suggs, J. William, E-mail: j_suggs@brown.edu [Department of Chemistry, Brown University, Providence, RI 02912-9108 (United States)

    2013-01-01

    Graphical abstract: In order to synthesize a carbon-metal or metal oxide combination sphere, carbonaceous resource furfural was introduced, which was nucleophilic treated with 1,1 Prime -dilithioferrocene to form a sugar-organometallic compound: ferrocenyl monosaccharide derivative 1,1 Prime -difurfurylferrocene, which can be hydrothermally treated in a microwave reactor to give 300-500 nm microspheres with the {alpha}-Fe{sub 2}O{sub 3} or Fe{sub 3}O{sub 4} formed on the surface, which may be favorable for new magnetic materials preparation or instead of iron with other metal ions, versatile carbon/metal composites will be possibly synthesized for catalysis, drug delivery and magnetic uses. Highlights: Black-Right-Pointing-Pointer We synthesized 1,1 Prime -difurfurylferrocene by nucleophilic treating furfural with 1,1 Prime -dilithioferrocene. Black-Right-Pointing-Pointer 1,1 Prime -Difurfurylferrocene can be hydrothermally treated by microwave to give microspheres with iron oxides on the surface. Black-Right-Pointing-Pointer 1,1 Prime -Difurfurylferrocene has 2 reactive furanose units, which form carbonspheres and ferrocenyl can give iron oxides. Black-Right-Pointing-Pointer REDOX atmosphere influences the coating structures. - Abstract: In order to synthesize a carbon-metal or metal oxide combination sphere, carbonaceous resource furfural 1 was introduced, which was nucleophilic treated with 1,1 Prime -dilithioferrocene 2 to form a sugar-organometallic compound: ferrocenyl monosaccharide derivative 1,1 Prime -difurfurylferrocene 3. 1,1 Prime -Difurfurylferrocene 3 can be hydrothermally treated in a microwave reactor to give 300-500 nm microspheres with the {alpha}-Fe{sub 2}O{sub 3} or Fe{sub 3}O{sub 4} nanocrystals formed on the surface, which may be favorable for new magnetic materials preparation or instead of iron with other metal ions, versatile carbon/metal composites will be possibly synthesized for catalysis, drug delivery and magnetic uses.

  20. Synthesis of a sugar-organometallic compound 1,1′-difurfurylferrocene and its microwave preparation of carbon/iron oxide nanocomposite

    International Nuclear Information System (INIS)

    Zhao Shanyu; Cooper, Daniel C.; Xu, Haixun; Zhu Pinghua; Suggs, J. William

    2013-01-01

    Graphical abstract: In order to synthesize a carbon–metal or metal oxide combination sphere, carbonaceous resource furfural was introduced, which was nucleophilic treated with 1,1′-dilithioferrocene to form a sugar-organometallic compound: ferrocenyl monosaccharide derivative 1,1′-difurfurylferrocene, which can be hydrothermally treated in a microwave reactor to give 300–500 nm microspheres with the α-Fe 2 O 3 or Fe 3 O 4 formed on the surface, which may be favorable for new magnetic materials preparation or instead of iron with other metal ions, versatile carbon/metal composites will be possibly synthesized for catalysis, drug delivery and magnetic uses. Highlights: ► We synthesized 1,1′-difurfurylferrocene by nucleophilic treating furfural with 1,1′-dilithioferrocene. ► 1,1′-Difurfurylferrocene can be hydrothermally treated by microwave to give microspheres with iron oxides on the surface. ► 1,1′-Difurfurylferrocene has 2 reactive furanose units, which form carbonspheres and ferrocenyl can give iron oxides. ► REDOX atmosphere influences the coating structures. - Abstract: In order to synthesize a carbon–metal or metal oxide combination sphere, carbonaceous resource furfural 1 was introduced, which was nucleophilic treated with 1,1′-dilithioferrocene 2 to form a sugar-organometallic compound: ferrocenyl monosaccharide derivative 1,1′-difurfurylferrocene 3. 1,1′-Difurfurylferrocene 3 can be hydrothermally treated in a microwave reactor to give 300–500 nm microspheres with the α-Fe 2 O 3 or Fe 3 O 4 nanocrystals formed on the surface, which may be favorable for new magnetic materials preparation or instead of iron with other metal ions, versatile carbon/metal composites will be possibly synthesized for catalysis, drug delivery and magnetic uses.

  1. Aligned carbon nanotube with electro-catalytic activity for oxygen reduction reaction

    Science.gov (United States)

    Liu, Di-Jia; Yang, Junbing; Wang, Xiaoping

    2010-08-03

    A catalyst for an electro-chemical oxygen reduction reaction (ORR) of a bundle of longitudinally aligned carbon nanotubes having a catalytically active transition metal incorporated longitudinally in said nanotubes. A method of making an electro-chemical catalyst for an oxygen reduction reaction (ORR) having a bundle of longitudinally aligned carbon nanotubes with a catalytically active transition metal incorporated throughout the nanotubes, where a substrate is in a first reaction zone, and a combination selected from one or more of a hydrocarbon and an organometallic compound containing an catalytically active transition metal and a nitrogen containing compound and an inert gas and a reducing gas is introduced into the first reaction zone which is maintained at a first reaction temperature for a time sufficient to vaporize material therein. The vaporized material is then introduced to a second reaction zone maintained at a second reaction temperature for a time sufficient to grow longitudinally aligned carbon nanotubes over the substrate with a catalytically active transition metal incorporated throughout the nanotubes.

  2. Efforts in Bologna on quasiparticle level density systematics and on comparison and development of different approaches to preequilibrium reaction mechanism

    International Nuclear Information System (INIS)

    Herman, M.; Reffo, G.; Weidenmueller, H.A.; Lenske, H.; Wolter, H.H.; Giardina, G.; Italiano, A.; Rosetti, M.

    1991-01-01

    We present a summary of activities carried out at ENEA in Bologna on the development of the preequilibrium emission models. We start with the first application of the Multistep Compound Model in the Heidelberg formulation, which is followed by the Multistep Direct calculations. Next, the comparison between the exciton and Multistep Compound model by Feshbach, Kerman, and Koonin is presented. Finally we discuss energy and isotope dependence of the average single particle level spacing. (author). Refs, 9 figs

  3. Development of cytomegalovirus (CMV) disease may be predicted in HIV-infected patients by CMV polymerase chain reaction and the antigenemia test

    DEFF Research Database (Denmark)

    Dodt, K K; Jacobsen, P H; Hofmann, B

    1997-01-01

    ; OR: CMV PCR 10.0, antigenemia test 4.4 and CMV cultures 4.3. No clinical parameters had any significant predictive value in the stepwise multivariate model. CONCLUSIONS: The CMV PCR and the CMV antigenemia tests are both sensitive methods that may predict development of CMV disease up to several...... evaluated PCR and the antigenemia tests as methods for early detection of CMV disease. METHODS: Two-hundred HIV-seropositive subjects with CD4 T-cell counts below 100 x 10(6)/l were monitored with CMV polymerase chain reaction (PCR), the antigenemia test, blood cultures and CMV immunoglobulin (Ig) G and Ig...... showed that the CMV PCR, the antigenemia test and blood cultures all had significant predictive values for subsequent development of CMV disease with odds ratios (OR) of 30, 22 and 20. CMV serology had no predictive value. Multivariate analysis showed that the PCR method was superior to the other tests...

  4. Studies in group IV organometallic chemistry XXX. Synthesis of compounds containing tin---titanium and tin---zirconium bonds

    NARCIS (Netherlands)

    Creemers, H.M.J.C.; Verbeek, F.; Noltes, J.G.

    1968-01-01

    Starting from the tetrakis(diethylamino) derivatives of titanium and zirconium and pheyltin hydrides six intermetalic compounds contianing up to nine tin and titanium(or zirconium) atoms have been obtained by hydrostannolysis type reactions.

  5. Effect of sulfur dioxide on the development of an anaphylactic reaction in guinea pigs sensitized by an immunosorbent

    Energy Technology Data Exchange (ETDEWEB)

    Khristova, L; Orlov, G

    1973-01-01

    The effect of sulfur dioxide on the development of experimentally- induced anaphylaxis in guinea pigs inhaling antigenic aerosol (egg albumin) was studied. The animals were sensitized in advance with a complex of protein and sefadex (immunosorbent). Animals exposed for 60 min to SO/sub 2/ showed more severe anaphylactic seizures immediately after aerosol provocation than did animals not exposed to SO/sub 2/. The use of the immunosorbent resulted in the formation of large amounts of antibodies and prolonged antibody response, indicating the suitability of this method for sensitization.

  6. Quasielastic reactions

    International Nuclear Information System (INIS)

    Hansen, O.

    1983-01-01

    A brief review is presented of the experimental and theoretical situation regarding transfer reactions and inelastic scattering. In the first category there is little (very little) precision data for heavy projectiles and consequently almost no experience with quantitative theoretical analysis. For the inelastic scattering the rather extensive data strongly supports the coupled channels models with collective formfactors. At the most back angles, at intensities about 10 -5 of Rutherford scattering, a second, compound-like mechanism becomes dominant. The description of the interplay of these two opposite mechanisms provides a new challenge for our understanding

  7. Development, improvement and calibration of neutronic reaction rate measurements: elaboration of a base of standard techniques; Developpement, amelioration et calibration des mesures de taux de reaction neutroniques: elaboration d`une base de techniques standards

    Energy Technology Data Exchange (ETDEWEB)

    Hudelot, J.P

    1998-06-19

    In order to improve and to validate the neutronic calculation schemes, perfecting integral measurements of neutronic parameters is necessary. This thesis focuses on the conception, the improvement and the development of neutronic reaction rates measurements, and aims at building a base of standard techniques. Two subjects are discussed. The first one deals with direct measurements by fission chambers. A short presentation of the different usual techniques is given. Then, those last ones are applied through the example of doubling time measurements on the EOLE facility during the MISTRAL 1 experimental programme. Two calibration devices of fission chambers are developed: a thermal column located in the central part of the MINERVE facility, and a calibration cell using a pulsed high flux neutron generator and based on the discrimination of the energy of the neutrons with a time-of-flight method. This second device will soon allow to measure the mass of fission chambers with a precision of about 1 %. Finally, the necessity of those calibrations will be shown through spectral indices measurements in core MISTRAL 1 (UO{sub 2}) and MISTRAL 2 (MOX) of the EOLE facility. In each case, the associated calculation schemes, performed using the Monte Carlo MCNP code with the ENDF-BV library, will be validated. Concerning the second one, the goal is to develop a method for measuring the modified conversion ratio of {sup 238}U (defined as the ratio of {sup 238}U capture rate to total fission rate) by gamma-ray spectrometry of fuel rods. Within the framework of the MISTRAL 1 and MISTRAL 2 programmes, the measurement device, the experimental results and the spectrometer calibration are described. Furthermore, the MCNP calculations of neutron self-shielding and gamma self-absorption are validated. It is finally shown that measurement uncertainties are better than 1 %. The extension of this technique to future modified conversion ratio measurements for {sup 242}Pu (on MOX rods) and

  8. Development and Implementation of an Automatic Continuous Online Monitoring and Control Platform for Polymerization Reactions to Sharply Boost Energy and Resource Efficiency in Polymer Manufacturing

    Energy Technology Data Exchange (ETDEWEB)

    Reed, Wayne [Tulane Univ., New Orleans, LA (United States); Drenski, Michael [Tulane Univ., New Orleans, LA (United States); Romagnoli, Jose [Tulane Univ., New Orleans, LA (United States)

    2017-10-16

    . Recognizing the industrial potential a patent on automatic production of multi-modal polymers was filed, and DoE acknowledged. In Fall 2016 the TF team developed a basic principles controller for copolymer composition and demonstrated it on aqueous free radical copolymerization of comonomers Am and styrene sulfonate, SS. TF then fused the Mw and composition controllers to achieve simultaneous control of both Mw and copolymer composition trajectories. Numerous simultaneous trajectories were demonstrated, including a trimodal composition distribution with constant Mw. Meanwhile, the LSU group developed a Kalman filter to improve the results of their automatic Mw and conversion controller and successful tests were made. During the project the TF team developed a means of computing full MWD during polymer synthesis without need for any chromatographic separation, based on model distributions. This means the polymer product is ‘born characterized’ and this can eliminate post-manufacture analytical laboratory quality control. TF filed a joint patent application on this new approach to chromatography-free determination of MWD with acknowledgment to DoE. The Tulane group obtained a 60MHz NMR during the project and recently completed the first work on separating three comonomers, Am, SS, and Na-acrylate, with a first demonstration of terpolymer composition control with the TF basic principles controller. Widespread dissemination of ACOMP/CI in the polymer manufacturing sector will bolster DoE goals of energy efficiency and reduced GHG emissions: The ability to monitor and actively control polymerization reactions will lead to more efficient use of energy and non-renewable resources, plant and labor time, increase the safety of manufacturing personnel, and will enhance product quality and lead to feasibility of manufacturing of polymers currently too complex for industrial scale production, while leading to less GHG emissions per kilo of product, and allowing for increased U

  9. The development of flux-split algorithms for flows with non-equilibrium thermodynamics and chemical reactions

    Science.gov (United States)

    Grossman, B.; Cinella, P.

    1988-01-01

    A finite-volume method for the numerical computation of flows with nonequilibrium thermodynamics and chemistry is presented. A thermodynamic model is described which simplifies the coupling between the chemistry and thermodynamics and also results in the retention of the homogeneity property of the Euler equations (including all the species continuity and vibrational energy conservation equations). Flux-splitting procedures are developed for the fully coupled equations involving fluid dynamics, chemical production and thermodynamic relaxation processes. New forms of flux-vector split and flux-difference split algorithms are embodied in a fully coupled, implicit, large-block structure, including all the species conservation and energy production equations. Several numerical examples are presented, including high-temperature shock tube and nozzle flows. The methodology is compared to other existing techniques, including spectral and central-differenced procedures, and favorable comparisons are shown regarding accuracy, shock-capturing and convergence rates.

  10. Development and evaluation of a novel low power, high frequency piezoelectric-based ultrasonic reactor for intensifying the transesterification reaction

    Directory of Open Access Journals (Sweden)

    Mortaza Aghbashlo

    2016-12-01

    Full Text Available In this study, a novel low power, high frequency piezoelectric-based ultrasonic reactor was developed and evaluated for intensifying the transesterification process. The reactor was equipped with an automatic temperature control system, a heating element, a precise temperature sensor, and a piezoelectric-based ultrasonic module. The conversion efficiency and specific energy consumption of the reactor were examined under different operational conditions, i.e., reactor temperature (40‒60 °C, ultrasonication time (6‒10 min, and alcohol/oil molar ratio (4:1‒8:1. Transesterification of waste cooking oil (WCO was performed in the presence of a base-catalyst (potassium hydroxide using methanol. According to the obtained results, alcohol/oil molar ratio of 6:1, ultrasonication time of 10 min, and reactor temperature of 60 °C were found as the best operational conditions. Under these conditions, the reactor converted WCO to biodiesel with a conversion efficiency of 97.12%, meeting the ASTM standard satisfactorily, while the lowest specific energy consumption of 378 kJ/kg was also recorded. It should be noted that the highest conversion efficiency of 99.3 %, achieved at reactor temperature of 60 °C, ultrasonication time of 10 min, and alcohol/oil molar ratio of 8:1, was not favorable as the associated specific energy consumption was higher at 395 kJ/kg. Overall, the low power, high frequency piezoelectric-based ultrasonic module could be regarded as an efficient and reliable technology for intensifying the transesterification process in terms of energy consumption, conversion efficiency, and processing time, in comparison with high power, low frequency ultrasonic system reported previously. Finally, this technology could also be considered for designing, developing, and retrofitting chemical reactors being employed for non-biofuel applications as well.

  11. Pengembangan Sejumlah Primer untuk Reverse Transcriptase Polymerase Chain Reaction Guna Melacak Virus Flu Burung di Indonesia (DEVELOPMENt OF PRIMERS FOR REVERSE TRANSCRIPTASE POLYMERASE CHAIN REACTION TO DETECT AVIAN INFLUENZA VIRUS IN INDONESIA

    Directory of Open Access Journals (Sweden)

    Ni Luh Putu Indi Dharmayanti

    2016-07-01

    Full Text Available Until recently, two clades of of avian influenza viruses (AIVs designated as 2.3.2 and 2.2.3 havebeen circulating in Indonesia. Mutations of AIV genes have cretaed many more variants of the virus. It istherefore important to evaluate the appropriate methods used for the detection and diagnosis of AI virusin the field. Reverse Transcriptase-Polymerase Chain Reaction (RT-PCR have been used as a standardmethod for detection of AIV in many laboratories in Indonesia. The success of RT-PCR for detection ofAIV virus is dependent on the nucleotide sequences of primer that match with the circulating of AIVs. Theaims of this study was to develop RT-PCR by designing primers for H5 subtype specific to the circulatingAIVs in the field. The primers were designed using Primer Design software, and optimization andvalidation of the primer were conducted using AIVs that have been characterized in the previous study.The primers were then used RT-PCR using AIV isolates from field samples and their sensitivity andspecificity were then determined. The results showed that the H5 primers designed in this study, H5-IDand H5-NLP, was able to detect the AIVs in field samples better than the H5-specific primers have beenused previously. In conclusion, H5 primers designed based on recent viruses in the field showed betterresults in the detection of AI virus as compared to the previous primers. As AIV-H5N1 subtype in the fieldwill continue to change and evolve, the use of primers designed in this study is recommended for diagnosisof H5 AIV.

  12. Proton scattering on unstable nuclei: study of 40S(p,p') and 43Ar(p,p') reactions, development of detection system MUST

    International Nuclear Information System (INIS)

    Marechal, F.

    1998-01-01

    We measured for the first time the elastic and inelastic proton scattering on the 40 S unstable nucleus. The experiment was performed in inverse kinematics at the NSCL AT Michigan State University with a 40 S secondary beam bombarding a CH 2 target at 30 MeV/A. We obtained the elastic scattering angular distribution and two points of the inelastic distribution to the first 2 + excited state found to be located at 860±90 KeV. With a coupled channel analysis, the β 2 quadrupolar deformation parameter is found to be equal to 0.35±0.05. This value can be compared to 0.28±0.02 obtained by coulomb excitation. A macroscopic analysis allowed us to extract the neutron and proton transition matrix element ratio M n /M p which is equal to 1.88±0.38. This value, greater than N/Z, could indicate an isovector effect in the first 2 + state excitation which could be due to a difference between the neutron and proton vibrations. The microscopic analysis gives the possibility to test the densities and the transition densities to the first 2 + state. The calculated densities for the 40 S nucleus show a neutron skin. However the microscopic analysis yields a M n /M p ratio of 1.40±0.20. A similar elastic and inelastic proton scattering experiment allowed us to get a deformation parameter of 0.25±0.03 for the 43 Ar nucleus. To develop the study of direct reactions induced by radioactive beams at GANIL, we have developed and built, in collaboration with the CEA-Saclay and the CEA-Bruyeres, the new detector MUST.It is based on the silicon strip technology, and is dedicated to the measurement of recoiling light particles emitted in these reactions. The results obtained with a 40 Ar beam at 77 Me V/A, have shown the good performances of the detector for the particle identification as well as for the resolutions, and allow us to consider now a large experimental programme concerning these direct reactions induced by radioactive beams. These tests allowed us to establish a reference

  13. Effects of chronic inflammatory reaction status on the development of complications in patients with chronic renal failure

    International Nuclear Information System (INIS)

    Wang Caili; Wei Feng; Shi Ping; Li Guiling

    2006-01-01

    Objective: To investigate the relationship between changes of serum contents of CRP, IL-6, TNF-α, IL-10 and the development of complications (anemia, malnutrition, atherosclerosis) in patients with chronic renal failure. Methods: Serum IL-6, TNF-α (with RIA) and CRP, IL-10 (with ELISA) levels were determined in 126 patients with chronic renal failure and 36 controls. Blood hemoglobin, albumin, glucose and triglycerides levels were also determined in all these patients. Echocardiography was performed in 95 patients. Results: (1) Serum contents of CRP, IL-6, TNF-α and IL-10 were all significantly higher in the patients than those in the controls (P 6mmol/L, n=83) were significantly higher than those in the corresponding patients without anemia, malnutrition and hyperglycemia ( all P 1.71mmol/L, n=68), the levels were lower than those in patients without high TG (P<0.001 for IL-6, P<0.01 for CRP and IL-10). In patients with aortic arteriosclerosis shown on echocardiography (n=37), levels of the markers were higher than those in patients without arteriosclerosis (n=58) (P<0.001 for IL-10, P<0.001 for CRP and IL-6, P<0.05 for TNF-α). Correlation studies showed that levels of all the four markers were negatively correlated with levels of hemoglobin and albumin, TNF-α levels were correlated with levels of glucose and CRP, IL-6, IL-10 levels were negatively correlated with triglyceride levels. (3) Levels of each of the pro-inflammatory markers (CRP, IL-6, TNF-α) were correlated with levels of the anti-inflammatory cytokine IL-10 (r=0.463, 0.546 and 0.402 respectively). Conclusion: (1) Serum levels of CRP, IL-6, TNF-α and IL-10 were increased in patients with chronic renal failure. (2) Levels of these markers were correlated in some degree with the development of complications (anemia, malnutrition, arteriosclerosis......) in the patients. (3) Levels of pro-inflammatory markers were correlated with levels of anti-inflammatory cytokine IL-10. (authors)

  14. Development of a multiplex polymerase chain reaction assay for simultaneous identification of human enterovirus 71 and coxsackievirus A16

    Science.gov (United States)

    Thao, Nguyen Thi Thanh; Ngoc, Nguyen Thi Kim; Tú, Phan Văn; Thúy, Trần Thi; Cardosa, Mary Jane; McMinn, Peter Charles; Phuektes, Patchara

    2010-01-01

    Human enterovirus 71 (HEV71) and coxsackievirus A16 (CVA16) are two major aetiological agents of hand, foot and mouth disease (HFMD) in children. Recently there have been several large outbreaks of HFMD in Vietnam and the Asia-Pacific region. In this study, a multiplex RT-PCR assay was developed in order to detect simultaneously HEV71, CVA16 and other human enteroviruses. Enterovirus detection was performed with a mixture of three pairs of oligonucleotide primers: one pair of published primers for amplifying all known enterovirus genomes and two new primer pairs specific for detection of the VP1 genes of HEV71 and CVA16. Enterovirus isolates, CVA16 and HEV71 strains identified previously from patients with HFMD were examined to evaluate the sensitivity and specificity of the multiplex RT-PCR assay. The assay was then applied to the direct detection of these viruses in clinical specimens obtained from HFMD cases identified at Children's Hospital Number 2, Ho Chi Minh City, Vietnam. The multiplex RT-PCR assay showed 100% specificity in screening for enteroviruses and in identifying HEV71 and CVA16. Similar results were obtained when using the multiplex RT-PCR assay to screen for enteroviruses and to identify HEV71 and CVA16 in clinical specimens obtained from HFMD cases identified at the hospital. This multiplex RT-PCR assay is a rapid, sensitive and specific assay for the diagnosis of HEV71 or CVA16 infection in cases of HFMD and is also potentially useful for molecular epidemiological investigations. PMID:20863857

  15. Application of microwave irradiation to organic liquid phase reactions

    International Nuclear Information System (INIS)

    Huang Kun; Liu Hua; Ji Xuelin

    1994-01-01

    Microwave irradiation has been used in organic liquid phase reactions to significantly reduce the reaction time and improve the yield. The proposed mechanism, the development of techniques and reactions, such as Diels-Alder, ene, rearrangement reactions etc., are discussed

  16. 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.

  17. Processing development for ceramic structural components: the influence of a presintering of silicon on the final properties of reaction bonded silicon nitride. Final technical report

    Energy Technology Data Exchange (ETDEWEB)

    1982-03-01

    The influence of a presintering of silicon on the final properties of reaction bonded silicon nitride has been studied using scanning electron and optical microscopy, x-ray diffraction analysis, 4 pt. bend test, and mecury intrusion porosimetry. It has been shown that presintering at 1050/sup 0/C will not affect the final nitrided properties. At 1200/sup 0/C, the oxide layer is removed, promoting the formation of B-phase silicon nitride. Presintering at 1200/sup 0/C also results in compact weight loss due to the volatilization of silicon, and the formation of large pores which severely reduce nitrided strength. The development of the structure of sintered silicon compacts appears to involve a temperature gradient, with greater sintering observed near the surface.

  18. Development of a Nuclear Reaction Database on Silicon for Simulation of Neutron-Induced Single-Event Upsets in Microelectronics and its Application

    International Nuclear Information System (INIS)

    Watanabe, Yukinobu; Kodama, Akihiro; Tukamoto, Yasuyuki; Nakashima, Hideki

    2005-01-01

    We have developed a cross-section database for neutron-induced reactions on 28Si in the energy range between 2 MeV and 3 GeV in order to analyze single-event upsets (SEUs) phenomena induced by cosmic-ray neutrons in microelectronic devices. A simplified spherical device model is proposed for simulation of the initial processes of SEUs. The model is applied to SEU cross-section calculations for semiconductor memory devices. The calculated results are compared with measured SEU cross sections and the other simulation result. The dependence of SEU cross sections on incident neutron energy and secondary ions having the most important effects on SEUs are discussed

  19. Study of two examples of non linear interaction of a laser wave with matter: laser-induced damage of dielectrics and non linear optical properties of organometallic molecules in solution

    International Nuclear Information System (INIS)

    Gaudry, Jean-Baptiste

    2000-01-01

    This research thesis reports the study of two mechanisms of non linear interaction of a laser wave with matter. More particularly, it reports the experimental investigation of non linear optical properties of organometallic molecules in solution, as well as the damage of perfect silica under laser irradiation by using simulation codes. As far as optical properties are concerned, the author highlights the influence of the electronic configuration of the metal present in the organometallic compound, and the influence of the ligand on the second-order non-linear response. As far as the simulation is concerned, some experimental results have been reproduced. This work can be useful for the investigation of the extrinsic damage of imperfect materials, and for the design of experiments of transient measurements of excited silica [fr

  20. Introduction to nuclear reactions

    International Nuclear Information System (INIS)

    Satchler, G.R.

    1980-01-01

    This introduction to nuclear reaction phenomena is aimed primarily but not exclusively at readers at the undergraduate student level. An overview of the subject is presented in the first two chapters entitled - Some background information and Introduction to nuclear reactions. The third chapter reviews scattering theory with emphasis on the underlying physical ideas and also provides schematic entrees to the more advanced topics. The physical models which have been developed to account for the various aspects of nuclear phenomena are described in more detail in chapter 4. References and exercises are appended to each chapter. (U.K.)