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Sample records for organometallic reactions applications

  1. Fundamental organometallic reactions: Applications on the CYBER 205

    NASA Technical Reports Server (NTRS)

    Rappe, A. K.

    1984-01-01

    Two of the most challenging problems of Organometallic chemistry (loosely defined) are pollution control with the large space velocities needed and nitrogen fixation, a process so capably done by nature and so relatively poorly done by man (industry). For a computational chemist these problems are on the fringe of what is possible with conventional computers (large models needed and accurate energetics required). A summary of the algorithmic modification needed to address these problems on a vector processor such as the CYBER 205 and a sketch of findings to date on deNOx catalysis and nitrogen fixation are presented.

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

    ERIC Educational Resources Information Center

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

    SciTech Connect

    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.

  4. [Mechanistic examination of organometallic electron transfer reactions: Annual report, 1989

    SciTech Connect

    Not Available

    1989-12-31

    Our mechanistic examination of electron transfer reactions between organometallic complexes has required data from our stopped-flow infrared spectrophotometer that was constructed in the first year. Our research on organometallic electron transfer reaction mechanisms was recognized by an invitation to the Symposium on Organometallic Reaction Mechanisms at the National ACS meeting in Miami. We have obtained a reasonable understanding of the electron transfer reactions between metal cations and anions and between metal carbonyl anions and metal carbonyl dimers. In addition we have begun to obtain data on the outer sphere electron transfer between metal carbonyl anions and coordination complexes and on reactions involving cluster anions.

  5. Recent applications of polymer supported organometallic catalysts in organic synthesis.

    PubMed

    Kann, Nina

    2010-09-07

    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.

  6. Patterns in Organometallic Chemistry with Application in Organic Synthesis.

    ERIC Educational Resources Information Center

    Schwartz, Jeffrey; Labinger, Jay A.

    1980-01-01

    Of interest in this discussion of organometallic complexes are stoichiometric or catalytic reagents for organic synthesis in the complex transformations observed during synthesis for transition metal organometallic complexes. Detailed are general reaction types from which the chemistry or many transition metal organometallic complexes can be…

  7. Physical organic studies of organometallic reactions

    SciTech Connect

    Bergman, Robert G.

    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.

  8. Organometallic perovskites for optoelectronic applications (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Levchuk, Levgen; Hoegl, Florian; Brandl, Marco; Osvet, Andres; Hock, Rainer; Herre, Patrick; Wolfgang, Wolfgang; Schweizer, Peter; Spiecker, Erdmann; Batentschuk, Miroslaw; Brabec, Christoph

    2016-09-01

    Organometallic halide perovskites CH3NH3BX3 (B= Pb, Sn, Ge; X = I, Br, Cl) have become one of the most promising semiconductors for solar cell applications, reaching power conversion efficiencies beyond 20%. Improving our ability to harness the full potential of organometal halide perovskites requires the development of more reliable synthesis routines of well defined, reproducible and defect free reference systems allowing to study the fundamental photo-physical processes. In this study we present size and band gap engineering for organo-lead perovskites crystallites with various shapes and sizes ranging from the 5 nm regime all the way to 1 cm. Colloidal nano-crystals, micro-crystlline particles as well as single crystals are demonstrated with excellent purity and control in shape and size are demonstrated. The structural, optical and photo-physical properties of these reference materials are investigated and analyzed as function of their size and shape.

  9. Reactivity of TEMPO toward 16- and 17-electron organometallic reaction intermediates: a time-resolved IR study.

    PubMed

    Lomont, Justin P; Nguyen, Son C; Harris, Charles B

    2013-07-31

    The (2,2,6,6-tetramethylpiperidin-1-yl)oxyl radical (TEMPO) has been employed for an extensive range of chemical applications, ranging from organometallic catalysis to serving as a structural probe in biological systems. As a ligand in an organometallic complex, TEMPO can exhibit several distinct coordination modes. Here we use ultrafast time-resolved infrared spectroscopy to study the reactivity of TEMPO toward coordinatively unsaturated 16- and 17-electron organometallic reaction intermediates. TEMPO coordinates to the metal centers of the 16-electron species CpCo(CO) and Fe(CO)4, and to the 17-electron species CpFe(CO)2 and Mn(CO)5, via an associative mechanism with concomitant oxidation of the metal center. In these adducts, TEMPO thus behaves as an anionic ligand, characterized by a pyramidal geometry about the nitrogen center. Density functional theory calculations are used to facilitate interpretation of the spectra and to further explore the structures of the TEMPO adducts. To our knowledge, this study represents the first direct characterization of the mechanism of the reaction of TEMPO with coordinatively unsaturated organometallic complexes, providing valuable insight into its reactions with commonly encountered reaction intermediates. The similar reactivity of TEMPO toward each of the species studied suggests that these results can be considered representative of TEMPO's reactivity toward all low-valent transition metal complexes.

  10. Design, synthesis, and carbon-heteroatom coupling reactions of organometallic nickel(IV) complexes.

    PubMed

    Camasso, Nicole M; Sanford, Melanie S

    2015-03-13

    Homogeneous nickel catalysis is used for the synthesis of pharmaceuticals, natural products, and polymers. These reactions generally proceed via nickel intermediates in the Ni(0), Ni(I), Ni(II), and/or Ni(III) oxidation states. In contrast, Ni(IV) intermediates are rarely accessible. We report herein the design, synthesis, and characterization of a series of organometallic Ni(IV) complexes, accessed by the reaction of Ni(II) precursors with the widely used oxidant S-(trifluoromethyl)dibenzothiophenium triflate. These Ni(IV) complexes undergo highly selective carbon(sp(3))-oxygen, carbon(sp(3))-nitrogen, and carbon(sp(3))-sulfur coupling reactions with exogenous nucleophiles. The observed reactivity has the potential for direct applications in the development of nickel-catalyzed carbon-heteroatom coupling reactions.

  11. Organometallic enantiomeric scaffolding. Sequential semipinacol/1,5-"Michael-like" reactions as a strategic approach to bridgehead-quaternary center aza[3.3.1]bicyclics: application to the total synthesis of (-)-adaline.

    PubMed

    Coombs, Thomas C; Zhang, Yongqiang; Garnier-Amblard, Ethel C; Liebeskind, Lanny S

    2009-01-28

    A nontraditional approach to the enantiocontrolled construction of quaternary center-bearing heteroatom-bridged bicyclo[3.3.1]nonanes (homotropanes) is reported that is based on organometallic enantiomeric scaffolding. This strategy takes advantage of the unique reactivity profiles of TpMo(CO)(2)(5-oxo-eta(3)-pyranyl) and TpMo(CO)(2)(5-oxo-eta(3)-pyridinyl) scaffolds, and features a molybdenum-mediated semipinacol/1,5-"Michael-like" reaction sequence to establish the quaternary center and synthesize the bridged bicyclic structure. An asymmetric total synthesis of (-)-adaline highlights this methodology.

  12. Single-Molecule Fluorescence Imaging for Studying Organic, Organometallic, and Inorganic Reaction Mechanisms

    SciTech Connect

    Blum, Suzanne A.

    2016-05-24

    The reactive behavior of individual molecules is seldom observed, because we usually measure the average properties of billions of molecules. What we miss is important: the catalytic activity of less than 1% of the molecules under observation can dominate the outcome of a chemical reaction seen at a macroscopic level. Currently available techniques to examine reaction mechanisms (such as nuclear magnetic resonance spectroscopy and mass spectrometry) study molecules as an averaged ensemble. These ensemble techniques are unable to detect minor components (under ~1%) in mixtures or determine which components in the mixture are responsible for reactivity and catalysis. In the field of mechanistic chemistry, there is a resulting heuristic device that if an intermediate is very reactive in catalysis, it often cannot be observed (termed “Halpern’s Rule” ). Ultimately, the development of single-molecule imaging technology could be a powerful tool to observe these “unobservable” intermediates and active catalysts. Single-molecule techniques have already transformed biology and the understanding of biochemical processes. The potential of single-molecule fluorescence microscopy to address diverse chemical questions, such as the chemical reactivity of organometallic or inorganic systems with discrete metal complexes, however, has not yet been realized. In this respect, its application to chemical systems lags significantly behind its application to biophysical systems. This transformative imaging technique has broad, multidisciplinary impact with the potential to change the way the chemistry community studies reaction mechanisms and reactivity distributions, especially in the core area of catalysis.

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

    SciTech Connect

    Cahoon, James Francis

    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.

  14. Theoretical and computational studies of organometallic reactions: successful or not?

    PubMed

    Sakaki, Shigeyoshi; Ohnishi, Yu-Ya; Sato, Hirofumi

    2010-03-01

    Theoretical and computational methods are powerful in studying transition metal complexes. Our theoretical studies of C-H sigma-bond activation of benzene by Pd(II)-formate complex and that of methane by Ti(IV)-imido complex successfully disclosed that these reactions are understood to undergo heterolytic sigma-bond activation and the driving force is the formation of strong O-H and N-H bonds in the former and the latter, respectively. Orbital interactions are considerably different from those of sigma-bond activation by oxidative addition. The transmetallation, which is a key process in the cross-coupling reaction, is understood to be heterolytic sigma-bond activation. Our theoretical study clarified how to accelerate this transmetallation. Also, we wish to discuss weak points in theoretical and computational studies of large systems including transition metal elements, such as the necessity to incorporate solvation effect and to present quantitatively correct numerical results. The importance of solvation effects is discussed in the oxidative addition of methyliodide to Pt(II) complex which occurs in a way similar to an S(N)2 substitution. To apply the CCSD(T) (coupled cluster singles and doubles with perturbative triples correction) method, which is the gold standard of electronic structure theory, to large system, we need to reduce the size of the system by employing a small model. But, such modeling induces neglects of electronic and steric effects of substituents which are replaced in the small model. Frontier-orbital-consistent quantum-capping potential (FOC-QCP) was recently proposed by our group to incorporate the electronic effects of the substituents neglected in the modeling. The CCSD(T) calculation with the FOC-QCP was successfully applied to large systems including transition metal elements.

  15. Group 9 organometallic compounds for therapeutic and bioanalytical applications.

    PubMed

    Ma, Dik-Lung; Chan, Daniel Shiu-Hin; Leung, Chung-Hang

    2014-12-16

    CONSPECTUS: Compared with organic small molecules, metal complexes offer several distinct advantages as therapeutic agents or biomolecular probes. Carbon atoms are typically limited to linear, trigonal planar, or tetrahedral geometries, with a maximum of two enantiomers being formed if four different substituents are attached to a single carbon. In contrast, an octahedral metal center with six different substituents can display up to 30 different stereoisomers. While platinum- and ruthenium-based anticancer agents have attracted significant attention in the realm of inorganic medicinal chemistry over the past few decades, group 9 complexes (i.e., iridium and rhodium) have garnered increased attention in therapeutic and bioanalytical applications due to their adjustable reactivity (from kinetically liable to substitutionally inert), high water solubility, stability to air and moisture, and relative ease of synthesis. In this Account, we describe our efforts in the development of group 9 organometallic compounds of general form [M(C(∧)N)2(N(∧)N)] (where M = Ir, Rh) as therapeutic agents against distinct biomolecular targets and as luminescent probes for the construction of oligonucleotide-based assays for a diverse range of analytes. Earlier studies by researchers had focused on organometallic iridium(III) and rhodium(III) half-sandwich complexes that show promising anticancer activity, although their precise mechanisms of action still remain unknown. More recently, kinetically-inert group 9 complexes have arisen as fascinating alternatives to organic small molecules for the specific targeting of enzyme activity. Research in our laboratory has shown that cyclometalated octahedral rhodium(III) complexes were active against Janus kinase 2 (JAK2) or NEDD8-activating enzyme (NAE) activity, or against NO production leading to antivasculogenic activity in cellulo. At the same time, recent interest in the development of small molecules as modulators of protein

  16. Organometallic nickel(III) complexes relevant to cross-coupling and carbon-heteroatom bond formation reactions.

    PubMed

    Zheng, Bo; Tang, Fengzhi; Luo, Jia; Schultz, Jason W; Rath, Nigam P; Mirica, Liviu M

    2014-04-30

    Nickel complexes have been widely employed as catalysts in C-C and C-heteroatom bond formation reactions. In addition to Ni(0) and Ni(II) intermediates, several Ni-catalyzed reactions are proposed to also involve odd-electron Ni(I) and Ni(III) oxidation states. We report herein the isolation, structural and spectroscopic characterization, and organometallic reactivity of Ni(III) complexes containing aryl and alkyl ligands. These Ni(III) species undergo transmetalation and/or reductive elimination reactions to form new C-C or C-heteroatom bonds and are also competent catalysts for Kumada and Negishi cross-coupling reactions. Overall, these results provide strong evidence for the direct involvement of organometallic Ni(III) species in cross-coupling reactions and oxidatively induced C-heteroatom bond formation reactions.

  17. Organometallic Bonding in an Ullmann-Type On-Surface Chemical Reaction Studied by High-Resolution Atomic Force Microscopy.

    PubMed

    Kawai, Shigeki; Sadeghi, Ali; Okamoto, Toshihiro; Mitsui, Chikahiko; Pawlak, Rémy; Meier, Tobias; Takeya, Jun; Goedecker, Stefan; Meyer, Ernst

    2016-10-01

    The on-surface Ullmann-type chemical reaction synthesizes polymers by linking carbons of adjacent molecules on solid surfaces. Although an organometallic compound is recently identified as the reaction intermediate, little is known about the detailed structure of the bonded organometallic species and its influence on the molecule and the reaction. Herein atomic force microscopy at low temperature is used to study the reaction with 3,9-diiododinaphtho[2,3-b:2',3'-d]thiophene (I-DNT-VW), which is polymerized on Ag(111) in vacuum. Thermally sublimated I-DNT-VW picks up a Ag surface atom, forming a CAg bond at one end after removing an iodine. The CAg bond is usually short-lived, and a CAgC organometallic bond immediately forms with an adjacent molecule. The existence of the bonded Ag atoms strongly affects the bending angle and adsorption height of the molecular unit. Density functional theory calculations reveal the bending mechanism, which reveals that charge from the terminus of the molecule is transferred via the Ag atom into the organometallic bond and strengths the local adsorption to the substrate. Such deformations vanish when the Ag atoms are removed by annealing and CC bonds are established.

  18. Computational Raman spectroscopy of organometallic reaction products in lithium and sodium-based battery systems.

    PubMed

    Sánchez-Carrera, Roel S; Kozinsky, Boris

    2014-11-28

    A common approach to understanding surface reaction mechanisms in rechargeable lithium-based battery systems involves spectroscopic characterization of the product mixtures and matching of spectroscopic features to spectra of pure candidate reference compounds. This strategy, however, requires separate chemical synthesis and accurate characterization of potential reference compounds. It also assumes that atomic structures are the same in the actual product mixture as in the reference samples. We propose an alternative approach that uses first-principles computations of spectra of the possible reaction products and by-products present in advanced battery systems. We construct a library of computed Raman spectra for possible products, achieving excellent agreement with reference experimental data, targeting solid-electrolyte interphase in Li-ion cells and discharge products of Li-air cells. However, the solid-state crystalline structure of Li(Na) metal-organic compounds is often not known, making the spectra computations difficult. We develop and apply a novel technique of simplifying spectra calculations by using dimer-like representations of the solid state structures. On the basis of a systematic investigation, we demonstrate that molecular dimers of Li(Na)-based organometallic material provide relevant information about the vibrational properties of many possible solid reaction products. Such an approach should serve as a basis to extend existing spectral libraries of molecular structures relevant for understanding the link between atomic structures and measured spectroscopic data of materials in novel battery systems.

  19. Method of Continuous Variations: Applications of Job Plots to the Study of Molecular Associations in Organometallic Chemistry[**

    PubMed Central

    Renny, Joseph S.; Tomasevich, Laura L.; Tallmadge, Evan H.; Collum, David B.

    2014-01-01

    Applications of the method of continuous variations—MCV or the Method of Job—to problems of interest to organometallic chemists are described. MCV provides qualitative and quantitative insights into the stoichiometries underlying association of m molecules of A and n molecules of B to form AmBn. Applications to complex ensembles probe associations that form metal clusters and aggregates. Job plots in which reaction rates are monitored provide relative stoichiometries in rate-limiting transition structures. In a specialized variant, ligand- or solvent-dependent reaction rates are dissected into contributions in both the ground states and transition states, which affords insights into the full reaction coordinate from a single Job plot. Gaps in the literature are identified and critiqued. PMID:24166797

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

    SciTech Connect

    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.

  1. Gas phase studies of the Pesci decarboxylation reaction: synthesis, structure, and unimolecular and bimolecular reactivity of organometallic ions.

    PubMed

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

    2015-02-17

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

  2. NEW APPLICATIONS OF LC-MS AND LC-MS2 TOWARD UNDERSTANDING THE ENVIRONMENTAL FATE OF ORGANOMETALLICS

    EPA Science Inventory

    Over the last 40 years, many organometallic compounds have been synthesized and used in a variety of consumer, agricultural, and industrial products. Including wastewater effluents, leaching, and direct land and water applications, there are many pathways that can disperse organo...

  3. Thermodynamic Properties of Organometallic Dihydrogen Complexes for Hydrogen Storage Applications

    NASA Astrophysics Data System (ADS)

    Abrecht, David Gregory

    appropriate ranges for hydrogen storage applications. Simulated thermodynamic values for Fe complexes were found to significantly underestimate experimental behavior, demonstrating the importance of the magnetic spin state of the molecule to hydrogen binding properties.

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

    SciTech Connect

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

    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.

  5. [Progress of organometallic complexes and their application to organic electroluminescent materials].

    PubMed

    Zhou, Rui; An, Zhong-Wei; Chai, Sheng-Yong

    2004-08-01

    Organic electroluminescent (EL) material is one of most prospective display materials in flat panel display. Organometallic complexes, which have five or six member ring structures, with high stability, high melting point and high fluorescence quantum efficiency, are widely applied in organic EL devices. The recent progress in organometallic complexes is summarized in terms of the electroluminescence of ligands and metal atoms.

  6. Synthesis, Characterization, and C-H Activation Reactions of Novel Organometallic O-donor Ligated Rh(III) Complexes

    SciTech Connect

    Tenn, William J.; Conley, Brian L.; Bischof, Steven M.; Periana, Roy A.

    2010-09-17

    The synthesis and characterization of the O-donor ligated, air and water stable organometallic complexes trans- (2), and cis-(hfac-O,O) 2Rh(CH3)(py) (3), trans-(hfac-O,O)2Rh(C6H5)(py) (4), cis-(hfac-O,O)2Rh(C6H5)(py) (5), and cis-(hfac-O,O)2Rh(Mes)(py) (6) (where hfac-O,O = κ 2-O,O-1,1,1,5,5,5-hexafluoroacetylacetonato) are reported. These compounds are analogues to the O-donor iridium complexes that are active catalysts for the hydroarylation and C–H activation reactions as well as the bis-acetylacetonato rhodium complexes, which we recently reported. The trans-complex 2 undergoes a quantitative trans to cis isomerization in cyclohexane to form 3, which activates C–H bonds in both benzene and mesitylene to form compounds 5 and 6, respectively. All of these compounds are air and water stable and do not lead to decomposition products. Complex 5 promotes hydroarylation of styrene by benzene to generate dihydrostilbene.

  7. Organometallic Radiopharmaceuticals

    NASA Astrophysics Data System (ADS)

    Alberto, Roger

    Although molecular imaging agents have to be synthesized ultimately from aqueous solutions, organometallic complexes are becoming more and more important as flexible yet kinetically stable building blocks for radiopharmaceutical drug discovery. The diversity of ligands, targets, and targeting molecules related to these complexes is an essential base for finding novel, noninvasive imaging agents to diagnose and eventually treat widespread diseases such as cancer. This review article covers the most important findings toward these objectives accomplished during the past 3-4 years. The two major available organometallic building blocks will be discussed in the beginning together with constraints for market introduction as imposed by science and industry. Since targeting radiopharmaceuticals are a major focus of current research in molecular imaging, attempts toward so-called technetium essential radiopharmaceuticals will be briefly touched in the beginning followed by the main discussion about the labeling of targeting molecules such as folic acid, nucleosides, vitamins, carbohydrates, and fatty acids. At the end, some new strategies for drug discovery will be introduced together with results from organometallic chemistry in water. The majority of the new results have been achieved with the [99mTc(OH2)3(CO)3]+ complex which will, though not exclusively, be a focus of this review.

  8. Application of Organometallic Catalysis to the Commercial Production of L-DOPA.

    ERIC Educational Resources Information Center

    Knowles, W. S.

    1986-01-01

    Shows how asymmetric organometallic catalysts can be used to make complex organic molecules with extremely high enantioselectivity. The molecule considered is l-3, 4-dihydroxyphenylalanine (L-DOPA), an amino acid which was found to be effective in the treatment of Parkinson's disease. (JN)

  9. Inorganic and Organometallic Polymers

    NASA Astrophysics Data System (ADS)

    Chandrasekhar, Vadapalli

    This textbook is intended to give an understanding of the basic principles that constitute the field of non-conventional polymers containing inorganic and organometalic units as the repeating units. Each chapter will be self-explanatory with a good background so that it can be easily understood at the senior undergraduate level. The principles involved in the preparation of these polymers, their characterisation and their applications will be discussed. Basic inorganic chemistry required for the understanding of each topic is presented so that the content of the chapter is readily understood.

  10. [Development of environmentally friendly organometallic catalysis for drug discovery and its application to heterocyclic chemistry].

    PubMed

    Arisawa, Mitsuhiro

    2007-09-01

    Two new catalysts, ruthenium hydride with a nitrogen-containing heterocyclic carbene (A) and an organopalladium catalyst supported on a sulfur-terminated semi-conductor, gallium arsenide (001) (B) were discovered. Both catalysts are environmentally benign, because A can yield indole derivatives with good atom economy, and B can catalyze the Mizoroki-Heck reaction more than 10 times with only trace amounts of leached palladium (ppb level). Substituted 1,2-dihydroquinoline, indole and 3-methylene-2,3-dihydroindole were also prepared selectively from the common starting material, N-allyl-o-vinylaniline, and catalyst by slight modification of the reaction conditions. These procedures address an important issue in diversity-oriented synthesis. These methods utility were demonstrated by application to biologically active natural products synthesis.

  11. Organometallic Polymers.

    ERIC Educational Resources Information Center

    Carraher, Charles E., Jr.

    1981-01-01

    Reactions utilized to incorporate a metal-containing moiety into a polymer chain (addition, condensation, and coordination) are considered, emphasizing that these reactions also apply to smaller molecules. (JN)

  12. Design and synthesis of novel organometallic dyes for NiO sensitization and photo-electrochemical applications.

    PubMed

    Massin, Julien; Lyu, Siliu; Pavone, Michele; Muñoz-García, Ana B; Kauffmann, Brice; Toupance, Thierry; Chavarot-Kerlidou, Murielle; Artero, Vincent; Olivier, Céline

    2016-08-02

    Two metallo-organic dyes were synthesized and used for NiO sensitization in view of their photoelectrochemical applications. The new dyes present an original π-conjugated structure containing the [Ru(dppe)2] metal fragment with a highly delocalized allenylidene ligand on one side and a σ-alkynyl ligand bearing an electron-rich group, i.e. a thiophene or triphenylamine unit, and one or two anchoring functions on the other side. The optoelectronic, electrochemical and photoelectrochemical properties of the dyes were systematically investigated. A broad photoresponse was observed with the absorption maximum at 600 nm. The X-ray crystal structure of one precursor was obtained to elucidate the structural conformation of the organometallic complexes and theoretical calculations were performed in order to address the photophysical properties of the new dyes. These photosensitizers were further implemented in NiO-based photocathodes and tested as photocurrent generators under pertinent aqueous conditions in association with [Co(NH3)5Cl]Cl2 as an irreversible electron acceptor. The dye-sensitized photocathodes provided good photocurrent densities (40 to 60 μA cm(-2)) at neutral pH in phosphate buffer and a high stability was observed for the two dyes.

  13. Nonsymmetrical 3,4-dithienylmaleimides by cross-coupling reactions with indium organometallics: synthesis and photochemical studies.

    PubMed

    Mosquera, Angeles; Férnandez, M Isabel; Canle Lopez, Moisés; Pérez Sestelo, José; Sarandeses, Luis A

    2014-10-27

    The synthesis and photochemical study of novel nonsymmetrical 1,2-dithienylethenes (DTEs) with a maleimide bridge have been carried out. The synthetic approach to the DTEs was based on successive selective palladium-catalyzed cross-coupling reactions of 5-susbtituted-2-methyl-3-thiophenyl indium reagents with 3,4-dichloromaleimides. The required organoindium reagents were prepared from 2-methyl-3,5-dibromothiophene by a selective (C-5) coupling reaction with triorganoindium compounds (R3 In) and subsequent metal-halogen exchange. The coupling reactions usually gave good yields and have a high atom economy with substoichiometric amounts of R3 In. The results of photochemical studies show that these novel dithienylmaleimides undergo a photocyclization reaction upon irradiation in the UV region and a photocycloreversion after excitation in the visible region, thus they can be used as photochemical switches. ON-OFF operations can be repeated in successive cycles without appreciable loss of effectiveness in the process.

  14. A four-component reaction involving in situ generated organometallic reagents: straightforward access to β-amino esters.

    PubMed

    Le Gall, Erwan; Léonel, Eric

    2013-04-22

    Four in one: A straightforward synthesis of β(2,3)-amino esters is described through a new zinc-mediated, cobalt-catalyzed four-component reaction between organic bromides, alkyl acrylates, amines, and aldehydes (see scheme). Synthesis involves a Mannich-related conjugate addition/aza-aldol domino sequence, allowing the formation of three single bonds in one step. A reaction mechanism, emphasizing the crucial role of zinc salts, is described.

  15. Applications of Reaction Rate

    ERIC Educational Resources Information Center

    Cunningham, Kevin

    2007-01-01

    This article presents an assignment in which students are to research and report on a chemical reaction whose increased or decreased rate is of practical importance. Specifically, students are asked to represent the reaction they have chosen with an acceptable chemical equation, identify a factor that influences its rate and explain how and why it…

  16. Organometallic Chemistry of Molybdenum.

    ERIC Educational Resources Information Center

    Lucas, C. Robert; Walsh, Kelly A.

    1987-01-01

    Suggests ways to avoid some of the problems students have learning the principles of organometallic chemistry. Provides a description of an experiment used in a third-year college chemistry laboratory on molybdenum. (TW)

  17. Group IV organometallic compounds based on dianionic "pincer" ligands: synthesis, characterization, and catalytic activity in intramolecular hydroamination reactions.

    PubMed

    Luconi, Lapo; Rossin, Andrea; Motta, Alessandro; Tuci, Giulia; Giambastiani, Giuliano

    2013-04-08

    Neutral Zr(IV) and Hf(IV) diamido complexes stabilized by unsymmetrical dianionic N,C,N' pincer ligands have been prepared through the simplest and convenient direct metal-induced Caryl-H bond activation. Simple ligand modification has contributed to highlight the non-innocent role played by the donor atom set in the control of the cyclometallation kinetics. The as-prepared bis-amido catalysts were found to be good candidates for the intramolecular hydroamination/cyclization of primary aminoalkenes. The ability of these compounds to promote such a catalytic transformation efficiently (by providing, in some cases, fast and complete substrate conversion at room temperature) constitutes a remarkable step forward toward catalytic systems that can operate at relatively low catalyst loading and under milder reaction conditions. Kinetic studies and substrate-scope investigations, in conjunction with preliminary DFT calculations on the real systems, were used to elucidate the effects of the substrate substitution on the catalyst performance and to support the most reliable mechanistic path operative in the hydroamination reaction.

  18. Selectivity in the Addition Reactions of Organometallic Reagents to Aziridine-2-carboxaldehydes: The Effects of Protecting Groups and Substitution Patterns

    PubMed Central

    Kulshrestha, Aman; Schomaker, Jennifer M.; Holmes, Daniel; Staples, Richard J.; Jackson, James E.; Borhan, Babak

    2014-01-01

    Good to excellent stereo-selectivity has been found in the addition reactions of Grignard and organo-zinc reagents to N-protected aziridine-2-carboxaldehydes. Specifically, high syn selectivity was obtained with benzyl-protected cis, tert-butyloxycar-bonyl-protected trans, and tosyl-pro-tected 2,3-disubstituted aziridine-2-car-boxaldehydes. Furthermore, rate and selectivity effects of ring substituents, temperature, solvent, and Lewis acid and base modifiers were studied. The diastereomeric preference of addition is dominated by the substrate aziri-dines’ substitution pattern and especially the electronic character and conformational preferences of the nitrogen protecting groups. To help rationalize the observed stereochemical outcomes, conformational and electronic structural analyses of a series of model systems representing the various substitution patterns have been explored by density functional calculations at the B3LYP/6–31G* level of theory with the SM8 solvation model to account for solvent effects. PMID:21928447

  19. Organometallic compounds: an opportunity for chemical biology?

    PubMed

    Patra, Malay; Gasser, Gilles

    2012-06-18

    Organometallic compounds are renowned for their remarkable applications in the field of catalysis, but much less is known about their potential in chemical biology. Indeed, such compounds have long been considered to be either unstable under physiological conditions or cytotoxic. As a consequence, little attention has been paid to their possible utilisation for biological purposes. Because of their outstanding physicochemical properties, which include chemical stability, structural diversity and unique photo- and electrochemical properties, however, organometallic compounds have the ability to play a leading role in the field of chemical biology. Indeed, remarkable examples of the use of such compounds-notably as enzyme inhibitors and as luminescent agents-have recently been reported. Here we summarise recent advances in the use of organometallic compounds for chemical biology purposes, an area that we define as "organometallic chemical biology". We also demonstrate that these recent discoveries are only a beginning and that many other organometallic complexes are likely to be found useful in this field of research in the near future.

  20. Synthesis of organometallic compounds: Final technical report

    SciTech Connect

    Parker, J.

    1987-01-28

    The object of this project is the establishment of procedures which would allow the practical production of solutions of organometallic compounds suitable for the deposition of conductive metal films at temperatures below 250/sup 0/C. Purdue University's Turner Laboratory developed the basic chemistry for the synthesis of these ''oxygen bridge'' organometallic compounds. A solution of a metal salt is combined with a solution of an ammonium (or amine) soap of an appropriate organic acid. The resulting product precipitate is cleaned, dried and dissolved in xylene. Control of reaction pH and reagent purity was essential in producing useful quantities of the organometallic compounds in better than 75% yields and at reasonable costs. Processes were developed for silver, bismuth, platinum, nickel, and gold organometallic products. The processes for the gold and platinum products remained difficult, giving low yields and evidence of poor product stability. It is anticipated that improvement in the removal of inorganic impurities from the product would enhance its stability. Thermal analyses were applied to the products to determine their decomposition characteristics, and rough cost studies were made to aid in comparisons with conventional metallization methods.

  1. Nuclear Reactions for Astrophysics and Other Applications

    SciTech Connect

    Escher, J E; Burke, J T; Dietrich, F S; Scielzo, N D; Ressler, J J

    2011-03-01

    Cross sections for compound-nuclear reactions are required for many applications. The surrogate nuclear reactions method provides an indirect approach for determining cross sections for reactions on unstable isotopes, which are difficult or impossible to measure otherwise. Current implementations of the method provide useful cross sections for (n,f) reactions, but need to be improved upon for applications to capture reactions.

  2. Mechanistic study of organometallic vapor phase epitaxy

    SciTech Connect

    Stringfellow, G.B.

    1990-12-31

    Only AsH{sub 3} and PH{sub 3} have been used as the group V source molecules for organometallic vapor phase epitaxy (OMVPE) of III/V semiconductors until recently, since they have been the only precursors yielding device quality materials. This paper reviews recent work on the pyrolysis of individual organometallic molecules, with emphasis on the group V sources, including: (1) the methylarsines, di- and tri-methylarsine, (2) the ethylarsines, mono-, di-, and tri-ethylarsine, and (3) the singly substituted tertiarybutyl arsine and phosphine molecules. The pyrolysis and growth reactions occurring when both group III and group V precursors are present simultaneously, i.e., the reactions occuring during OMVPE growth of several III/V semiconductors, are also briefly reviewed.

  3. Mechanistic study of organometallic vapor phase epitaxy

    SciTech Connect

    Stringfellow, G.B.

    1990-01-01

    Only AsH{sub 3} and PH{sub 3} have been used as the group V source molecules for organometallic vapor phase epitaxy (OMVPE) of III/V semiconductors until recently, since they have been the only precursors yielding device quality materials. This paper reviews recent work on the pyrolysis of individual organometallic molecules, with emphasis on the group V sources, including: (1) the methylarsines, di- and tri-methylarsine, (2) the ethylarsines, mono-, di-, and tri-ethylarsine, and (3) the singly substituted tertiarybutyl arsine and phosphine molecules. The pyrolysis and growth reactions occurring when both group III and group V precursors are present simultaneously, i.e., the reactions occuring during OMVPE growth of several III/V semiconductors, are also briefly reviewed.

  4. Tailored Organometallic Polymers

    DTIC Science & Technology

    1993-01-31

    ORGANOMETALLIC POLYMERS (Unclassified) 12. PERSONAL AUTHOR(S) R.M. Laine, C. Viney and R.J.P. Corriu (Addresses listed on following page) 13a. TYPE OF...MI 48109-2136 Christopher Viney Center for Bioengineering WD-12 University of Washington Seattle, W,’ 98195 Reproduced From Best Available Copy Robert...RECOGNIZING SUPPORT FROM CONTRACT F49620-89-C-0059 R.M. Laine and C. Viney welcome requests for reprints of articles that they authored. 1

  5. Chemistry related to semiconductor growth involving organometallics

    NASA Astrophysics Data System (ADS)

    Husk, G. R.; Jones, K. A.; Paur, R. J.; Prater, J. T.

    1990-05-01

    OMVPE (OrganoMetallic Vapor-Phase Epitaxy) technology requirements for III-V compounds and chemistry related to semiconductor growth involving organometallics are discussed. The following subject areas are covered: semiconductor device requirements; Army II-VI deposition program/MOMBE (Metal Organic Molecular Beam Epitaxy) for IR detector applications; epitaxial growth of III-V's and II-VI's using organometallics; electrical device requirements; environmental and safety issues in MOVPE; quantum chemistry of vapor phase; carbon doping and selective epitaxy (tailoring growth chemistry in MOVPE); TBA/TBP precursors in GaAs and InP MOCVD; single source precursors for III-V OMCVD (OrganoMetallic Chemical Vapor Deposition) growth; alternate sources for MOMBE of AlGaAs; mechanism of incorporation of impurities and analysis of carbon contamination; growth on nonplanar and patterned substrates; CBE growth mechanisms; TriMethylamine Alane (a new robust precursor for MOMBE growth of AlGaAs); real-time determinations of OMCVD growth kinetics on GaAs by reflectance-difference spectroscopy; photoreflectance measurements; growth and doping mechanisms for HgCdTe; photoassisted CBE (Chemical Beam Epitaxy) of CdTe and HgCdTe alloys; in-situ analysis of ZnSe growth by OMCVD using X-ray scattering; biodegradation of GaAs IC chips and wafers; detailed models of compound semiconductor growth by MOCVD; gas phase probes of GaAs cluster chemistry; photodecomposition of organometallic compounds at 193 nm; manufacturing issues in MOCVD compound semiconductor technology.

  6. Ligand Rearrangements of Organometallic Complexes inSolution

    SciTech Connect

    Shanoski, Jennifer E.

    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.

  7. 2011 Organometallic Chemistry (July 10-15, 2011, Salve Regina University, Newport, RI)

    SciTech Connect

    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.

  8. Organometallic Chemistry. Final Progress Report

    SciTech Connect

    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.

  9. 2012 ORGANOMETALLIC CHEMISTRY GRC/GRS, JULY 7-13, 2012

    SciTech Connect

    Hillhouse, Gregory

    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.

  10. Half-metallicity in 2D organometallic honeycomb frameworks.

    PubMed

    Sun, Hao; Li, Bin; Zhao, Jin

    2016-10-26

    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.

  11. Half-metallicity in 2D organometallic honeycomb frameworks

    NASA Astrophysics Data System (ADS)

    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.

  12. Molecular dynamics simulation of organometallic reaction dynamics, and, Enhancing achievement in chemistry for African American students through innovations in pedagogy aligned with supporting assessment and curriculum and integrated under an alternative research paradigm

    NASA Astrophysics Data System (ADS)

    Mebane, Sheryl Dee

    Part I. Molecular dynamics simulation of organometallic reaction dynamics. To study the interplay of solute and solvent dynamics, large-scale molecular dynamics simulations were employed. Lennard-Jones and electrostatic models of potential energies from solvent-only studies were combined with solute potentials generated from ab-initio calculations. Radial distribution functions and other measures revealed the polar solvent's response to solute dynamics following CO dissociation. In future studies, the time-scale for solvent coordination will be confirmed with ultrafast spectroscopy data. Part II. Enhancing achievement in chemistry for African American students through innovations in pedagogy aligned with supporting assessment and curriculum and integrated under an alternative research paradigm. Much progress has been made in the area of research in education that focuses on teaching and learning in science. Much effort has also centered on documenting and exploring the disparity in academic achievement between underrepresented minority students and students comprising a majority in academic circles. However, few research projects have probed educational inequities in the context of mainstream science education. In order to enrich this research area and to better reach underserved learning communities, the educational experience of African American students in an ethnically and academically diverse high school science class has been examined throughout one, largely successful, academic year. The bulk of data gathered during the study was obtained through several qualitative research methods and was interpreted using research literature that offered fresh theoretical perspectives on equity that may better support effective action.

  13. Photochemical reaction dynamics

    SciTech Connect

    Moore, B.C.

    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.

  14. Organometallic chemistry in non-classical environments.

    PubMed

    Dyson, Paul J

    2011-01-01

    A summary of our on-going research on organometallic chemistry is provided with an emphasis on the function, reactivity and mechanisms of organometallic compounds in water, ionic liquids and in living systems. The role of organometallic compounds in both catalysis and medicinal chemistry are briefly described.

  15. A One-Pot Self-Assembly Reaction to Prepare a Supramolecular Palladium(II) Cyclometalated Complex: An Undergraduate Organometallic Laboratory Experiment

    ERIC Educational Resources Information Center

    Fernandez, Alberto; Lopez-Torres, Margarita; Fernandez, Jesus J.; Vazquez-Garcia, Digna; Vila, Jose M.

    2012-01-01

    A laboratory experiment for students in advanced inorganic chemistry is described. Students prepare palladium(II) cyclometalated complexes. A terdentate [C,N,O] Schiff base ligand is doubly deprotonated upon reaction with palladium(II) acetate in a self-assembly process to give a palladacycle with a characteristic tetranuclear structure. This…

  16. ROMP Synthesis of Iron-Containing Organometallic Polymers.

    PubMed

    Dragutan, Ileana; Dragutan, Valerian; Filip, Petru; Simionescu, Bogdan C; Demonceau, Albert

    2016-02-06

    The paper overviews iron-containing polymers prepared by controlled "living" ring-opening metathesis polymerization (ROMP). Developments in the design and synthesis of this class of organometallic polymers are highlighted, pinpointing methodologies and newest trends in advanced applications of hybrid materials based on polymers functionalized with iron motifs.

  17. π-Conjugated Organometallic Isoindigo Oligomer and Polymer Chromophores: Singlet and Triplet Excited State Dynamics and Application in Polymer Solar Cells.

    PubMed

    Goswami, Subhadip; Gish, Melissa K; Wang, Jiliang; Winkel, Russell W; Papanikolas, John M; Schanze, Kirk S

    2015-12-09

    An isoindigo based π-conjugated oligomer and polymer that contain cyclometalated platinum(II) "auxochrome" units were subjected to photophysical characterization, and application of the polymer in bulk heterojunction polymer solar cells with PCBM acceptor was examined. The objective of the study was to explore the effect of the heavy metal centers on the excited state properties, in particular, intersystem crossing to a triplet (exciton) state, and further how this would influence the performance of the organometallic polymer in solar cells. The materials were characterized by electrochemistry, ground state absorption, emission, and picosecond-nanosecond transient absorption spectroscopy. Electrochemical measurements indicate that the cyclometalated units have a significant impact on the HOMO energy level of the chromophores, but little effect on the LUMO, which is consistent with localization of the LUMO on the isoindigo acceptor unit. Picosecond-nanosecond transient absorption spectroscopy reveals a transient with ∼100 ns lifetime that is assigned to a triplet excited state that is produced by intersystem crossing from a singlet state on a time scale of ∼130 ps. This is the first time that a triplet state has been observed for isoindigo π-conjugated chromophores. The performance of the polymer in bulk heterojunction solar cells was explored with PC61BM as an acceptor. The performance of the cells was optimum at a relatively high PCBM loading (1:6, polymer:PCBM), but the overall efficiency was relatively low with power conversion efficiency (PCE) of 0.22%. Atomic force microscopy of blend films reveals that the length scale of the phase separation decreases with increasing PCBM content, suggesting a reason for the increase in PCE with acceptor loading. Energetic considerations show that the triplet state in the polymer is too low in energy to undergo charge separation with PCBM. Further, due to the relatively low LUMO energy of the polymer, charge transfer

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

    NASA Astrophysics Data System (ADS)

    Vodák, Jiří; Nečas, David; Pavliňák, David; Macak, Jan M.; Řičica, Tomáš; Jambor, Roman; Ohlídal, Miloslav

    2017-02-01

    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.

  19. Organometallic neptunium(III) complexes.

    PubMed

    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.

  20. Perfluorinated Ligands in Organometallic Chemistry

    DTIC Science & Technology

    1989-12-12

    Decacarbonyldimanganese. Organometallics, 1986, 1,2391. W.P. Henry and R.P. Hughes, Organic Synthesis Using Carbon Monoxide. Regiospecific Cobalt Mediated...Pentamethylcyclopentadiene with Decacarbonyldi manganese. Organometalllcs, 1986, 1,2391. 4. W.P. Henry and R.P. Hughes, Organic Synthesis Using Carbon

  1. Organometallic neptunium(III) complexes

    NASA Astrophysics Data System (ADS)

    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. Strategies to prepare and use functionalized organometallic reagents.

    PubMed

    Klatt, Thomas; Markiewicz, John T; Sämann, Christoph; Knochel, Paul

    2014-05-16

    Polyfunctional zinc and magnesium organometallic reagents occupy a central position in organic synthesis. Most organic functional groups are tolerated by zinc organometallic reagents, and Csp(2)-centered magnesium organometallic reagents are compatible with important functional groups, such as the ester, aryl ketone, nitro, cyano, and amide functions. This excellent chemoselectivity gives zinc- and magnesium-organometallic reagents a central position in modern organic synthesis. Efficient and general preparations of these organometallic reagents, as well as their most practical and useful reactions, are presented in this Perspective. As starting materials, a broad range of organic halides (iodides, bromides, and also to some extent chlorides) can be used for the direct insertion of magnesium or zinc powder; the presence of LiCl very efficiently promotes such insertions. Alternatively, aromatic or heterocyclic bromides also undergo a smooth bromine-magnesium exchange when treated with i-PrMgCl·LiCl. Alternative precursors of zinc and magnesium reagents are polyfunctionalized aryl and heteroaryl molecules, which undergo directed metalations with sterically hindered TMP bases (TMP = 2,2,6,6-tetramethylpiperide) of magnesium and zinc. This powerful C-H functionalization method gives access to polyfunctional heterocyclic zinc and magnesium reagents, which undergo efficient reactions with numerous electrophiles. The compatibility of the strong TMP-bases with BF3·OEt2 (formation of frustrated Lewis pairs) dramatically increases the scope of these metalations, giving for example, a practical access to magnesiated pyridines and pyrazines, which can be used as convenient building blocks for the preparation of biologically active molecules.

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

    DOEpatents

    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.

  4. Progress towards bioorthogonal catalysis with organometallic compounds.

    PubMed

    Völker, Timo; Dempwolff, Felix; Graumann, Peter L; Meggers, Eric

    2014-09-22

    The catalysis of bioorthogonal transformations inside living organisms is a formidable challenge--yet bears great potential for future applications in chemical biology and medicinal chemistry. We herein disclose highly active organometallic ruthenium complexes for bioorthogonal catalysis under biologically relevant conditions and inside living cells. The catalysts uncage allyl carbamate protected amines with unprecedented high turnover numbers of up to 270 cycles in the presence of water, air, and millimolar concentrations of thiols. By live-cell imaging of HeLa cells and with the aid of a caged fluorescent probe we could reveal a rapid development of intense fluorescence within the cellular cytoplasm and therefore support the proposed bioorthogonality of the catalysts. In addition, to illustrate the manifold applications of bioorthogonal catalysis, we developed a method for catalytic in-cell activation of a caged anticancer drug, which efficiently induced apoptosis in HeLa cells.

  5. Organometallic Chemistry and Catalysis in Industry.

    ERIC Educational Resources Information Center

    Parshall, George W.; Putscher, Richard E.

    1986-01-01

    Traces the growth in the industrial usage of organometallic chemistry from 1950 to 1977, pointing out that this growth involved the production of commodity chemicals. Indicates that one of the early successes of organometallic chemistry was the discovery of ethylene polymerization catalysts. (JN)

  6. Chromo- and Fluorogenic Organometallic Sensors

    NASA Astrophysics Data System (ADS)

    Fletcher, Nicholas C.; Lagunas, M. Cristina

    Compounds that change their absorption and/or emission properties in the presence of a target ion or molecule have been studied for many years as the basis for optical sensing. Within this group of compounds, a variety of organometallic complexes have been proposed for the detection of a wide range of analytes such as cations (including H+), anions, gases (e.g. O2, SO2, organic vapours), small organic molecules, and large biomolecules (e.g. proteins, DNA). This chapter focuses on work reported within the last few years in the area of organometallic sensors. Some of the most extensively studied systems incorporate metal moieties with intense long-lived metal-to-ligand charge transfer (MLCT) excited states as the reporter or indicator unit, such as fac-tricarbonyl Re(I) complexes, cyclometallated Ir(III) species, and diimine Ru(II) or Os(II) derivatives. Other commonly used organometallic sensors are based on Pt-alkynyls and ferrocene fragments. To these reporters, an appropriate recognition or analyte-binding unit is usually attached so that a detectable modification on the colour and/or the emission of the complex occurs upon binding of the analyte. Examples of recognition sites include macrocycles for the binding of cations, H-bonding units selective to specific anions, and DNA intercalating fragments. A different approach is used for the detection of some gases or vapours, where the sensor's response is associated with changes in the crystal packing of the complex on absorption of the gas, or to direct coordination of the analyte to the metal centre.

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

    DOEpatents

    Li, Zaiwei; Tang, Yongchun; Cheng; Jihong

    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.

  8. Organometallic Polymeric Conductors

    NASA Technical Reports Server (NTRS)

    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. The highest conductivities reported (approximately 4/Scm) were achieved with polythiophene in a polystyrene host polymer. The best films using a polyamide as base polymer were four orders of magnitude less conductive than the polystyrene films. The authors suggested that this was because polyimides were unable to swell sufficiently for infiltration of monomer as in the polystyrene. It was not clear, however, if the different conductivities obtained were merely the result of differing oxidation conditions. Oxidation time, temperature and oxidant concentration varied widely among the studies.

  9. Organometallic Polymeric Conductors

    NASA Technical Reports Server (NTRS)

    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

  10. Supercritical fluids: Reactions, materials and applications

    SciTech Connect

    Tumas, W.; Jacobson, G.B.; Josephsohn, N.S.; Brown, G.H.

    1999-04-09

    A number of important processes utilizing supercritical fluids have been either implemented or are emerging for extractions, separations and a wide range of cleaning applications. Supercritical fluids can be reasonable solvents yet share many of the advantages of gases including miscibility with other gases (i.e. hydrogen and oxygen), low viscosities and high diffusivities. Carbon dioxide has the further advantages of being nontoxic, nonflammable, inexpensive and currently unregulated. The use of compressed gases, either as liquids or supercritical fluids, as reaction media offers the opportunity to replace conventional hazardous solvents and also to optimize and potentially control the effect of solvent on chemical and material processing. The last several years has seen a significant growth in advances in chemical synthesis, catalytic transformations and materials synthesis and processing. The authors report on results from an exploratory program at Los Alamos National Laboratory aimed at investigating the use of dense phase fluids, particularly carbon dioxide, as reaction media for homogeneous, heterogeneous and phase-separable catalytic reactions in an effort to develop new, environmentally-friendly methods for chemical synthesis and processing. This approach offers the possibility of opening up substantially different chemical pathways, increasing selectivity at higher reaction rates, facilitating downstream separations and mitigating the need for hazardous solvents. Developing and understanding chemical and catalytic transformations in carbon dioxide could lead to greener chemistry at three levels: (1) Solvent replacement; (2) Better chemistry (e.g. higher reactivity, selectivity, less energy consumption); and (3) New chemistry (e.g. novel separations, use of COP{sub 2} as a C-1 source).

  11. Detection of Metal and Organometallic Compounds with Bioluminescent Bacterial Bioassays.

    PubMed

    Durand, M J; Hua, A; Jouanneau, S; Cregut, M; Thouand, G

    2015-10-17

    Chemical detection of metal and organometallic compounds is very specific and sensitive, but these techniques are time consuming and expensive. Although these techniques provide information about the concentrations of compounds, they fail to inform us about the toxicity of a sample. Because the toxic effects of metals and organometallic compounds are influenced by a multitude of environmental factors, such as pH, the presence of chelating agents, speciation, and organic matter, bioassays have been developed for ecotoxicological studies. Among these bioassays, recombinant luminescent bacteria have been developed over the past 20 years, and many of them are specific for the detection of metals and metalloids. These bioassays are simple to use, are inexpensive, and provide information on the bioavailable fraction of metals and organometals. Thus, they are an essential complementary tool for providing information beyond chemical analysis. In this chapter, we propose to investigate the detection of metals and organometallic compounds with bioluminescent bacterial bioassays and the applications of these bioassays to environmental samples. Graphical Abstract.

  12. Sizable band gap in organometallic topological insulator

    NASA Astrophysics Data System (ADS)

    Derakhshan, V.; Ketabi, S. A.

    2017-01-01

    Based on first principle calculation when Ceperley-Alder and Perdew-Burke-Ernzerh type exchange-correlation energy functional were adopted to LSDA and GGA calculation, electronic properties of organometallic honeycomb lattice as a two-dimensional topological insulator was calculated. In the presence of spin-orbit interaction bulk band gap of organometallic lattice with heavy metals such as Au, Hg, Pt and Tl atoms were investigated. Our results show that the organometallic topological insulator which is made of Mercury atom shows the wide bulk band gap of about ∼120 meV. Moreover, by fitting the conduction and valence bands to the band-structure which are produced by Density Functional Theory, spin-orbit interaction parameters were extracted. Based on calculated parameters, gapless edge states within bulk insulating gap are indeed found for finite width strip of two-dimensional organometallic topological insulators.

  13. Supported organometallic complexes, surface chemistry, spectroscopy, and catalysis

    SciTech Connect

    Marks, T.J.

    1993-04-01

    Goal is to elucidate and understand the surface chemistry and catalytic properties of well-defined, highly-reactive organometallic molecules (principally based upon abundant actinide, lanthanide, and early transition elements) adsorbed on metal oxides and halides. Nature of adsorbed species is probed by a battery of chemical and physicochemical techniques, to understand the nature of the molecule-surface coordination chemistry and how this can give rise to extremely high catalytic activity. A complementary objective is to delineate the scope and mechanisms of the heterogeneous catalytic reactions, as well as to relate them both conceptually and functionally to model systems generated in solution.

  14. The direct synthesis of organic and organometallic-containing MICA-type aluminosilicates

    SciTech Connect

    Carrado, K.A.; Awaluddin, A.

    1993-08-01

    Layer-silicate clay structures can provide supramolecular organization for catalysis, chiral reactions, colloid science, and electron transfer. The authors have successfully modified the experimental preparations of several different layer silicates in order to incorporate a wide variety of organic and organometallic molecules in the clay galleries. Synthesis and physical characterization of these materials are described and compared to ion-exchanged natural clay analogs. In addition, the photophysical properties of organometallic Ru(II) complexes incorporated by direct hydrothermal crystallization into synthetic clays were measured. 3 tabs, 21 refs.

  15. An organometallic guide to the chemistry of hydrocarbon moieties on transition metal surfaces

    SciTech Connect

    Zaera, F.

    1995-12-01

    In this review what is known about the chemistry of hydrocarbon molecules on transition metal surfaces will be surveyed. Here the authors discuss the results reported to date on the structure and reactivity of the different types of hydrocarbon moieties that form on transition metal surfaces. One of the goals of this review is to provide an organometallic guide for the possible interactions of hydrocarbons with transition metals with the idea of examining their relation to the corresponding surface chemistry. The authors however limit the review of the organometallic literature to the information relevant to the surface systems, and also narrow the field to cover only molecules with carbon and hydrogen atoms; compounds containing other atoms (O, S, N) will be excluded. The present review is organized in the following manner. First, a brief discussion of the experimental techniques used to characterize both organometallic and surface systems is presented. A discussion of the coordination and structure of the different types of organic moieties, first in organometallic compounds and then on metal surfaces, follows. Here the systems are classified according to the type of bonding between the molecules and the metals. Next, the different elementary steps that such systems can undergo are summarized: C-H and C-C bond-breaking and bond-forming reactions, isomerizations, and others. Again, the chemistry of organometallic compounds is discussed first, and the surface chemistry is presented subsequently. A brief description of a few key nonelementary reactions is also given, including some catalytic processes. Lastly, a brief discussion on the main similarities and differences found so far between surface and organometallic systems, and on possible future directions for this field, is offered.

  16. Investigation of the Hydrolysis of Perovskite Organometallic Halide CH3NH3PbI3 in Humidity Environment

    NASA Astrophysics Data System (ADS)

    Zhao, Jiangtao; Cai, Bing; Luo, Zhenlin; Dong, Yongqi; Zhang, Yi; Xu, Han; Hong, Bin; Yang, Yuanjun; Li, Liangbin; Zhang, Wenhua; Gao, Chen

    2016-02-01

    Instability of emerging perovskite organometallic halide in humidity environment is the biggest obstacle for its potential applications in solar energy harvest and electroluminescent display. Understanding the detailed decay mechanism of these materials in moisture is a critical step towards the final appropriate solutions. As a model study presented in this work, in situ synchrotron radiation x-ray diffraction was combined with microscopy and gravimetric analysis to study the degradation process of CH3NH3PbI3 in moisture, and the results reveal that: 1) intermediate monohydrated CH3NH3PbI3·H2O is detected in the degradation process of CH3NH3PbI3 and the final decomposition products are PbI2 and aqueous CH3NH3I; 2) the aqueous CH3NH3I could hardly further decompose into volatile CH3NH2, HI or I2; 3) the moisture disintegrate CH3NH3PbI3 and then alter the distribution of the decomposition products, which leads to an incompletely-reversible reaction of CH3NH3PbI3 hydrolysis and degrades the photoelectric properties. These findings further elucidate the picture of hydrolysis process of perovskite organometallic halide in humidity environment.

  17. Combinatorial sythesis of organometallic materials

    DOEpatents

    Schultz, Peter G.; Xiang, Xiaodong; Goldwasser, Isy

    2002-07-16

    Methods and apparatus for the preparation and use of a substrate having an array of diverse materials in predefined regions thereon. A substrate having an array of diverse materials thereon is generally prepared by delivering components of materials to predefined regions on a substrate, and simultaneously reacting the components to form at least two materials. Materials which can be prepared using the methods and apparatus of the present invention include, for example, covalent network solids, ionic solids and molecular solids. More particularly, materials which can be prepared using the methods and apparatus of the present invention include, for example, inorganic materials, intermetallic materials, metal alloys, ceramic materials, organic materials, organometallic materials, non-biological organic polymers, composite materials (e.g., inorganic composites, organic composites, or combinations thereof), etc. Once prepared, these materials can be screened for useful properties including, for example, electrical, thermal, mechanical, morphological, optical, magnetic, chemical, or other properties. Thus, the present invention provides methods for the parallel synthesis and analysis of novel materials having useful properties.

  18. Application of the organic on water reactions to prebiotic chemistry

    NASA Astrophysics Data System (ADS)

    Kolb, Vera M.

    2012-10-01

    The old view that prebiotic reactions in water are hampered by the low solubility of the organic compounds in water is now being revised due to the discoveries of the reactions "on water". These reactions occur in the heterogeneous system comprising of the organic compounds and water. Unexpectedly, such reactions are extremely efficient; they often give quantitative yields, and are accelerated in the presence of water as compared to the organic solvents. These "on water" reactions are not the same as the "in water" reactions, which occur in solution, and are thus homogenous. Examples of the "on water" reactions include Diels-Alder, Claisen, Passerini and Ugi reactions, among many others. Some of these reactions are multicomponent, but give a single product. We survey a selected number of the "on water" reactions, which have a potential prebiotic applications.

  19. A golden future in medicinal inorganic chemistry: the promise of anticancer gold organometallic compounds.

    PubMed

    Bertrand, Benoît; Casini, Angela

    2014-03-21

    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 coordination compounds. In fact, several studies have proved that they can be used to develop highly efficient metal-based drugs with possible applications in the treatment of cancer. This Perspective summarizes the results obtained for different families of bioactive organometallic gold compounds including cyclometallated gold(iii) complexes with C,N-donor ligands, gold(I) and gold(I/III) N-heterocyclic (NHC) carbene complexes, as well as gold(I) alkynyl complexes, with promising anticancer effects. Most importantly, we will focus on recent developments in the field and discuss the potential of this class of organometallic compounds in relation to their versatile chemistry and innovative mechanisms of action.

  20. (Comparison of group transfer, inner sphere and outer sphere electron transfer mechanisms of organometallic complexes: Progress report)

    SciTech Connect

    Atwood, J.

    1990-01-01

    We have constructed an infrared stopped-flow spectrophotometer and initiated a study of the mechanisms of reactions that involve a change in the oxidation state of organometallic complexes. In this summary we highlight our results on reactions (1) that formally involve exchange of a charged species between two metal carbonyl anions, (2) that involve addition of an electron to, or removal of an electron from organometallic complexes that contain a metal-metal bond, and (3) between coordination complexes and metal carbonyl anions.

  1. [Comparison of group transfer, inner sphere and outer sphere electron transfer mechanisms of organometallic complexes: Progress report

    SciTech Connect

    Atwood, J.

    1990-12-31

    We have constructed an infrared stopped-flow spectrophotometer and initiated a study of the mechanisms of reactions that involve a change in the oxidation state of organometallic complexes. In this summary we highlight our results on reactions (1) that formally involve exchange of a charged species between two metal carbonyl anions, (2) that involve addition of an electron to, or removal of an electron from organometallic complexes that contain a metal-metal bond, and (3) between coordination complexes and metal carbonyl anions.

  2. Application of metal-based reagents and catalysts in microstructured flow devices.

    PubMed

    Chinnusamy, Tamilselvi; Yudha, Salprima S; Hager, Markus; Kreitmeier, Peter; Reiser, Oliver

    2012-02-13

    Over the years, organic synthesis has witnessed several improvements through the development of new chemical transformations or more efficient reagents for known processes. Likewise, technological advances, aiming at speeding up reactions and facilitating their work-up, have established themselves in academic as well as in industrial laboratories. In this Minireview, we highlight very recent developments in flow chemistry, focusing on organometallic reagents and catalysts. First, we describe reactions with homogeneous catalysts immobilized on different support materials using the concept of packed bed reactors. In the last chapter, we will discuss applications that utilize organometallic reagents.

  3. Organometallic chemistry meets crystal engineering to give responsive crystalline materials.

    PubMed

    Bacchi, A; Pelagatti, P

    2016-01-25

    Dynamically porous crystalline materials have been obtained by engineering organometallic molecules. This feature article deals with organometallic wheel-and-axle compounds, molecules with two relatively bulky groups (wheels) connected by a linear spacer. The wheels are represented by half-sandwich Ru(ii) moieties, while the spacer can be covalent or supramolecular in character. Covalent spacers are obtained using divergent bidentate ligands connecting two [(arene)RuX2] groups. Supramolecular spacers are instead obtained by exploiting the dimerization of COOH or C(O)NH2 groups appended to N-based ligands. A careful choice of ligand functional groups and X ligands leads to the isolation of crystalline materials with remarkable host-guest properties, evidenced by the possibility of reversibly capturing/releasing volatile guests through heterogenous solid-gas reactions. Structural correlations between the crystalline arrangement of the apohost and the host-guest compounds allow us to envisage the structural path followed by the system during the exchange processes.

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

    SciTech Connect

    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.

  5. Artificial Force Induced Reaction Method for Systematic Determination of Complex Reaction Mechanisms.

    PubMed

    Sameera, W M C; Kumar Sharma, Akhilesh; Maeda, Satoshi; Morokuma, Keiji

    2016-10-01

    Nowadays, computational studies are very important for the elucidation of reaction mechanisms and selectivity of complex reactions. However, traditional computational methods usually require an estimated reaction path, mainly driven by limited experimental implications, intuition, and assumptions of stationary points. However, the artificial force induced reaction (AFIR) method in the global reaction route mapping (GRRM) strategy can be used for unbiased and automatic reaction path searches for complex reactions. In this account, we highlight applications of the AFIR method to a variety of reactions (organic, organometallic, enzymatic, and photochemical) of complex molecular systems. In addition, the AFIR method has been successfully used to rationalise the origin of stereo- and regioselectivity. The AFIR method can be applied from small to large molecular systems, and will be a very useful tool for the study of complex molecular problems in many areas of chemistry, biology, and material sciences.

  6. Organometallics in High Energy Chemistry.

    DTIC Science & Technology

    1983-10-31

    C Comments on the Mechanisms of Heterogeneous Catalysis of the Hydrodenitrogenat ion Reaction D Metallic Palladium, the Actual Catalyst in Lindlar...CO Pressure Studies These reactions were run following procedure A with the amine concentration for Et3N and Pr3N set at 0.74 N and with methanol as... reactions were run following procedure A. Experiments were conducted in methanol under 100 psig of CO at 1600C. The total amine concentration was 4.36 M

  7. Atherton–Todd reaction: mechanism, scope and applications

    PubMed Central

    Le Corre, Stéphanie S; Berchel, Mathieu; Couthon-Gourvès, Hélène; Haelters, Jean-Pierre

    2014-01-01

    Summary Initially, the Atherton–Todd (AT) reaction was applied for the synthesis of phosphoramidates by reacting dialkyl phosphite with a primary amine in the presence of carbon tetrachloride. These reaction conditions were subsequently modified with the aim to optimize them and the reaction was extended to different nucleophiles. The mechanism of this reaction led to controversial reports over the past years and is adequately discussed. We also present the scope of the AT reaction. Finally, we investigate the AT reaction by means of exemplary applications, which mainly concern three topics. First, we discuss the activation of a phenol group as a phosphate which allows for subsequent transformations such as cross coupling and reduction. Next, we examine the AT reaction applied to produce fire retardant compounds. In the last section, we investigate the use of the AT reaction for the production of compounds employed for biological applications. The selected examples to illustrate the applications of the Atherton–Todd reaction mainly cover the past 15 years. PMID:24991268

  8. Click Reaction: An Applicable Radiolabeling Method for Molecular Imaging.

    PubMed

    Choi, Ji Young; Lee, Byung Chul

    2015-12-01

    In recent years, the click reaction has found rapidly growing applications in the field of radiochemistry, ranging from a practical labeling method to molecular imaging of biomacromolecules. This present review details the development of highly reliable, powerful and selective click chemistry reactions for the rapid synthesis of new radiotracers for molecular imaging.

  9. Synthesis of Some "Cobaloxime" Derivatives: A Demonstration of "Umpolung" in the Reactivity of an Organometallic Complex

    NASA Astrophysics Data System (ADS)

    Jameson, Donald L.; Grzybowski, Joseph J.; Hammels, Deb E.; Castellano, Ronald K.; Hoke, Molly E.; Freed, Kimberly; Basquill, Sean; Mendel, Angela; Shoemaker, William J.

    1998-04-01

    This article describes a four-reaction sequence for the synthesis of two organometallic "cobaloxime" derivatives. The concept of "Umpolung" or reversal of reactivity is demonstrated in the preparation of complexes. The complex Co(dmgH)2(4-t-BuPy)Et is formed by the reaction of a cobalt (I) intermediate (cobalt in the role of nucleophile) with ethyl iodide. The complex Co(dmgH)2(4-t-BuPy)Ph is formed by the reaction of PhMgBr with a cobalt (III) intermediate (cobalt in the role of electrophile). All the products contain cobalt in the diamagnetic +3 oxidation state and are readily characterized by proton and carbon NMR. The four reaction sequence may be completed in two 4-hour lab periods. Cobaloximes are well known as model complexes for Vitamin B-12 and the experiment exposes students to aspects of classical coordination chemistry, organometallic chemistry and bioinorganic chemistry. The experiment also illustrates an important reactivity parallel between organic and organometallic chemistry.

  10. Magnetic Exchange Interactions in Long Range Ordered Diluted Organometallic Semiconductors

    NASA Astrophysics Data System (ADS)

    Rawat, Naveen; Manning, Lane; Furis, Madalina

    2015-03-01

    Exchange Interactions in diluted organometallic crystalline thin films of Phthalocyanines made of a mixture of organo-soluble derivatives of metal-free (H2Pc) molecule and MnPc is investigated. The tuning of optical and magnetic properties in organometallics is driven by their emergence in optoelectronic applications involving flexible electronics. Thin films with metal to metal-free Pc ratios ranging from 1: 1 to 1:10 were fabricated using solution processing that produces macroscopic grains. In the case of Mn-Pc, our previos measurements showed enhanced hybridization of ligand π-electronic states with the Mn d-orbitals as well as indirect exchange interaction similar to that of RKKY type exchange. The evolution of Zeeman splitting of specific MCD-active states resulted in enhanced effective π-electrons g-factors, analogous to diluted magnetic semiconductors (DMS) systems. Recent Variable temperature Magnetic Circular Dichroism (VTVH-MCD) measurements has now revealed that the exchange interaction is Antiferromagnetic. Recent MCD data for mixed derivatives will be presented along with their temperature dependance that further probes this exchange interaction. NSF award 1056589

  11. Two-Photon Absorption in Organometallic Bromide Perovskites.

    PubMed

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

    2015-09-22

    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.

  12. (Comparison of group transfer, inner sphere and outer sphere electron transfer mechanisms of organometallic complexes)

    SciTech Connect

    Atwood, J.

    1990-01-01

    During the course of Grant ER13775 we have constructed an infrared stopped-flow spectrophotometer and initiated a study of the mechanisms of reactions that involve a change in the oxidation state of organometallic complexes. The spectrometer combined conventional stopped-flow techniques with an infrared optical system comprised of a carbon monoxide laser, an IRTRAN flow-through cell and a mercury-cadium-telluride detector. In this summary we will highlight our results on reactions: (1) that formally involve exchange of a charged species between two metal carbonyl anions, (2) that involve additional of an electron to, or removal of an electron from organometallic complexes that contain a metal-metal bond, and (3) between coordination complexes and metal carbonyl anions. 12 refs.

  13. A biocompatible, highly efficient click reaction and its applications.

    PubMed

    Yuan, Yue; Liang, Gaolin

    2014-02-14

    Herein, we review the development, optimization, applications and potential prospects of a novel click reaction based on the condensation reaction between 2-cyanobenzothiazole (CBT) and D-cysteine (D-Cys) in fireflies. This click condensation reaction has obvious advantages in biocompatibility, efficiency and stability in aqueous environments. Optimization of this click reaction has been carried out so that it can be controlled by pH change, reduction, or enzymatic cleavage to synthesize large molecules and self-assembled nanostructures, or enhance probe signals. Consequently, this CBT-based click reaction has been and could be successfully applied to a wide range of biomedical applications such as molecular imaging (e.g., optical imaging, nuclear imaging and magnetic resonance imaging), biomolecular detection, drug delivery and other potentialities.

  14. Nuclear reaction modeling, verification experiments, and applications

    SciTech Connect

    Dietrich, F.S.

    1995-10-01

    This presentation summarized the recent accomplishments and future promise of the neutron nuclear physics program at the Manuel Lujan Jr. Neutron Scatter Center (MLNSC) and the Weapons Neutron Research (WNR) facility. The unique capabilities of the spallation sources enable a broad range of experiments in weapons-related physics, basic science, nuclear technology, industrial applications, and medical physics.

  15. Heavy Ion Reaction Modeling for Hadrontherapy Applications

    SciTech Connect

    Cerutti, F.; Ferrari, A.; Enghardt, W.; Gadioli, E.; Mairani, A.; Parodi, K.; Sommerer, F.

    2007-10-26

    A comprehensive and reliable description of nucleus-nucleus interactions represents a crucial need in different interdisciplinary fields. In particular, hadrontherapy monitoring by means of in-beam positron emission tomography (PET) requires, in addition to measuring, the capability of calculating the activity of {beta}{sup +}-decaying nuclei produced in the irradiated tissue. For this purpose, in view of treatment monitoring at the Heidelberg Ion Therapy (HIT) facility, the transport and interaction Monte Carlo code FLUKA is a promising candidate. It is provided with the description of heavy ion reactions at intermediate and low energies by two specific event generators. In-beam PET experiments performed at GSI for a few beam-target combinations have been simulated and first comparisons between the measured and calculated {beta}{sup +}-activity are available.

  16. Organometallic NLO Polymers. Accordian Main-Chain NLO Polymers of Ferrocene

    DTIC Science & Technology

    1991-12-13

    suggest that the reaction conditions required to carry out the Lewis acid catalyzed transesterification polycondensation are having deleterious effects on...organometallic main-chain NLO polymers. Our research 1"n -U has continued to f--cus on ferrocene based NLO polymers . MFP because of the outstanding results...under rt-ad pressure. The crude product wargood functional group tolerance because of the mild base (i.e. dissolved in chloroform and precipitated in

  17. Access to organometallic arylcobaltcorrins through radical synthesis: 4-ethylphenylcobalamin, a potential "antivitamin B(12)".

    PubMed

    Ruetz, Markus; Gherasim, Carmen; Gruber, Karl; Fedosov, Sergey; Banerjee, Ruma; Kräutler, Bernhard

    2013-02-25

    Locked B(12): 4-Ethylphenylcobalamin, a novel organometallic arylcobalamin, has been synthesized in a radical reaction. This vitamin B(12) antimetabolite features a strong Co-C bond, and represents a "locked" form of vitamin B(12) . It may be used in animal studies to induce functional vitamin B(12) deficiency artificially to help clarify still controversial issues related to the pathophysiology of vitamin B(12) deficiency.

  18. Ultrafast studies of organometallic photochemistry: The mechanism of carbon-hydrogen bond activation in solution

    SciTech Connect

    Bromberg, S.E.

    1998-05-01

    When certain organometallic compounds are photoexcited in room temperature alkane solution, they are able to break or activate the C-H bonds of the solvent. Understanding this potentially practical reaction requires a detailed knowledge of the entire reaction mechanism. Because of the dynamic nature of chemical reactions, time-resolved spectroscopy is commonly employed to follow the important events that take place as reactants are converted to products. For the organometallic reactions examined here, the electronic/structural characteristics of the chemical systems along with the time scales for the key steps in the reaction make ultrafast UV/Vis and IR spectroscopy along with nanosecond Step-Scan FTIR spectroscopy the ideal techniques to use for this study. An initial study of the photophysics of (non-activating) model metal carbonyls centering on the photodissociation of M(CO){sub 6} (M = Cr, W, Mo) was carried out in alkane solutions using ultrafast IR spectroscopy. Next, picosecond UV/vis studies of the C-H bond activation reaction of Cp{sup *}M(CO){sub 2} (M = Rh, Ir), conducted in room temperature alkane solution, are described in an effort to investigate the origin of the low quantum yield for bond cleavage ({approximately}1%). To monitor the chemistry that takes place in the reaction after CO is lost, a system with higher quantum yield is required. The reaction of Tp{sup *}Rh(CO){sub 2} (Tp{sup *} = HB-Pz{sub 3}{sup *}, Pz{sup *} = 3,5-dimethylpyrazolyl) in alkanes has a quantum yield of {approximately}30%, making time resolved spectroscopic measurements possible. From ultrafast IR experiments, two subsequently formed intermediates were observed. The nature of these intermediates are discussed and the first comprehensive reaction mechanism for a photochemical C-H activating organometallic complex is presented.

  19. Organometallic chemistry: A new metathesis

    NASA Astrophysics Data System (ADS)

    Hennessy, Elisabeth T.; Jacobsen, Eric N.

    2016-08-01

    Carbonyls and alkenes, two of the most common functional groups in organic chemistry, generally do not react with one another. Now, a simple Lewis acid has been shown to catalyse metathesis between alkenes and ketones in a new carbonyl olefination reaction.

  20. Clinical applications of pharmacogenomics to adverse drug reactions.

    PubMed

    Issa, Amalia M

    2008-03-01

    The problem of adverse drug reactions is a well-documented global public health problem. Recent withdrawals of several widely used prescription medications in the USA and other countries have raised concerns among patients, clinicians, scientists and policy makers. The increasing interest and concern regarding withdrawal of previously approved prescription medications and drug safety has prompted renewed research efforts aimed at improving surveillance of approved drugs and reducing adverse drug reactions. Pharmacogenomics research is increasingly directed at developing genomic diagnostics and tests with predictive ability for adverse drug reactions. This paper focuses on the problem of adverse drug reactions and reviews the evidence and the state of the science for the application of pharmacogenomics to adverse drug reactions.

  1. Thiol-addition reactions and their applications in thiol recognition.

    PubMed

    Yin, Caixia; Huo, Fangjun; Zhang, Jingjing; Martínez-Máñez, Ramón; Yang, Yutao; Lv, Haigang; Li, Sidian

    2013-07-21

    Because of the biological importance of thiols, the development of probes for thiols has been an active research area in recent years. In this review, we summarize the results of recent exciting reports regarding thiol-addition reactions and their applications in thiol recognition. The examples reported can be classified into four reaction types including 1,1, 1,2, 1,3, 1,4 addition reactions, according to their addition mechanisms, based on different Michael acceptors. In all cases, the reactions are coupled to color and/or emission changes, although some examples dealing with electrochemical recognition have also been included. The use of thiol-addition reactions is a very simple and straightforward procedure for the preparation of thiol-sensing probes.

  2. Switching on elusive organometallic mechanisms with photoredox catalysis.

    PubMed

    Terrett, Jack A; Cuthbertson, James D; Shurtleff, Valerie W; MacMillan, David W C

    2015-08-20

    Transition-metal-catalysed cross-coupling reactions have become one of the most used carbon-carbon and carbon-heteroatom bond-forming reactions in chemical synthesis. Recently, nickel catalysis has been shown to participate in a wide variety of C-C bond-forming reactions, most notably Negishi, Suzuki-Miyaura, Stille, Kumada and Hiyama couplings. Despite the tremendous advances in C-C fragment couplings, the ability to forge C-O bonds in a general fashion via nickel catalysis has been largely unsuccessful. The challenge for nickel-mediated alcohol couplings has been the mechanistic requirement for the critical C-O bond-forming step (formally known as the reductive elimination step) to occur via a Ni(III) alkoxide intermediate. Here we demonstrate that visible-light-excited photoredox catalysts can modulate the preferred oxidation states of nickel alkoxides in an operative catalytic cycle, thereby providing transient access to Ni(III) species that readily participate in reductive elimination. Using this synergistic merger of photoredox and nickel catalysis, we have developed a highly efficient and general carbon-oxygen coupling reaction using abundant alcohols and aryl bromides. More notably, we have developed a general strategy to 'switch on' important yet elusive organometallic mechanisms via oxidation state modulations using only weak light and single-electron-transfer catalysts.

  3. Switching on elusive organometallic mechanisms with photoredox catalysis

    NASA Astrophysics Data System (ADS)

    Terrett, Jack A.; Cuthbertson, James D.; Shurtleff, Valerie W.; MacMillan, David W. C.

    2015-08-01

    Transition-metal-catalysed cross-coupling reactions have become one of the most used carbon-carbon and carbon-heteroatom bond-forming reactions in chemical synthesis. Recently, nickel catalysis has been shown to participate in a wide variety of C-C bond-forming reactions, most notably Negishi, Suzuki-Miyaura, Stille, Kumada and Hiyama couplings. Despite the tremendous advances in C-C fragment couplings, the ability to forge C-O bonds in a general fashion via nickel catalysis has been largely unsuccessful. The challenge for nickel-mediated alcohol couplings has been the mechanistic requirement for the critical C-O bond-forming step (formally known as the reductive elimination step) to occur via a Ni(III) alkoxide intermediate. Here we demonstrate that visible-light-excited photoredox catalysts can modulate the preferred oxidation states of nickel alkoxides in an operative catalytic cycle, thereby providing transient access to Ni(III) species that readily participate in reductive elimination. Using this synergistic merger of photoredox and nickel catalysis, we have developed a highly efficient and general carbon-oxygen coupling reaction using abundant alcohols and aryl bromides. More notably, we have developed a general strategy to `switch on' important yet elusive organometallic mechanisms via oxidation state modulations using only weak light and single-electron-transfer catalysts.

  4. Switching on Elusive Organometallic Mechanisms with Photoredox Catalysis

    PubMed Central

    Terrett, Jack A.; Cuthbertson, James D.; Shurtleff, Valerie W.; MacMillan, David W. C.

    2015-01-01

    Transition metal-catalyzed cross-coupling reactions have become one of the most utilized carbon–carbon and carbon–heteroatom bond-forming reactions in chemical synthesis. More recently, nickel catalysis has been shown to participate in a wide variety of C–C bond forming reactions, most notably Negishi, Suzuki–Miyaura, Stille, Kumada, and Hiyama couplings1,2. Despite the tremendous advances in C–C fragment couplings, the ability to forge C–O bonds in a general fashion via nickel catalysis has been largely unsuccessful. The challenge for nickel-mediated alcohol couplings has been the mechanistic requirement for the critical C–O bond forming step (formally known as the reductive elimination step) to occur via a Ni(III) alkoxide intermediate. In this manuscript, we demonstrate that visible light-excited photoredox catalysts can modulate the preferred oxidation states of nickel alkoxides in an operative catalytic cycle, thereby providing transient access to Ni(III) species that readily participate in reductive elimination. Using this synergistic merger of photoredox and nickel catalysis, we have developed a highly efficient and general carbon–oxygen coupling reaction using abundant alcohols and aryl bromides. More significantly, we have developed a general strategy to “switch on” important yet elusive organometallic mechanisms via oxidation state modulations using only weak light and single-electron transfer (SET) catalysts. PMID:26266976

  5. Zirconocene and Si-tethered diynes: a happy match directed toward organometallic chemistry and organic synthesis.

    PubMed

    Zhang, Wen-Xiong; Zhang, Shaoguang; Xi, Zhenfeng

    2011-07-19

    Characterizing reactive organometallic intermediates is critical for understanding the mechanistic aspects of metal-mediated organic reactions. Moreover, the isolation of reactive organometallic intermediates can often result in the ability to design new synthetic methods. In this Account, we outline synthetic methods that we developed for a variety of diverse Zr/Si organo-bimetallic compounds and Si/N heteroatom-organic compounds through the detailed study of zirconacyclobutene-silacyclobutene fused compounds. Two basic components are involved in this chemistry. The first is the Si-tethered diyne, which owes its rich reactive palette to the combination of the Si-C bond and the C≡C triple bond. The second is the low-valent zirconocene species Cp(2)Zr(II), which has proven very useful in organic synthesis. The reaction of these two components affords the zirconacyclobutene-silacyclobutene fused compound, which is the key reactive Zr/Si organo-bimetallic intermediate discussed here. We discuss the three types of reactions that have been developed for the zirconacyclobutene-silacyclobutene fused intermediate. The reaction with nitriles (the C≡N triple bond) is introduced in the first section. In this one-pot reaction, up to four different components can be combined: the Si-tethered diyne can be reacted with three identical nitriles, with differing nitriles, or with a nitrile and other unsaturated organic substrates such as formamides, isocyanides, acid chlorides, aldehydes, carbodiimides, and azides. Several unexpected multiring, fused Zr/Si organo-bimetallic intermediates were isolated and characterized. A wide variety of N-heterocycles, such as 5-azaindole, pyrrole, and pyrroloazepine derivatives, were obtained. We then discuss the reaction with alkynes (the C≡C triple bond). A consecutive skeletal rearrangement, differing from that observed in the reactions with nitriles, takes place in this reaction. Finally, we discuss the reaction with the C═X substrates

  6. Anticancer Organometallic Osmium(II)-p-cymene Complexes.

    PubMed

    Păunescu, Emilia; Nowak-Sliwinska, Patrycja; Clavel, Catherine M; Scopelliti, Rosario; Griffioen, Arjan W; Dyson, Paul J

    2015-09-01

    Osmium compounds are attracting increasing attention as potential anticancer drugs. In this context, a series of bifunctional organometallic osmium(II)-p-cymene complexes functionalized with alkyl or perfluoroalkyl groups were prepared and screened for their antiproliferative activity. Three compounds from the series display selectivity toward cancer cells, with moderate cytotoxicity observed against human ovarian carcinoma (A2780) cells, whereas no cytotoxicity was observed on non-cancerous human embryonic kidney (HEK-293) cells and human endothelial (ECRF24) cells. Two of these three cancer-cell-selective compounds induce cell death largely via apoptosis and were also found to disrupt vascularization in the chicken embryo chorioallantoic membrane (CAM) model. Based on these promising properties, these compounds have potential clinical applications.

  7. Organometallic Antitumour Agents with Alternative Modes of Action

    NASA Astrophysics Data System (ADS)

    Casini, Angela; Hartinger, Christian G.; Nazarov, Alexey A.; Dyson, Paul J.

    The therapeutic index of drugs that target DNA, a ubiquitous target present in nearly all cells, is low. Nevertheless, DNA has remained the primary target for medicinal chemists developing metal-based anticancer drugs, although DNA has been essentially abandoned in favour of non-genomic targets by medicinal chemists developing organic drugs. A number of organometallic drugs that target proteins/enzymes have been developed and these compounds, based on ruthenium, osmium and gold, are described in this chapter. Targets include cathepsin B, thioredoxin reductases, multidrug resistance protein (Pgp), glutathione S-transferases and kinases. It is found that compounds that inhibit these various targets are active against metastatic tumours, or tumours that are resistant to classical DNA damaging agents such as cisplatin, and therefore offer considerable potential in clinical applications.

  8. Cytotoxic properties of a new organometallic platinum(II) complex and its gold(I) heterobimetallic derivatives.

    PubMed

    Serratrice, Maria; Maiore, Laura; Zucca, Antonio; Stoccoro, Sergio; Landini, Ida; Mini, Enrico; Massai, Lara; Ferraro, Giarita; Merlino, Antonello; Messori, Luigi; Cinellu, Maria Agostina

    2016-01-14

    A novel platinum(ii) organometallic complex, [Pt(pbi)(Me)(DMSO)], bearing the 2-(2'-pyridyl)-benzimidazole (pbiH) ligand, was synthesized and fully characterized. Interestingly, the reaction of this organometallic platinum(ii) complex with two distinct gold(i) phosphane compounds afforded the corresponding heterobimetallic derivatives with the pbi ligand bridging the two metal centers. The antiproliferative properties in vitro of [Pt(pbi)(Me)(DMSO)] and its gold(i) derivatives as well as those of the known coordination platinum(ii) and palladium(ii) complexes with the same ligand, of the general formula [MCl2(pbiH)], were comparatively evaluated against A2780 cancer cells, either sensitive or resistant to cisplatin. A superior biological activity of the organometallic compound clearly emerged compared to the corresponding platinum(ii) complex; the antiproliferative effects are further enhanced upon attaching the gold(i) triphenylphosphine moiety to the organometallic Pt compound. Remarkably, these novel metal species are able to overcome nearly complete resistance to cisplatin. Significant mechanistic insight into the study compounds was gained after investigating their reactions with a few representative biomolecules by electrospray mass spectrometry and X-ray crystallography. The obtained results are comprehensively discussed.

  9. Transuranic organometallics: The next generation

    SciTech Connect

    Zwick, B.D.; Sattelberger, A.P.; Avens, L.R.

    1990-01-01

    Neptunium and plutonium metal react cleanly with 3/2 equiv. I{sub 2} in aprotic ligating solvents, L, such as tetrahydrofuran (THF), pyridine (Py), and dimethylsulfoxide (DMSO) to give the triiodide complexes as tetrasolvates, AnI{sub 3}(L){sub 4} (An = Np, L = THF (1)); An = Pu, L = THF (2a), Py (2b), and DMSO (2c). These triiodide complexes are convenient precursors to new transuranic compounds. Reaction of the triiodide complexes 1 and 2a hexane with 3 equiv. of sodium bis(trimethylsilyl)amide give the volatile, solvate-free tris(silylamide) complexes, An(N(SiMe{sub 3}){sub 2}){sub 3} (An = Np, 3; An = Pu, 4). The silylamide complexes 3 and 4 undergo rapid reaction in hexane upon stoichiometric addition of HO-2,6-(t-C{sub 4}H{sub 9}){sub 2}C{sub 6}H{sub 3} to give the aryl oxide complexes An(O-2,6-(t-C{sub 4}H{sub 9}){sub 2}C{sub 6}H{sub 3}){sub 3} (An = Np, 5; An = Pu, 6). Preliminary investigations suggest that the aryl oxide complexes 5 and 6 react with lithium bis(trimethylsilyl)methanide, Li{sup +} CH(SiMe{sub 3}){sub 2}, in hexane to give the homoleptic alkyl complexes An(CH(SiMe{sub 3}){sub 2}){sub 3} (An = Np, 7; An = Pu, 8). The homoleptic silylamide, aryl oxide, and alkyl complexes are the first to be reported for transuranic elements. 17 refs.

  10. Relativistic effects for the reaction Sg + 6 CO → Sg(CO)6: Prediction of the mean bond energy, atomization energy, and existence of the first organometallic transactinide superheavy hexacarbonyl Sg(CO)6.

    PubMed

    Malli, Gulzari L

    2015-02-14

    Our ab initio all-electron fully relativistic Dirac-Fock (DF) and nonrelativistic (NR) Hartree-Fock calculations predict the DF relativistic and NR energies for the reaction: Sg + 6 CO → Sg(CO)6 as -7.39 and -6.96 eV, respectively, i.e., our calculated ground state total DF relativistic and NR energies for the reaction product Sg(CO)6 are lower by 7.39 and 6.96 eV than the total DF and NR ground state energies of the reactants, viz., one Sg atom plus six CO molecules, respectively. Our calculated DF relativistic and NR atomization energies (Ae) are 65.23 and 64.82 eV, respectively, and so the contribution of relativistic effects to the Ae of ∼0.40 eV is marginal. The Sg-C and C-O optimized bond distances for the octahedral geometry as calculated in our DF (NR) calculations are 2.151 (2.318 Å) and 1.119 (1.114 Å), respectively. The BSSE correction calculated using the DIRAC code ∼14 kcal/mol. The relativistic DF and NR mean energies predicted by us are 118.8 and 111.9 kJ/mol, respectively, and the contribution of ∼7 kJ/mol due to relativistic effects to the mean energy of Sg(CO)6 is negligible. Ours are the first calculations of the relativistic effects for the atomization energy, mean bond energy, and energy of the reaction for possible formation of Sg(CO)6, and both our relativistic DF and the NR treatments clearly predict for the first time the existence of hexacarbonyl of the transactinide superheavy element seaborgium Sg. In conclusion, relativistic effects are not significant for Sg(CO)6.

  11. Relativistic effects for the reaction Sg + 6 CO → Sg(CO){sub 6}: Prediction of the mean bond energy, atomization energy, and existence of the first organometallic transactinide superheavy hexacarbonyl Sg(CO){sub 6}

    SciTech Connect

    Malli, Gulzari L.

    2015-02-14

    Our ab initio all-electron fully relativistic Dirac–Fock (DF) and nonrelativistic (NR) Hartree-Fock calculations predict the DF relativistic and NR energies for the reaction: Sg + 6 CO → Sg(CO){sub 6} as −7.39 and −6.96 eV, respectively, i.e., our calculated ground state total DF relativistic and NR energies for the reaction product Sg(CO){sub 6} are lower by 7.39 and 6.96 eV than the total DF and NR ground state energies of the reactants, viz., one Sg atom plus six CO molecules, respectively. Our calculated DF relativistic and NR atomization energies (Ae) are 65.23 and 64.82 eV, respectively, and so the contribution of relativistic effects to the Ae of ∼0.40 eV is marginal. The Sg–C and C–O optimized bond distances for the octahedral geometry as calculated in our DF (NR) calculations are 2.151 (2.318 Å) and 1.119 (1.114 Å), respectively. The BSSE correction calculated using the DIRAC code ∼14 kcal/mol. The relativistic DF and NR mean energies predicted by us are 118.8 and 111.9 kJ/mol, respectively, and the contribution of ∼7 kJ/mol due to relativistic effects to the mean energy of Sg(CO){sub 6} is negligible. Ours are the first calculations of the relativistic effects for the atomization energy, mean bond energy, and energy of the reaction for possible formation of Sg(CO){sub 6}, and both our relativistic DF and the NR treatments clearly predict for the first time the existence of hexacarbonyl of the transactinide superheavy element seaborgium Sg. In conclusion, relativistic effects are not significant for Sg(CO){sub 6}.

  12. Relativistic effects for the reaction Sg + 6 CO → Sg(CO)6: Prediction of the mean bond energy, atomization energy, and existence of the first organometallic transactinide superheavy hexacarbonyl Sg(CO)6

    NASA Astrophysics Data System (ADS)

    Malli, Gulzari L.

    2015-02-01

    Our ab initio all-electron fully relativistic Dirac-Fock (DF) and nonrelativistic (NR) Hartree-Fock calculations predict the DF relativistic and NR energies for the reaction: Sg + 6 CO → Sg(CO)6 as -7.39 and -6.96 eV, respectively, i.e., our calculated ground state total DF relativistic and NR energies for the reaction product Sg(CO)6 are lower by 7.39 and 6.96 eV than the total DF and NR ground state energies of the reactants, viz., one Sg atom plus six CO molecules, respectively. Our calculated DF relativistic and NR atomization energies (Ae) are 65.23 and 64.82 eV, respectively, and so the contribution of relativistic effects to the Ae of ˜0.40 eV is marginal. The Sg-C and C-O optimized bond distances for the octahedral geometry as calculated in our DF (NR) calculations are 2.151 (2.318 Å) and 1.119 (1.114 Å), respectively. The BSSE correction calculated using the DIRAC code ˜14 kcal/mol. The relativistic DF and NR mean energies predicted by us are 118.8 and 111.9 kJ/mol, respectively, and the contribution of ˜7 kJ/mol due to relativistic effects to the mean energy of Sg(CO)6 is negligible. Ours are the first calculations of the relativistic effects for the atomization energy, mean bond energy, and energy of the reaction for possible formation of Sg(CO)6, and both our relativistic DF and the NR treatments clearly predict for the first time the existence of hexacarbonyl of the transactinide superheavy element seaborgium Sg. In conclusion, relativistic effects are not significant for Sg(CO)6.

  13. Base reaction optimization of redundant manipulators for space applications

    NASA Technical Reports Server (NTRS)

    Chung, C. L.; Desa, S.; Desilva, C. W.

    1988-01-01

    One of the problems associated with redundant manipulators which were proposed for space applications is that the reactions transmitted to the base of the manipulator as a result of the motion of the manipulator will cause undesirable effects on the dynamic behavior of the supporting space structure. It is therefore necessary to minimize the magnitudes of the forces and moments transmitted to the base. It is shown that kinematic redundancy can be used to solve the dynamic problem of minimizing the magnitude of the base reactions. The methodology described is applied to a four degree-of-freedom spatial manipulator with one redundant degree-of-freedom.

  14. Organometallic Palladium Reagents for Cysteine Bioconjugation

    PubMed Central

    Vinogradova, Ekaterina V.; Zhang, Chi; Spokoyny, Alexander M.; Pentelute, Bradley L.; Buchwald, Stephen L.

    2015-01-01

    Transition-metal based reactions have found wide use in organic synthesis and are used frequently to functionalize small molecules.1,2 However, there are very few reports of using transition-metal based reactions to modify complex biomolecules3,4, which is due to the need for stringent reaction conditions (for example, aqueous media, low temperature, and mild pH) and the existence of multiple, reactive functional groups found in biopolymers. Here we report that palladium(II) complexes can be used for efficient and highly selective cysteine conjugation reactions. The bioconjugation reaction is rapid and robust under a range of biocompatible reaction conditions. The straightforward synthesis of the palladium reagents from diverse and easily accessible aryl halide and trifluoromethanesulfonate precursors makes the method highly practical, providing access to a large structural space for protein modification. The resulting aryl bioconjugates are stable towards acids, bases, oxidants, and external thiol nucleophiles. The broad utility of the new bioconjugation platform was further corroborated by the synthesis of new classes of stapled peptides and antibody-drug conjugates. These palladium complexes show potential as a new set of benchtop reagents for diverse bioconjugation applications. PMID:26511579

  15. Reactivity of seventeen- and nineteen-valence electron complexes in organometallic chemistry

    NASA Technical Reports Server (NTRS)

    Stiegman, Albert E.; Tyler, David R.

    1986-01-01

    A guideline to the reactivity of 17- and 19-valence electron species in organometallic chemistry is proposed which the authors believe will supersede all others. The thesis holds that the reactions of 17-electron metal radicals are associatively activated with reactions proceeding through a 19-valence electron species. The disparate reaction chemistry of the 17-electron metal radicals are unified in terms of this associative reaction pathway, and the intermediacy of 19-valence electron complexes in producing the observed products is discussed. It is suggested that related associatively activated pathways need to be considered in some reactions that are thought to occur by more conventional routes involving 16- and 18-electron intermediates. The basic reaction chemistry and electronic structures of these species are briefly discussed.

  16. Structure investigations of group 13 organometallic carboxylates.

    PubMed

    Justyniak, Iwona; Prochowicz, Daniel; Tulewicz, Adam; Bury, Wojciech; Goś, Piotr; Lewiński, Janusz

    2017-01-17

    The octet-compliant group 13 organometallics with highly polarized bonds in the metal coordination sphere exhibit a significant tendency to maximize their coordination number through the formation of adducts with a wide range of neutral donor ligands or by self-association to give aggregates containing tetrahedral and higher coordinated aluminium centres, and even in some cases molecular complexes equilibrate with ionic species of different coordination numbers of the metal centre. This work provides a comprehensive overview of the structural chemistry landscape of the group 13 carboxylates. Aside from a more systematic approach to the general structural chemistry of the title compounds, the structure investigations of [R2M(μ-O2CPh)]2-type benzoate complexes (where M = B, Al and Ga) and their Lewis acid-base adducts [(R2M)(μ-O2CPh)(py-Me)] are reported. DFT calculations were also performed to obtain a more in-depth understanding of both the changes in the bonding of group 13 organometallic carboxylate adducts with a pyridine ligand.

  17. Antimicrobial Organometallic Dendrimers with Tunable Activity against Multidrug-Resistant Bacteria.

    PubMed

    Abd-El-Aziz, Alaa S; Agatemor, Christian; Etkin, Nola; Overy, David P; Lanteigne, Martin; McQuillan, Katherine; Kerr, Russell G

    2015-11-09

    Multidrug-resistant pathogens are an increasing threat to public health. In an effort to curb the virulence of these pathogens, new antimicrobial agents are sought. Here we report a new class of antimicrobial organometallic dendrimers with tunable activity against multidrug-resistant Gram-positive bacteria that included methicillin-resistant Staphylococcus aureus and vancomycin-resistant Enterococcus faecium. Mechanistically, these redox-active, cationic organometallic dendrimers induced oxidative stress on bacteria and also disrupted the microbial cell membrane. The minimum inhibitory concentrations, which provide a quantitative measure of the antimicrobial activity of these dendrimers, were in the low micromolar range. AlamarBlue cell viability assay also confirms the antimicrobial activity of these dendrimers. Interestingly, these dendrimers were noncytotoxic to epidermal cell lines and to mammalian red blood cells, making them potential antimicrobial platforms for topical applications.

  18. The "click" reaction involving metal azides, metal alkynes, or both: an exploration into multimetal structures.

    PubMed

    Casarrubios, Luis; de la Torre, María C; Sierra, Miguel A

    2013-03-11

    Cu(I) -catalyzed 1,3-cycloaddition of azides and alkynes (CuAAC) is one of the most powerful synthetic methodologies known. However, its use to prepare well-defined multimetallic structures is underdeveloped. Apart from the applications of this reaction to anchor different organometallic reagents to surfaces, polymers, and dendrimers, only isolated examples of CuAAC with metal-η(1) -alkyne and metal-azide complexes to prepare multimetal entities have been reported. This concept sketches the potential of these reactions not only to prepare "a la carte" multimetal 1,2,3-triazole derivatives, but also to discover new and unprecedented reactions.

  19. Allenes and computational chemistry: from bonding situations to reaction mechanisms.

    PubMed

    Soriano, Elena; Fernández, Israel

    2014-05-07

    The present review is focused on the application of computational/theoretical methods to the wide and rich chemistry of allenes. Special emphasis is made on the interplay and synergy between experimental and computational methodologies, rather than on recent developments in methods and algorithms. Therefore, this review covers the state-of-the-art applications of computational chemistry to understand and rationalize the bonding situation and vast reactivity of allenes. Thus, the contents of this review span from the most fundamental studies on the equilibrium structure and chirality of allenes to recent advances in the study of complex reaction mechanisms involving allene derivatives in organic and organometallic chemistry.

  20. A simplified hydrocarbon reaction mechanism for combustion applications

    NASA Technical Reports Server (NTRS)

    Jachimowski, C. J.

    1985-01-01

    A simplified chemical kinetic reaction mechanism for the combustion of a hydrocarbon fuel is presented and discussed. The observed kinetic behavior of propane combustion as determined in shock tube studies and the calculated kinetic behavior of propane/air mixtures as derived from a detailed propane combustion mechanism were used as a data base for constructing and refining the mechanism. The mechanism contains 13 chemical species and 26 chemical reactions. Numerical studies revealed that the simplified mechanism can reproduce the observed kinetic behavior of propane/air mixtures, including laminar flame speeds, over a wide range of temperatures and pressures. It is anticipated that the mechanism can be used in various combustion applications and provide a more realistic description of the combustion process than can be achieved using global reaction mechanisms.

  1. Surface organometallic chemistry on metals. III. Formation of a bimetallic Ni-Sn phase generated by reaction of a Sn(n-C sub 4 H sub 9 ) sub 4 and silica-supported nickel oxide

    SciTech Connect

    Agnelli, M.; Candy, J.P.; Basset, J.M. ); Bournonville, J.P.; Ferretti, O.A. )

    1990-02-01

    Reaction of Sn(n-C{sub 4}H{sub 9}){sub 4} with NiO/SiO{sub 2} occurs above 423 K according to the apparent following stoichiometry: NiO + xSn(n-C{sub 4}H{sub 9}){sub 4} {yields} NiSn{sub x} + (2x + 1)C{sub 4}H{sub 8} + (2x {minus} 1)C{sub 4}H{sub 10} + H{sub 2}O. Various compositions of the bimetallic phase can be achieved by changing the initial Sn/Ni ratio. The obtained catalysts were very active and selective in the hydrogenation of ethyl acetate to ethanol. Characterization of the bimetallic phase has shown that the particles are bimetallic (STEM). As a result of chemisorption IR, and magnetic measurements, it appears that the presence of tin has four effects: (i) it decreases significantly the amount of CO and H{sub 2} adsorbed; (ii) it isolates nickel atoms from their neighbors; (iii) it increases electron density on nickel; and (IV) it suppresses the magnetic properties of nickel. Redox behavior of Ni-Sn/SiO{sub 2} toward surface OH indicates that surface hydroxyls can oxidize Sn{sup (0)}, probably to Sn{sup (II)} with evolution of H{sub 2}, the process being reversible with H{sub 2}. It is suggested that during this oxidation process, tin migrates to the periphery of the bimetallic particle with formation of (chemical bond Si-O){sub 2}Sn{sup (II)} surface species.

  2. The Development and Study of Surface Bound Ruthenium Organometallic Complexes

    NASA Astrophysics Data System (ADS)

    Abbott, Geoffrey Reuben

    large way. With a better understanding of the effects of surface binding on the complexes, the study turned to possible applications, as either sensors or catalysts. Recently the bound complexes have been found to be very useful as toxic metal sensors, as the free amines left on the surface could bind toxic metal ions in close proximity leading to either a quenching or enhancement of the luminescence of the complexes, depending on the metal ion. This process was determined to be a static process, requiring the toxic metal to remain bound to the surface in order to affect the luminescence of the Ru complex. The quenching is thought to be due to a metal-centered electron-transfer reaction, in which the excited-state electron is transferred from the Ru to the toxic metal, but relaxes back to the Ru center. The enhancement of luminescence is due to the external heavy-atom effect, in which heavier atoms mixes MLCT singlet state with the triplet state through spin-orbit coupling.

  3. Organometallic palladium reagents for cysteine bioconjugation

    NASA Astrophysics Data System (ADS)

    Vinogradova, Ekaterina V.; Zhang, Chi; Spokoyny, Alexander M.; Pentelute, Bradley L.; Buchwald, Stephen L.

    2015-10-01

    Reactions based on transition metals have found wide use in organic synthesis, in particular for the functionalization of small molecules. However, there are very few reports of using transition-metal-based reactions to modify complex biomolecules, which is due to the need for stringent reaction conditions (for example, aqueous media, low temperature and mild pH) and the existence of multiple reactive functional groups found in biomolecules. Here we report that palladium(II) complexes can be used for efficient and highly selective cysteine conjugation (bioconjugation) reactions that are rapid and robust under a range of bio-compatible reaction conditions. The straightforward synthesis of the palladium reagents from diverse and easily accessible aryl halide and trifluoromethanesulfonate precursors makes the method highly practical, providing access to a large structural space for protein modification. The resulting aryl bioconjugates are stable towards acids, bases, oxidants and external thiol nucleophiles. The broad utility of the bioconjugation platform was further corroborated by the synthesis of new classes of stapled peptides and antibody-drug conjugates. These palladium complexes show potential as benchtop reagents for diverse bioconjugation applications.

  4. Organometallic palladium reagents for cysteine bioconjugation.

    PubMed

    Vinogradova, Ekaterina V; Zhang, Chi; Spokoyny, Alexander M; Pentelute, Bradley L; Buchwald, Stephen L

    2015-10-29

    Reactions based on transition metals have found wide use in organic synthesis, in particular for the functionalization of small molecules. However, there are very few reports of using transition-metal-based reactions to modify complex biomolecules, which is due to the need for stringent reaction conditions (for example, aqueous media, low temperature and mild pH) and the existence of multiple reactive functional groups found in biomolecules. Here we report that palladium(II) complexes can be used for efficient and highly selective cysteine conjugation (bioconjugation) reactions that are rapid and robust under a range of bio-compatible reaction conditions. The straightforward synthesis of the palladium reagents from diverse and easily accessible aryl halide and trifluoromethanesulfonate precursors makes the method highly practical, providing access to a large structural space for protein modification. The resulting aryl bioconjugates are stable towards acids, bases, oxidants and external thiol nucleophiles. The broad utility of the bioconjugation platform was further corroborated by the synthesis of new classes of stapled peptides and antibody-drug conjugates. These palladium complexes show potential as benchtop reagents for diverse bioconjugation applications.

  5. Non-metallocene organometallic complexes and related methods and systems

    DOEpatents

    Agapie, Theodor; Golisz, Suzanne Rose; Tofan, Daniel; Bercaw, John E.

    2010-12-07

    A non-metallocene organometallic complex comprising a tridentate ligand and a metal bonded to a tridentate ligand, wherein two substituted aryl groups in the tridentate ligand are connected to a cyclic group at the ortho position via semi-rigid ring-ring linkages, and selected so to provide the resulting non-metallocene organometallic complex with a C.sub.S geometry, a C.sub.1 geometry, a C.sub.2 geometry or a C.sub.2v geometry. Method for performing olefin polymerization with a non-metallocene organometallic complex as a catalyst, related catalytic systems, tridentate ligand and method for providing a non-metallocene organometallic complex.

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

    PubMed

    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.

  7. Supported organometallic complexes, surface chemistry, spectroscopy, and catalysis. Progress report, September 15, 1992--November 14, 1993

    SciTech Connect

    Marks, T.J.

    1993-04-01

    Goal is to elucidate and understand the surface chemistry and catalytic properties of well-defined, highly-reactive organometallic molecules (principally based upon abundant actinide, lanthanide, and early transition elements) adsorbed on metal oxides and halides. Nature of adsorbed species is probed by a battery of chemical and physicochemical techniques, to understand the nature of the molecule-surface coordination chemistry and how this can give rise to extremely high catalytic activity. A complementary objective is to delineate the scope and mechanisms of the heterogeneous catalytic reactions, as well as to relate them both conceptually and functionally to model systems generated in solution.

  8. 'Clickable' ZnO nanocrystals: the superiority of a novel organometallic approach over the inorganic sol-gel procedure.

    PubMed

    Grala, Agnieszka; Wolska-Pietkiewicz, Małgorzata; Danowski, Wojciech; Wróbel, Zbigniew; Grzonka, Justyna; Lewiński, Janusz

    2016-05-31

    We demonstrate for the first time a highly efficient Cu(i)-catalyzed alkyne-azide cycloaddition reaction on the surface of ZnO nanocrystals with retention of their photoluminescence properties. Our comparative studies highlight the superiority of a novel self-supporting organometallic method for the preparation of brightly luminescent and well-passivated ZnO nanocrystals over the traditional sol-gel procedure.

  9. Synthesis and Migratory-Insertion Reactivity of CpMo(CO)[subscript3](CH[subscript3]): Small-Scale Organometallic Preparations Utilizing Modern Glovebox Techniques

    ERIC Educational Resources Information Center

    Whited, Matthew T.; Hofmeister, Gretchen E.

    2014-01-01

    Experiments are described for the reliable small-scale glovebox preparation of CpMo(CO)[subscript 3](CH[subscript 3]) and acetyl derivatives thereof through phosphine-induced migratory insertion. The robust syntheses introduce students to a variety of organometallic reaction mechanisms and glovebox techniques, and they are easily carried out…

  10. One- and two-dimensional infrared spectroscopic studies of solution-phase homogeneous catalysis and spin-forbidden reactions

    SciTech Connect

    Sawyer, Karma Rae

    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.

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

    PubMed

    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

  12. Spin-State Effects on the Thermal Dihydrogen Release from Solid-State [MH(η2-H2)dppe2]+ (M = Fe, Ru, Os) Organometallic Complexes for Hydrogen Storage Applications

    PubMed Central

    2015-01-01

    Mössbauer spectroscopy, experimental thermodynamic measurements, and computational studies were performed to investigate the properties of molecular hydrogen binding to the organometallic fragments [MHdppe2]+ (M = Fe, Ru, Os; dppe =1,2-bis(diphenylphosphino)ethane) to form the dihydrogen complex fragments [MH(η2-H2)dppe2]+. Mössbauer spectroscopy showed that the dehydrogenated complex [FeHdppe2]+ adopts a geometry consistent with the triplet spin state, transitioning to a singlet state complex upon addition of the dihydrogen molecule in a manner similar to the previously studied dinitrogen complexes. From simulations, this spin transition behavior was found to be responsible for the strong binding behavior experimentally observed in the iron complex. Spin-singlet to spin-singlet transitions were found to exhibit thermodynamics consistent with the 5d > 3d > 4d binding trend observed for other transition metal dihydrogen complexes. Finally, the method for distinguishing between dihydrogen and dihydride complexes based on partial quadrupole splittings observed in Mössbauer spectra was confirmed, providing a tool for further characterization of these unique species for Mössbauer active compounds. PMID:24803973

  13. Reaction Mechanisms of Magnesium Potassium Phosphate Cement and its Application

    NASA Astrophysics Data System (ADS)

    Qiao, Fei

    Magnesium potassium phosphate cement (MKPC) is a kind of cementitious binder in which the chemical bond is formed via a heterogeneous acid-base reaction between dead burned magnesia powder and potassium phosphate solution at room temperature. Small amount of boron compounds can be incorporated in the cement as a setting retarder. The final reaction product of MgO-KH2PO4-H 2O ternary system is identified as magnesium potassium phosphate hexahydrate, MgKPO4·6H2O. However, the mechanisms and procedures through which this crystalline product is formed and the conditions under which the crystallization process would be influenced are not yet clear. Understanding of the reaction mechanism of the system is helpful for developing new methodologies to control the rapid reaction process and furthermore, to adjust the phase assemblage of the binder, and to enhance the macroscopic properties. This study is mainly focused on the examination of the reaction mechanism of MKPC. In addition, the formulation optimization, microstructure characterization and field application in rapid repair are also systematically studied. The chemical reactions between magnesia and potassium dihydrogen phosphate are essentially an acid-base reaction with strong heat release, the pH and temperature variation throughout the reaction process could provide useful information to disclose the different stages in the reaction. However, it would be very difficult to conduct such tests on the cement paste due to the limited water content and fast setting. In the current research, the reaction mechanism of MKPC is investigated on the diluted MKPC system through monitoring the pH and temperature development, identification of the solid phase formed, and measurement of the ionic concentration of the solution. The reaction process can be explained as follows: when magnesia and potassium phosphate powder are mixed with water, phosphate is readily dissolved, which is instantly followed by the dissociation of

  14. Sulfur-bonded thiophenes in organometallic rhenium complexes and adsorption of isocyanides on gold

    SciTech Connect

    Robertson, Mitchell Joe

    1993-08-01

    This dissertation contains results of research conducted in two different areas: (1) organometallic synthesis and reactivity, and (2) organometallic surface chemistry. In the synthesis and reactivity studies, sulfur coordination of thiophene and benzo[b]thiophene to the metal center in organometallic rhenium complexes is examined. In the surface chemistry studies, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) is used to analyze the adsorption of several isocyanides on the surface of gold powder. Results are compared and contrasted to known organometallic chemistry.

  15. Radical SAM catalysis via an organometallic intermediate with an Fe-[5'-C]-deoxyadenosyl bond.

    PubMed

    Horitani, Masaki; Shisler, Krista; Broderick, William E; Hutcheson, Rachel U; Duschene, Kaitlin S; Marts, Amy R; Hoffman, Brian M; Broderick, Joan B

    2016-05-13

    Radical S-adenosylmethionine (SAM) enzymes use a [4Fe-4S] cluster to cleave SAM to initiate diverse radical reactions. These reactions are thought to involve the 5'-deoxyadenosyl radical intermediate, which has not yet been detected. We used rapid freeze-quenching to trap a catalytically competent intermediate in the reaction catalyzed by the radical SAM enzyme pyruvate formate-lyase activating enzyme. Characterization of the intermediate by electron paramagnetic resonance and (13)C, (57)Fe electron nuclear double-resonance spectroscopies reveals that it contains an organometallic center in which the 5' carbon of a SAM-derived deoxyadenosyl moiety forms a bond with the unique iron site of the [4Fe-4S] cluster. Discovery of this intermediate extends the list of enzymatic bioorganometallic centers to the radical SAM enzymes, the largest enzyme superfamily known, and reveals intriguing parallels to B12 radical enzymes.

  16. Organic or organometallic template mediated clay synthesis

    SciTech Connect

    Gregar, K.C.; Winans, R.E.; Botto, R.E.

    1992-12-31

    A method is given 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 LiF for 2 days with 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 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 US patent No. 3,887,454 issued to Hickson, June 13, 1975; however, a variety of intercalants or templates may be introduced. The intercalants or templates should have water-solubility, positive charge, and thermal stability under moderately basic (pH 9-10) aqueous reflux conditions or hydrothermal pressurized conditions for the montmorillonite-type clays.

  17. Combinatorial screening of inorganic and organometallic materials

    DOEpatents

    Schultz, Peter G.; Xiang, Xiaodong; Goldwasser, Isy

    2002-01-01

    Methods and apparatus for the preparation and use of a substrate having an array of diverse materials in predefined regions thereon. A substrate having an array of diverse materials thereon is generally prepared by delivering components of materials to predefined regions on a substrate, and simultaneously reacting the components to form at least two materials. Materials which can be prepared using the methods and apparatus of the present invention include, for example, covalent network solids, ionic solids and molecular solids. More particularly, materials which can be prepared using the methods and apparatus of the present invention include, for example, inorganic materials, intermetallic materials, metal alloys, ceramic materials, organic materials, organometallic materials, non-biological organic polymers, composite materials (e.g., inorganic composites, organic composites, or combinations thereof), etc. Once prepared, these materials can be screened for useful properties including, for example, electrical, thermal, mechanical, morphological, optical, magnetic, chemical, or other properties. Thus, the present invention provides methods for the parallel synthesis and analysis of novel materials having useful properties.

  18. Organic or organometallic template mediated clay synthesis

    DOEpatents

    Gregar, K.C.; Winans, R.E.; Botto, R.E.

    1994-05-03

    A method is described for incorporating diverse varieties of intercalates 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 intercalate 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 intercalates or templates may be introduced. The intercalates 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. 22 figures.

  19. Organic or organometallic template mediated clay synthesis

    DOEpatents

    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.

  20. Mining unexpected temporal associations: applications in detecting adverse drug reactions.

    PubMed

    Jin, Huidong Warren; Chen, Jie; He, Hongxing; Williams, Graham J; Kelman, Chris; O'Keefe, Christine M

    2008-07-01

    In various real-world applications, it is very useful mining unanticipated episodes where certain event patterns unexpectedly lead to outcomes, e.g., taking two medicines together sometimes causing an adverse reaction. These unanticipated episodes are usually unexpected and infrequent, which makes existing data mining techniques, mainly designed to find frequent patterns, ineffective. In this paper, we propose unexpected temporal association rules (UTARs) to describe them. To handle the unexpectedness, we introduce a new interestingness measure, residual-leverage, and develop a novel case-based exclusion technique for its calculation. Combining it with an event-oriented data preparation technique to handle the infrequency, we develop a new algorithm MUTARC to find pairwise UTARs. The MUTARC is applied to generate adverse drug reaction (ADR) signals from real-world healthcare administrative databases. It reliably shortlists not only six known ADRs, but also another ADR, flucloxacillin possibly causing hepatitis, which our algorithm designers and experiment runners have not known before the experiments. The MUTARC performs much more effectively than existing techniques. This paper clearly illustrates the great potential along the new direction of ADR signal generation from healthcare administrative databases.

  1. New methodologies for construction of hyperbranched organic and organometallic polymers

    NASA Astrophysics Data System (ADS)

    Xu, Kaitian

    2000-10-01

    A series of completely soluble hyperbranched polymers were synthesized by polycyclotrimerization of diynes for the first time. TaCl5-Ph 4Sn was found to be the effective catalyst and toluene to be the efficient solvent. A possible polycyclotrimerization mechanism via tantalacyclopentadiene intermediates is proposed. The polymerization processes including initiation, propagation and termination are analyzed. The unique backbiting reaction was found to be a plausible way to terminate the propagation chain. Conformations of the diynes greatly affect the occurrence of backbiting reaction and affect the solubility of resultant polymers to certain extent. Diynes with short spacers such as 1,5-hexadiyne (21 ); 1,6-heptadiyne (22); 1,7-octadiyne (23); and 1,8-nonadiyne (17); possess a conformation in which the two triple bonds locate closely. Such a conformation makes the backbiting termination to occur easily. Thus, soluble polymers are readily formed from these diynes. For the diynes of long spacers, a conformation with two far-separating triple bonds dramatically reduces the chance of backbiting reaction. Consequently, only partially soluble or insoluble polymers could be prepared. In the polycyclotrimerization of internal diynes, hexasubstituted benzene rings were formed. The steric effect of the terminal substituents plays an important role in the polymerization reaction. Internal diynes with bulky substituents such as 1,9-bis(trimethylsilyl)-1,8-nonadiyne (74), 1,6-bis(dimethylphenylsilyl)-1,5-hexadiyne (75), 1,8-bis(dimethylphenylsilyl)-1,7-octadiyne (76) gave little amount of polymers. Internal diynes with less bulky substituents and short spacers [e.g. 3,9-dodecadiyne (78) and 2,9-undecadiyne (79)] offered soluble polymers. In the study on hyperbranched organometallic polymers, a new methodology for the preparation of hyperbranched polysilynes was developed. Ceramization of the hyperbranched polymers produced mesoporous magnetoceramic materials. The compositions

  2. A "Classic Papers" Approach to Teaching Undergraduate Organometallic Chemistry

    NASA Astrophysics Data System (ADS)

    Duncan, Andrew P.; Johnson, Adam R.

    2007-03-01

    We have structured an upper-level undergraduate course in organometallic chemistry on a selection of "classic" publications in the field. This approach offers students a richly contextual introduction to many of the fundamental tenets of the discipline. After a brief introduction to the field led by the faculty, the students themselves are responsible for researching and presenting selected papers to their classmates for analysis and discussion. Beyond mastery of basic organometallic principles, course goals for the students include improved proficiency in using the primary chemical literature and increased experience and confidence in researching, preparing, and delivering an informative oral presentation in individual and collaborative settings. Student performance is assessed based on performance on open-ended, take-home exams, quality of presentations, and contribution to in-class discussions. Student end-of-term survey responses indicate that this class model is successful as an introduction to organometallic chemistry.

  3. Patients' Reactions to Local Anaesthetic Application Devices in Paediatric Dentistry.

    PubMed

    Bajrić, Elmedin; Kobasglija, Sedin; Jurić, Hrvoje

    2015-09-01

    Local anaesthesia is the most common medium for pain control in most dental treatments. Physical appearance of syringe itself can be considered as a provoking factor for the emergence of dental fear and anxiety (DFA). In this research the patient reactions to local anaesthesia application devices, as one of the main causes for DFA emergence, were inquired. The sample comprised of 120 patients, divided in three age groups, formed of 40 patients aged 8, 12 and 15 years. DFA prevalence was quantified by Children Fear Survey Schedule-Dental Subscale (CFSS-DS). Three different syringes were offered to the patients. Reasons for choosing one of the syringes were detected. Patients assigned statistically highest rank to plastic syringe. Boys chose metal and intraligamental syringe statistically more often than girls. Patients with higher CFSS-DS scores chose metal syringe as last option. None of the reasons for selection was dominant, except pain that could be caused by usage of any of the three syringes. A large number of patients did not mention any of the reasons for choosing particular syringes. Plastic syringe represented the most acceptable device for local anaesthetic application to our patients. Patients often linked pain with dental syringes.

  4. Conjugated organometallic materials containing tungsten centers

    NASA Astrophysics Data System (ADS)

    Jones, Marya

    Our group is interested in the optical and electronic properties of organometallic analogues of conjugated organic compounds. Specifically, in this thesis we will discuss the properties of complexes in which W≡C moieties replace C≡C fragments within the framework of oligo(phenyleneethynylenes) and a C4-polyyne. A family of derivatives of the type Ph(C≡CC6H4 )m(L)4W≡C(C6H 4C≡C)nPh (m = 0, 1; n = 0, 1, 2) have been prepared and characterized by X-ray crystallography, electronic-absorption spectroscopy, and electrochemistry. This substitution has allowed us to directly compare the electronic and optical properties of these organometallic complexes with those of their organic analogues. We found that while these systems exhibit redox and spectroscopic properties similar to those of their organic counterparts they also exhibit new characteristics that are due to the incorporation of the metal center. The design of these compounds has also allowed us to address how the position of the metal within the backbone affects the electronic and optical properties of these compounds. We found that the position of the metal is important in controlling the electronic structure of the material, thus suggesting that the properties of these compounds can be further tuned by changing the position of the metal within the conjugated carbon chain. In addition, we have appended sulfur and isocyanide functionalities to oligo(phenyleneethynylene) analogues. A family of compounds of the type Cl(dppe) 2W(≡CC6H4-4-(C≡CC6H 4)m-4'-R) (m = l, 2; R = N≡C, SCH2CH 2Si(CH3)3) have been prepared and characterized by electronic-absorption spectroscopy and electrochemistry. Differences between the sulfur and isocyanide functionalities are examined, along with the effects of extending conjugation along the arylidyne chain. Evidence that the sulfur-containing arylidyne complexes form self-assembled monolayers on Au and Pt electrodes is presented. In addition, the electron-transfer rates for

  5. Extracellular photosensitization reaction progress and effect on myocardial cell necrosis for arrhythmia treatment application

    NASA Astrophysics Data System (ADS)

    Ogawa, Emiyu; Takahashi, Mei; Ito, Arisa; Arai, Tsunenori

    2013-06-01

    We investigated detailed extracellular photosensitization reaction effect on rat myocardial cells and the photosensitization reaction progress in a well to study a new application of photodynamic therapy for arrhythmia therapy.

  6. Artificial Force Induced Reaction (AFIR) Method for Exploring Quantum Chemical Potential Energy Surfaces.

    PubMed

    Maeda, Satoshi; Harabuchi, Yu; Takagi, Makito; Taketsugu, Tetsuya; Morokuma, Keiji

    2016-10-01

    In this account, a technical overview of the artificial force induced reaction (AFIR) method is presented. The AFIR method is one of the automated reaction-path search methods developed by the authors, and has been applied extensively to a variety of chemical reactions, such as organocatalysis, organometallic catalysis, and photoreactions. There are two modes in the AFIR method, i.e., a multicomponent mode and a single-component mode. The former has been applied to bimolecular and multicomponent reactions and the latter to unimolecular isomerization and dissociation reactions. Five numerical examples are presented for an Aldol reaction, a Claisen rearrangement, a Co-catalyzed hydroformylation, a fullerene structure search, and a nonradiative decay path search in an electronically excited naphthalene molecule. Finally, possible applications of the AFIR method are discussed.

  7. New Chemical and Stereochemical Applications of Organoiron Complexes

    PubMed Central

    Fatiadi, Alexander J.

    1991-01-01

    The objective of this review is to provide a current overview of the rapidly developing chemistry of organometallic complexes and particularly organoiron complexes useful in asymmetric and stereoselective reactions. Also covered are stereoselective reactions of α, β-unsaturated acyl ligands bound to the chiral auxiliary [(η5-C5H5) Fe(CO)(PPh3)] and new applications of organoiron complexes in the synthesis of natural products. The mechanistic aspects and stabilizing effects of the Fe(CO)3 group for alkenes or conjugated dienes are discussed. A brief summary of recent work on the special role of iron in biological reactions is also included. PMID:28184103

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

    NASA Astrophysics Data System (ADS)

    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.

  9. Precursor nuclearity effects in supported vanadium oxides prepared by organometallic grafting.

    SciTech Connect

    Wegener, S. L.; Kim, H.; Marks, T. J.; Stair, P. C.

    2011-01-01

    Despite widespread importance in catalysis, the active and selective sites of supported vanadium oxide (VO{sub x}) catalysts are not well understood. Such catalysts are of great current interest because of their industrial significance and potential for selective oxidation processes. However, the fact that the nature of the active and selective sites is ambiguous hinders molecular level understanding of catalytic reactions and the development of new catalysts. Furthermore, complete structural elucidation requires isolation and characterization of specific vanadium oxide surface species, the preparation of which presents a significant synthetic challenge. In this study, we utilize the structural uniformity inherent in organometallic precursors for the preparation of supported vanadium oxide catalysts. The resulting catalysts are characterized by UV-visible diffuse reflectance spectroscopy (UV-vis DRS), X-ray absorption spectroscopy (XAS), UV-Raman spectroscopy, and H{sub 2}-temperature programmed reduction (H{sub 2}-TPR). Significant structural and reactivity differences are observed in catalysts prepared from different organometallic precursors, indicating that the chemical nature of surface vanadia can be influenced by the nuclearity of the precursor used for grafting.

  10. Functionalization of a ruthenium-diacetylide organometallic complex as a next-generation push-pull chromophore.

    PubMed

    De Sousa, Samuel; Ducasse, Laurent; Kauffmann, Brice; Toupance, Thierry; Olivier, Céline

    2014-06-02

    The design and preparation of an asymmetric ruthenium-diacetylide organometallic complex was successfully achieved to provide an original donor-π-[M]-π-acceptor architecture, in which [M] corresponds to the [Ru(dppe)2] (dppe: bisdiphenylphosphinoethane) metal fragment. The charge-transfer processes occurring upon photoexcitation of the push-pull metal-dialkynyl σ complex were investigated by combining experimental and theoretical data. The novel push-pull complex, appropriately end capped with an anchoring carboxylic acid function, was further adsorbed onto a semiconducting metal oxide porous thin film to serve as a photosensitizer in hybrid solar cells. The resulting photoactive material, when embedded in dye-sensitized solar cell devices, showed a good spectral response with a broad incident photon-to-current conversion efficiency profile and a power conversion efficiency that reached 7.3 %. Thus, this material paves the way to a new generation of organometallic chromophores for photovoltaic applications.

  11. A robust microfluidic device for the synthesis and crystal growth of organometallic polymers with highly organized structures.

    PubMed

    Liu, Xiao; Yi, Qiaolian; Han, Yongzhen; Liang, Zhenning; Shen, Chaohua; Zhou, Zhengyang; Sun, Jun-Liang; Li, Yizhi; Du, Wenbin; Cao, Rui

    2015-02-02

    A simple and robust microfluidic device was developed to synthesize organometallic polymers with highly organized structures. The device is compatible with organic solvents. Reactants are loaded into pairs of reservoirs connected by a 15 cm long microchannel prefilled with solvents, thus allowing long-term counter diffusion for self-assembly of organometallic polymers. The process can be monitored, and the resulting crystalline polymers are harvested without damage. The device was used to synthesize three insoluble silver acetylides as single crystals of X-ray diffraction quality. Importantly, for the first time, the single-crystal structure of silver phenylacetylide was determined. The reported approach may have wide applications, such as crystallization of membrane proteins, synthesis and crystal growth of organic, inorganic, and polymeric coordination compounds, whose single crystals cannot be obtained using traditional methods.

  12. Organometalic carbosilane polymers containing vanadium and their preparation

    NASA Technical Reports Server (NTRS)

    Yajima, S.; Okamura, K.; Shishido, T.; Fukuda, K.

    1983-01-01

    The present invention concerns a new organometallic polymer material containing in part a vanadium-siloxane linkage (V-0-Si), which has excellent resistance to heat and oxidation and a high residue ratio after high temperature treatment in a non-oxidizing atmosphere, for example, nitrogen, argon, helium, ammonia, or hydrogen.

  13. In –Situ Spectroscopic Investigation of Immobilized Organometallic Catalysts

    SciTech Connect

    Davis, Robert, J.

    2007-11-14

    Immobilized organometallic catalysts, in principle, can give high rates and selectivities like homogeneous catalysts with the ease of separation enjoyed by heterogeneous catalysts. However, the science of immobilized organometallics has not been developed because the field lies at the interface between the homogeneous and heterogeneous catalysis communities. By assembling an interdisciplinary research team that can probe all aspects of immobilized organometallic catalyst design, the entire reacting system can be considered, where the transition metal complex, the complex-support interface and the properties of the support can all be considered simultaneously from both experimental and theoretical points of view. Researchers at Georgia Tech and the University of Virginia are studying the fundamental principles that can be used to understand and design future classes of immobilized organometallic catalysts. In the framework of the overall collaborative project with Georgia Tech, our work focused on (a) the X-ray absorption spectroscopy of an immobilized Pd-SCS-O complex (b) the mode of metal leaching from supported Pd catalysts during Heck catalysis and (c) the mode of deactivation of Jacobsen’s Co-salen catalysts during the hydrolytic kinetic resolution of terminal epoxides. Catalysts containing supported Pd pincer complexes, functionalized supports containing mercapto and amine groups, and oligomeric Co-salen catalysts were synthesized at Georgia Tech and sent to the University of Virginia. Incorporation of Pd onto several different kinds of supports (silica, mercapto-functionalized silica, zeolite Y) was performed at the University of Virginia.

  14. Rational design of an organometallic glutathione transferase inhibitor

    SciTech Connect

    Ang, W.H.; Parker, L.J.; De Luca, A.; Juillerat-Jeanneret, L.; Morton, C.J.; LoBello, M.; Parker, M.W.; Dyson, P.J.

    2010-08-17

    A hybrid organic-inorganic (organometallic) inhibitor was designed to target glutathione transferases. The metal center is used to direct protein binding, while the organic moiety acts as the active-site inhibitor. The mechanism of inhibition was studied using a range of biophysical and biochemical methods.

  15. Preparation of activated carbons with mesopores by use of organometallics

    SciTech Connect

    Yamada, Yoshio; Yoshizawa, Noriko; Furuta, Takeshi

    1996-12-31

    Activated carbons are commercially produced by steam or CO{sub 2} activation of coal, coconut shell and so on. In general the carbons obtained give pores with a broad range of distribution. The objective of this study was to prepare activated carbons from coal by use of various organometallic compounds. The carbons were evaluated for pore size by nitrogen adsorption experiments.

  16. The application of BTEM to UV-vis and UV-vis CD spectroscopies: the reaction of Rh4(CO)12 with chiral and achiral ligands.

    PubMed

    Cheng, Shuying; Gao, Feng; Krummel, Karl I; Garland, Marc

    2008-02-15

    Two different organometallic ligand substitution reactions were investigated: (1) an achiral reactive system consisting of Rh(4)(CO)(12)+PPh(3)right harpoon over left harpoonRh(4)(CO)(11)PPh(3)+CO in n-hexane under argon; and (2) a chiral reactive system consisting of Rh(4)(CO)(12)+(S)-BINAPright harpoon over left harpoonRh(4)(CO)(10)BINAP+2CO in cyclohexane under argon. These two reactions were run at ultra high dilution. In both multi-component reactive systems the concentrations of all the solutes were less than 40ppm and many solute concentrations were just 1-10ppm. In situ spectroscopic measurements were carried out using UV-vis (Ultraviolet-visible) spectroscopy and UV-vis CD spectroscopy on the reactive organometallic systems (1) and (2), respectively. The BTEM algorithm was applied to these spectroscopic data sets. The reconstructed UV-vis pure component spectra of Rh(4)(CO)(12), Rh(4)(CO)(11)PPh(3) and Rh(4)(CO)(10)BINAP as well as the reconstructed UV-vis CD pure component spectra of Rh(4)(CO)(10)BINAP were successfully obtained from BTEM analyses. All these reconstructed pure component spectra are in good agreement with the experimental reference spectra. The concentration profiles of the present species were obtained by performing a least square fit with mass balance constraints for the reactions (1) and (2). The present results indicate that UV-vis and UV-vis-CD spectroscopies can be successfully combined with an appropriate chemometric technique in order to monitor reactive organometallic systems having UV and Vis chromophores.

  17. A thermochemically derived global reaction mechanism for detonation application

    NASA Astrophysics Data System (ADS)

    Zhu, Y.; Yang, J.; Sun, M.

    2012-07-01

    A 4-species 4-step global reaction mechanism for detonation calculations is derived from detailed chemistry through thermochemical approach. Reaction species involved in the mechanism and their corresponding molecular weight and enthalpy data are derived from the real equilibrium properties. By substituting these global species into the results of constant volume explosion and examining the evolution process of these global species under varied conditions, reaction paths and corresponding rates are summarized and formulated. The proposed mechanism is first validated to the original chemistry through calculations of the CJ detonation wave, adiabatic constant volume explosion, and the steady reaction structure after a strong shock wave. Good agreement in both reaction scales and averaged thermodynamic properties has been achieved. Two sets of reaction rates based on different detailed chemistry are then examined and applied for numerical simulations of two-dimensional cellular detonations. Preliminary results and a brief comparison between the two mechanisms are presented. The proposed global mechanism is found to be economic in computation and also competent in description of the overall characteristics of detonation wave. Though only stoichiometric acetylene-oxygen mixture is investigated in this study, the method to derive such a global reaction mechanism possesses a certain generality for premixed reactions of most lean hydrocarbon mixtures.

  18. 2013 INORGANIC REACTION MECHANISMS GORDON RESEARCH CONFERENCE (MARCH 3-8, 2013 - HOTEL GALVEZ, GALVESTON TX)

    SciTech Connect

    Abu-Omar, Mahdi M.

    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.

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

    SciTech Connect

    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.

  20. Cation Clock Reactions for the Determination of Relative Reaction Kinetics in Glycosylation Reactions: Applications to Gluco- and Mannopyranosyl Sulfoxide and Trichloroacetimidate Type Donors

    PubMed Central

    Adero, Philip O.; Furukawa, Takayuki; Huang, Min; Mukherjee, Debaraj; Retailleau, Pascal; Bohé, Luis

    2015-01-01

    The development of a cation clock method based on the intramolecular Sakurai reaction for probing the concentration dependence of the nucleophile in glycosylation reactions is described. The method is developed for the sulfoxide and trichloroacetimidate glycosylation protocols. The method reveals that O-glycosylation reactions have stronger concentration dependencies than C-glycosylation reactions consistent with a more associative, SN2-like character. For the 4,6-O-benzylidene-directed mannosylation reaction a significant difference in concentration dependence is found for the formation of the β- and α-anomers suggesting a difference in mechanism and a rationale for the optimization of selectivity regardless of the type of donor employed. In the mannose series the cyclization reaction employed as clock results in the formation of cis and trans-fused oxabicyclo[4,4,0]decanes as products with the latter being strongly indicative of the involvement of a conformationally mobile transient glycosyl oxocarbenium ion. With identical protecting group arrays cyclization in the glucopyranose series is more rapid than in the mannopyranose manifold. The potential application of related clock reactions in other carbenium ion-based branches of organic synthesis is considered. PMID:26207807

  1. Jet-A reaction mechanism study for combustion application

    NASA Technical Reports Server (NTRS)

    Lee, Chi-Ming; Kundu, Krishna; Acosta, Waldo

    1991-01-01

    Simplified chemical kinetic reaction mechanisms for the combustion of Jet A fuel was studied. Initially, 40 reacting species and 118 elementary chemical reactions were chosen based on a literature review. Through a sensitivity analysis with the use of LSENS General Kinetics and Sensitivity Analysis Code, 16 species and 21 elementary chemical reactions were determined from this study. This mechanism is first justified by comparison of calculated ignition delay time with the available shock tube data, then it is validated by comparison of calculated emissions from the plug flow reactor code with in-house flame tube data.

  2. Jet-A reaction mechanism study for combustion application

    NASA Technical Reports Server (NTRS)

    Lee, Chi-Ming; Kundu, Krishna; Acosta, Waldo

    1991-01-01

    Simplified chemical kinetic reaction mechanisms for the combustion of Jet A fuel are studied. Initially 40 reacting species and 118 elementary chemical reactions were chosen based on the literature review of previous works. Through a sensitivity analysis with the use of LSENS General Kinetics and Sensitivity Analysis Code, 16 species and 21 elementary chemical reactions were determined from this study. This mechanism is first justified by comparison of calculated ignition delay time with available shock tube data, then it is validated by comparison of calculated emissions from plug flow reactor code with in-house flame tube data.

  3. PALLADIUM-CATALYZED OXIDATION OF STYRENE AND ALKENES IN PRESENCE OF IONIC LIQUIDS (WACKER REACTION)

    EPA Science Inventory

    The use of ionic liquids in various synthetic transformations is gaining significance due to the enhanced reaction rates, potential for recycling and compatibility with various organic compounds and organometallic catalysts. Palladium-catalyzed oxidation of styrene and other alk...

  4. Atomic-scale insight into the formation, mobility and reaction of Ullmann coupling intermediates.

    PubMed

    Lewis, Emily A; Murphy, Colin J; Liriano, Melissa L; Sykes, E Charles H

    2014-01-28

    The Ullmann reaction of bromobenzene, the simplest coupling reagent, to form biphenyl on a Cu surface proceeds via a highly mobile organometallic intermediate in which two phenyl groups extract and bind a single surface Cu atom.

  5. Absorption of organic compounds and organometallics on ceramic substrates for wear reduction

    SciTech Connect

    Kennedy, P.J.; Agarwala, V.S.

    1996-12-31

    The concept of employing thermally stable compounds (that is, metal oxides) as high temperature vapor phase ceramic lubricants was investigated. A major part of this study was devoted to the development of various calorimetric and tribological techniques that could be used to determine interfacial reactions between thermally stable compounds and ceramic substrates such as zirconia and alumina. This interaction is pivotal in understanding the mechanism of high temperature lubricity. The approach consisted of selecting low sublimation temperature materials and measuring their thermodynamic interactions as vapors with the ceramic substrates. The materials studied included two easily sublimable organic compounds (that is, naphthalene and salicylic acid) and several organometallics (for example, copper phthalocyanine). Thermodynamic data such as heat of adsorption, packing density, and reversibility of the adsorption were obtained on some of these compounds and were related to wear characteristics. All of these compounds provided effective lubrication at room temperature. Copper phthalocyanine was an effective lubricant at temperatures up to 400 C.

  6. Anodic Deposition of a Robust Iridium-Based Water-Oxidation Catalyst from Organometallic Precursors

    SciTech Connect

    Blakemore, James D; Schley, Nathan D; Olack, G.; Incarvito, Christopher D; Brudvig, Gary W; Crabtree, Robert H

    2011-01-01

    Artificial photosynthesis, modeled on natural light-driven oxidation of water in Photosystem II, holds promise as a sustainable source of reducing equivalents for producing fuels. Few robust water-oxidation catalysts capable of mediating this difficult four-electron, four-proton reaction have yet been described. We report a new method for generating an amorphous electrodeposited material, principally consisting of iridium and oxygen, which is a robust and long-lived catalyst for water oxidation, when driven electrochemically. The catalyst material is generated by a simple anodic deposition from Cp*Ir aqua or hydroxo complexes in aqueous solution. This work suggests that organometallic precursors may be useful in electrodeposition of inorganic heterogeneous catalysts.

  7. Evaluation of charged-particle reactions for fusion applications

    SciTech Connect

    White, R.M.; Resler, D.A.; Warshaw, S.I.

    1991-01-01

    New evaluations of the total reaction cross sections for {sup 2}H(d,n){sup 3}He, {sup 2}H(d,p){sup 3}H, {sup 3}H(t,2n){sup 4}He,{sup 3}H(d,n){sup 4}He, and {sup 3}He(d,p){sup 4}He have been completed. These evaluations are based on all known published data from 1946 to 1990 and include over 1150 measured data points from 67 references. The purpose of this work is to provide a consistent and well-documented set of cross sections for use in calculations relating to fusion energy research. A new thermonuclear data file, TDF, and a library of FORTRAN subprograms to read the file have been developed. Calculated from the new evaluations, the TDF file contains information on the Maxwellian-averaged reaction rates as a function of reaction and plasma temperature and the Maxwellian-averaged average energy of the interacting particles and reaction products. Routines are included that provide thermally-broadened spectral information for the secondary reaction products. 67 refs., 18 figs.

  8. Bu4N+ alkoxide-initiated/autocatalytic addition reactions with organotrimethylsilanes.

    PubMed

    Das, Manas; O'Shea, Donal F

    2014-06-20

    The use of Me3SiO(-)/Bu4N(+) as a general activator of organotrimethylsilanes for addition reactions has been established. The broad scope of the method offers trimethylsilanes (including acetate, allyl, propargyl, benzyl, dithiane, heteroaryl, and aryl derivatives) as bench-stable organometallics that can be readily utilized as carbanion equivalents for synthesis. Reactions are achieved at rt without the requirement of specialized precautions that are commonplace for other organometallics.

  9. Effectiveness of various organometallics as antiwear additives in mineral oil

    NASA Technical Reports Server (NTRS)

    Buckley, D. H.

    1977-01-01

    Sliding friction experiments were conducted with 1045 steel contacting 302 stainless steel and lubricated with various organometallics in mineral oil. Auger emission spectroscopy was used to determine the element present in the wear contact zone. The results indicate that there are organometallics which are as effective an antiwear additives as the commonly used zinc dialkyl dithiophosphate. These include dimethyl cadmium, triphenyl lead thiomethoxide, and triphenyl tin chloride. The additives were examined in concentrations to 1 weight percent. With dimethyl cadmium at concentrations of 0.5 weight percent and above, cadmium was detected in the contact zone. Coincident with the detection of cadmium, a marked decrease in the friction coefficient was observed. All additives examined reduced friction, but only the aforementioned reduced wear to a level comparable to that observed with zinc dialkyl dithiophosphate.

  10. Metal-organometallic polymers and frameworks derived from facially metalated arylcarboxylates

    NASA Astrophysics Data System (ADS)

    Kumalah Robinson, Sayon A.

    The interest in coordination polymers, also known as metal-organic frameworks, has risen drastically over the past 2 decades. In this time, the field has matured and given rise to a diverse range of crystalline structures possessing various functionalities. Coordination polymers are typically formed from the self assembly of metal ions which serve as nodes and organic ligands which act as bridges. By the careful selection of the organic ligand and the metal ion, the overall physical properties of the material may be tuned. In this work, the use of organometallic bridging ligands are explored using facially metalated aryl carboxylates ligands to synthesize metal-organometallic frameworks (MOMFs). Therefore, with the aim of synthesizing [CpM]+-functionalized (M = FeII, RuII; Cp = cyclopentadienyl) coordination polymers and metal organic frameworks, various [CpFe]+and [CpRu] + functionalized aryl carboxylates were synthesized and characterized. In particular, the [CpFe]+-functionalized benzoic, terephthalic and trimesic acids as well as the [CpRu]+-functionalized terephthalic acid were made. Using the [CpFe]+ complexes of the benzoic and terephthalic acid as bridging ligands, a number of 1D and 2D coordination polymers were synthesized. For instance, the reaction of [CpFe]+-functionalized benzoic acid with CdCl2 yielded the 1D chain of [Cd(benzoate)Cl 2]˙H2O whilst the reaction of [CpFe]+-functionalized terephthalic acid with Cu(NO3)2˙6H2O yielded a 2D square grid sheet. Using the [CpFe]+-functionalized terephthalic acid, a series of polymorphic, 3D metal-organometallic frameworks of the general formula [M3(terephthalate)4(mu-H2O)2(H 2O)2][NO3]2˙xsolvent (M = Co II, NiII ; solvent = EtOH, DMF, H2O) were synthesized and fully characterized. The polymorphic nature of these frameworks may be attributed to the different orientations that the [CpFe]+ moiety may adapt within the cavities in the 3D frameworks. The selectivity of the desolvated forms of the polymorphs for

  11. An Organometallic Future in Green and Energy Chemistry?

    SciTech Connect

    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.

  12. Organometallic nanoprobe to enhance optical response on the polycyclic aromatic hydrocarbon benzo[a]pyrene immunoassay using SERS technology.

    PubMed

    Dribek, Mohamed; Rinnert, Emmanuel; Colas, Florent; Crassous, Marie-Pierre; Thioune, Néné; David, Catalina; de la Chapelle, Marc; Compère, Chantal

    2014-08-12

    We demonstrated the use of a new organometallic nanoprobe for competitive surface-enhanced Raman scattering (SERS) immunoassay devoted to the detection of polycyclic aromatic hydrocarbons (PAH) such as benzo[a]pyrene (BaP) in seawater. The nanoprobes are gold nanoparticles (GNPs) labeled by a Raman reporter, the 5,5'-dithiobis(succinimidyl-2-nitrobenzoate) (DSNB) and functionalized with monoclonal antibodies anti-BaP. The antibodies are bound with a high specificity to the analyte while the GNPs enhanced the Raman scattering of the DSNB. This type of immunoassay involved the grafting of BaP onto a sensing surface. Thus, NH2-terminated self-assembled monolayer is formed on the surface of gold substrate using cysteamine. Amines finally reacted with 6-formylbenzo[a]pyrene. So, this SERS detection involves four steps: (i) the nanoprobes are incubated with the sample; (ii) a drop of the mixture is then put onto the substrate; (iii) the surface is rinsed; and (iv) the surface is analyzed by Raman spectroscopy. To synthesize the nanoprobes, firstly, we prepared GNPs according to Frens' method. Then, GNPs were spontaneously labeled by the DSNB Raman reporter, thanks to a strong gold-sulfur interaction. Thereafter, BaP antibodies were cross-linked to the DSNB labeled GNPs by reaction of proteins primary amino groups with N-hydroxyl succinimide (NHS). Before use in SERS detection, their activity was controlled by surface plasmon resonance technique. The present method allows us to detect BaP at trace concentration (2 nmol/L). The results demonstrate that the proposed method has a great potential for application in the monitoring of seawater.

  13. Titanium-nitrogen reaction investigated for application to gettering systems

    NASA Technical Reports Server (NTRS)

    Arntzen, J. D.; Coleman, L. F.; Kyle, M. L.; Pierce, R. D.

    1968-01-01

    Titanium is one of several gettering materials available for removing nitrogen from inert gases. The reaction rate of titanium-metal sponge and nitrogen in argon-nitrogen mixtures was studied at 900 degrees C. The rate was found to depend upon the partial pressure of nitrogen in the gas phase. Mathematical relationships simulate titanium systems.

  14. Kinetic modelling of GlmU reactions - prioritization of reaction for therapeutic application.

    PubMed

    Singh, Vivek K; Das, Kaveri; Seshadri, Kothandaraman

    2012-01-01

    Mycobacterium tuberculosis(Mtu), a successful pathogen, has developed resistance against the existing anti-tubercular drugs necessitating discovery of drugs with novel action. Enzymes involved in peptidoglycan biosynthesis are attractive targets for antibacterial drug discovery. The bifunctional enzyme mycobacterial GlmU (Glucosamine 1-phosphate N-acetyltransferase/ N-acetylglucosamine-1-phosphate uridyltransferase) has been a target enzyme for drug discovery. Its C- and N- terminal domains catalyze acetyltransferase (rxn-1) and uridyltransferase (rxn-2) activities respectively and the final product is involved in peptidoglycan synthesis. However, the bifunctional nature of GlmU poses difficulty in deciding which function to be intervened for therapeutic advantage. Genetic analysis showed this as an essential gene but it is still unclear whether any one or both of the activities are critical for cell survival. Often enzymatic activity with suitable high-throughput assay is chosen for random screening, which may not be the appropriate biological function inhibited for maximal effect. Prediction of rate-limiting function by dynamic network analysis of reactions could be an option to identify the appropriate function. With a view to provide insights into biochemical assays with appropriate activity for inhibitor screening, kinetic modelling studies on GlmU were undertaken. Kinetic model of Mtu GlmU-catalyzed reactions was built based on the available kinetic data on Mtu and deduction from Escherichia coli data. Several model variants were constructed including coupled/decoupled, varying metabolite concentrations and presence/absence of product inhibitions. This study demonstrates that in coupled model at low metabolite concentrations, inhibition of either of the GlmU reactions cause significant decrement in the overall GlmU rate. However at higher metabolite concentrations, rxn-2 showed higher decrement. Moreover, with available intracellular concentration of the

  15. Steroselective synthesis with and without organometallics

    SciTech Connect

    Ghosez, L.

    1995-12-31

    Cycloaddition and cyclocondensation reactions are of great synthetic importance for the formation of monocyclic and polycyclic carbocycles and heterocycles. Also they make a maximum use of the atomic content of the starting material and show therefore a maximum {open_quotes}atomic efficiency{close_quotes}.

  16. Simplified jet fuel reaction mechanism for lean burn combustion application

    NASA Technical Reports Server (NTRS)

    Lee, Chi-Ming; Kundu, Krishna; Ghorashi, Bahman

    1993-01-01

    Successful modeling of combustion and emissions in gas turbine engine combustors requires an adequate description of the reaction mechanism. Detailed mechanisms contain a large number of chemical species participating simultaneously in many elementary kinetic steps. Current computational fluid dynamic models must include fuel vaporization, fuel-air mixing, chemical reactions, and complicated boundary geometries. A five-step Jet-A fuel mechanism which involves pyrolysis and subsequent oxidation of paraffin and aromatic compounds is presented. This mechanism is verified by comparing with Jet-A fuel ignition delay time experimental data, and species concentrations obtained from flametube experiments. This five-step mechanism appears to be better than the current one- and two-step mechanisms.

  17. The application of a monolithic triphenylphosphine reagent for conducting Ramirez gem-dibromoolefination reactions in flow

    PubMed Central

    Roper, Kimberley A; Berry, Malcolm B

    2013-01-01

    Summary The application of a monolithic form of triphenylphosphine to the Ramirez gem-dibromoolefination reaction using flow chemistry techniques is reported. A variety of gem-dibromides were synthesised in high purity and excellent yield following only removal of solvent and no further off-line purification. It is also possible to perform the Appel reaction using the same monolith and the relationship between the mechanisms of the two reactions is discussed. PMID:24062843

  18. Bifurcation of Singular Solutions in Reversible Systems and Applications to Reaction-Diffusion Equations.

    DTIC Science & Technology

    1981-08-01

    bifurcation of trajectories connecting saddle points from stationary solutions is studied. As an application, reaction-diffusion models in one space...to reaction- diffusion models are discussed. We obtain solutions, which may be considered *one-dimensional analogues of the patterns of concentric...Oscillating sina,!ar solutions connected with Hopf bifurcations We consider a general chemical reaction model given by an equation 2au _2u (6.1) =F( ,u) + D

  19. Sunlight induced cycloaddition and host-guest property of self-assembled organometallic macrocycles based on a versatile building block.

    PubMed

    Wu, Tong; Weng, Lin-Hong; Jin, Guo-Xin

    2012-05-11

    Organometallic rectangle 1 which undergoes [2+2] cycloaddition upon irradiation with sunlight and organometallic prism 3 which displayed interesting host-guest property were self-assembled based on a versatile building block.

  20. Photo Lewis acid generators: photorelease of B(C6F5)3 and applications to catalysis.

    PubMed

    Khalimon, Andrey Y; Shaw, Bryan K; Marwitz, Adam J V; Piers, Warren E; Blackwell, James M; Parvez, Masood

    2015-11-07

    A series of molecules capable of releasing of the strong organometallic Lewis acid B(C6F5)3 upon exposure to 254 nm light have been developed. These photo Lewis acid generators (PhLAGs) can now serve as photoinitiators for several important B(C6F5)3-catalyzed reactions. Herein is described the synthesis of the triphenylsulfonium and diphenyliodonium salts of carbamato- and hydridoborates, their establishment as PhLAGs, and studies aimed at defining the mechanism of borane release. Factors affecting these photolytic reactions and the application of this concept to photoinduced hydrosilylation reactions and construction of siloxane scaffolds are also discussed.

  1. Applications of a superconducting solenoidal separator in the experimental investigation of nuclear reactions

    NASA Astrophysics Data System (ADS)

    Hinde, D. J.; Carter, I. P.; Dasgupta, M.; Simpson, E. C.; Cook, K. J.; Kalkal, Sunil; Luong, D. H.; Williams, E.

    2017-01-01

    This paper describes applications of a novel superconducting solenoidal separator, with magnetic fields up to 8 Tesla, for studies of nuclear reactions using the Heavy Ion Accelerator Facility at the Australian National University.

  2. Ab initio Quantum Chemical Reaction Kinetics: Recent Applications in Combustion Chemistry (Briefing Charts)

    DTIC Science & Technology

    2015-06-28

    Charts 3. DATES COVERED (From - To) June 2015-June 2015 4. TITLE AND SUBTITLE AB INITIO QUANTUM CHEMICAL REACTION KINETICS: RECENT APPLICATIONS IN...Unlimited. 13. SUPPLEMENTARY NOTES Briefing Charts presented at 9th Int. Conf. Chemical Kinetics; Ghent, Belgium; 28 Jun 2015. PA#15351. 14. ABSTRACT...ghanshyam.vaghjiani@us.af.mil Ab initio Quantum Chemical Reaction Kinetics: Recent Applications in Combustion Chemistry Ghanshyam L. Vaghjiani* DISTRIBUTION A

  3. Divergence between organometallic and single-electron-transfer mechanisms in copper(II)-mediated aerobic C-H oxidation.

    PubMed

    Suess, Alison M; Ertem, Mehmed Z; Cramer, Christopher J; Stahl, Shannon S

    2013-07-03

    Copper(II)-mediated C-H oxidation is the subject of extensive interest in synthetic chemistry, but the mechanisms of many of these reactions are poorly understood. Here, we observe different products from Cu(II)-mediated oxidation of N-(8-quinolinyl)benzamide, depending on the reaction conditions. Under basic conditions, the benzamide group undergoes directed C-H methoxylation or chlorination. Under acidic conditions, the quinoline group undergoes nondirected chlorination. Experimental and computational mechanistic studies implicate an organometallic C-H activation/functionalization mechanism under the former conditions and a single-electron-transfer mechanism under the latter conditions. This rare observation of divergent, condition-dependent mechanisms for oxidation of a single substrate provides a valuable foundation for understanding Cu(II)-mediated C-H oxidation reactions.

  4. A Photoferroelectric Perovskite-Type Organometallic Halide with Exceptional Anisotropy of Bulk Photovoltaic Effects.

    PubMed

    Sun, Zhihua; Liu, Xitao; Khan, Tariq; Ji, Chengmin; Asghar, Muhammad Adnan; Zhao, Sangen; Li, Lina; Hong, Maochun; Luo, Junhua

    2016-05-23

    Perovskite-type ferroelectrics composed of organometallic halides are emerging as a promising alternative to conventional photovoltaic devices because of their unique photovoltaic effects (PVEs). A new layered perovskite-type photoferroelectric, bis(cyclohexylaminium) tetrabromo lead (1), is presented. The material exhibits an exceptional anisotropy of bulk PVEs. Upon photoexcitation, superior photovoltaic behaviors are created along its inorganic layers, which are composed of corner-sharing PbBr6 octahedra. Semiconducting activity with remarkable photoconductivity is achieved in the vertical direction, showing sizeable on/off current ratios (>10(4) ), which compete with the most active photovoltaic material CH3 NH3 PbI3 . In 1 the temperature-dependence of photovoltage coincides fairly well with that of polarization, confirming the dominant role of ferroelectricity in such highly anisotropic PVEs. This finding sheds light on bulk PVEs in ferroelectric materials, and promotes their application in optoelectronic devices.

  5. Application of semiclassical methods to reaction rate theory

    SciTech Connect

    Hernandez, Rigoberto

    1993-11-01

    This work is concerned with the development of approximate methods to describe relatively large chemical systems. This effort has been divided into two primary directions: First, we have extended and applied a semiclassical transition state theory (SCTST) originally proposed by Miller to obtain microcanonical and canonical (thermal) rates for chemical reactions described by a nonseparable Hamiltonian, i.e. most reactions. Second, we have developed a method to describe the fluctuations of decay rates of individual energy states from the average RRKM rate in systems where the direct calculation of individual rates would be impossible. Combined with the semiclassical theory this latter effort has provided a direct comparison to the experimental results of Moore and coworkers. In SCTST, the Hamiltonian is expanded about the barrier and the ``good`` action-angle variables are obtained perturbatively; a WKB analysis of the effectively one-dimensional reactive direction then provides the transmission probabilities. The advantages of this local approximate treatment are that it includes tunneling effects and anharmonicity, and it systematically provides a multi-dimensional dividing surface in phase space. The SCTST thermal rate expression has been reformulated providing increased numerical efficiency (as compared to a naive Boltzmann average), an appealing link to conventional transition state theory (involving a ``prereactive`` partition function depending on the action of the reactive mode), and the ability to go beyond the perturbative approximation.

  6. Application of cycloaddition reactions to the syntheses of novel boron compounds.

    PubMed

    Zhu, Yinghuai; Siwei, Xiao; Maguire, John A; Hosmane, Narayan S

    2010-12-21

    This review covers the application of cycloaddition reactions in forming the boron-containing compounds such as symmetric star-shaped boron-enriched dendritic molecules, nano-structured boron materials and aromatic boronic esters. The resulting boron compounds are potentially important reagents for both materials science and medical applications such as in boron neutron capture therapy (BNCT) in cancer treatment and as drug delivery agents and synthetic intermediates for carbon-carbon cross-coupling reactions. In addition, the use of boron cage compounds in a number of cycloaddition reactions to synthesize unique aromatic species will be reviewed briefly.

  7. Ruthenium-Catalyzed Azide Alkyne Cycloaddition Reaction: Scope, Mechanism, and Applications.

    PubMed

    Johansson, Johan R; Beke-Somfai, Tamás; Said Stålsmeden, Anna; Kann, Nina

    2016-12-14

    The ruthenium-catalyzed azide alkyne cycloaddition (RuAAC) affords 1,5-disubstituted 1,2,3-triazoles in one step and complements the more established copper-catalyzed reaction providing the 1,4-isomer. The RuAAC reaction has quickly found its way into the organic chemistry toolbox and found applications in many different areas, such as medicinal chemistry, polymer synthesis, organocatalysis, supramolecular chemistry, and the construction of electronic devices. This Review discusses the mechanism, scope, and applications of the RuAAC reaction, covering the literature from the last 10 years.

  8. Sterically Hindered Square-Planar Nickel(II) Organometallic Complexes: Preparation, Characterization, and Substitution Behavior

    ERIC Educational Resources Information Center

    Martinez, Manuel; Muller, Guillermo; Rocamora, Merce; Rodriguez, Carlos

    2007-01-01

    The series of experiments proposed for advanced undergraduate students deal with both standard organometallic preparative methods in dry anaerobic conditions and with a kinetic study of the mechanisms operating in the substitution of square-planar complexes. The preparation of organometallic compounds is carried out by transmetallation or…

  9. New Twists and Turns for Actinide Chemistry: Organometallic Infinite Coordination Polymers of Thorium Diazide.

    PubMed

    Monreal, Marisa J; Seaman, Lani A; Goff, George S; Michalczyk, Ryszard; Morris, David E; Scott, Brian L; Kiplinger, Jaqueline L

    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.

  10. Discriminatory Questions and Applicant Reactions in the Employment Interview.

    ERIC Educational Resources Information Center

    Saks, Alan M.; And Others

    This study investigated the effects of discriminatory interview questions on applicants' perceptions and intentions toward an organization. Participants included 118 graduate business students (59 percent male), average age of 31 with more than eight years of full-time work experience. Discriminatory questions addressed handicaps, plans for…

  11. Nonlinear phenomena at geological reaction fronts with energy applications

    SciTech Connect

    Ortoleva, P.

    1989-01-01

    Interaction of aqueous fluids with the rock matrix within which they reside can yield a variety of phenomena due to the coupling of reaction transport and mechanical processes; many of these have potentially important implications for exploration and exploitation of energy and mineral resources. We investigated effects of nucleation to produce banded precipitation; Darcy-mineral dissolution coupling to produce scalloped, fingered and more complex alteration front morphologies, and diagenetic alteration in chemically complex, multi-mineralic systems. Migration of methane driven by buoyancy effects was shown to lead to cellular and temporally oscillatory flows. Sandstones at depth experiencing pressure solution display unstable compaction leading to formation of stylolites and band-like regions of augmented compaction alternating with low porosity bands with augmented overgrowth. It was shown that transfer of natural gas from shale source rock into neighboring sandstones could occur through a series of discrete pulsatile events through a cycle of fracturing and healing.

  12. Organometallic Chemical Vapor Deposition Growth of Antimony Compounds

    NASA Astrophysics Data System (ADS)

    Chiang, Peng-Kuen

    This research is motivated by the desire to synthesize Sb III-V materials, including GaAs(,1-x)Sb(,x), InSb, and InAs(,1-x)Sb(,x). Ga-As-Sb system is known to have a significant solid phase miscibility gap from x = 0.2 to x = 0.8 at 600(DEGREES)C using a liquid phase epitaxy (LPE) growth technique. In this work, organometallic chemical vapor deposition (OM-CVD) has been shown to be a suitable growth technique for growing GaAs(,1-x)Sb(,x) alloys lying in the region of solid immiscibility. Conditions for growth of GaAs(,1-x)Sb(,x) layers with x as high as 0.7 on GaAs substrates are described for temperatures between 580 and 650(DEGREES)C. Effects of substrate orientation on growth characteristics are noted, and comparisons of growth on (511) and (100) GaAs faces are made. The experimental results indicate that growth is being controlled by surface reaction kinetics. A simple model based on kinetic control is presented. InSb is one of the most extensively examined semiconductors because of the small energy bandgap which is suitable for 3-5 (mu)m wavelength detection, and it also has highest mobility of any III-V compounds. OM-CVD has been used to epitaxially grow high quality InSb for the first time in this work. InSb with excellent morphology was achieved on both (100) and (111)B InSb substrates. The measured electron mobility at 300(DEGREES)K of undoped InSb grown on (100) GaAs semi-insulating substrates was 40,000 cm('2)/V -sec at a carrier concentration of N(,D)-N(,A) = 1.2 x 10('15)cm(' -3) has been measured at 77(DEGREES)K.Experimental data suggests that a dislocation scattering mechanism represents a significant mobility limiting process. InAs(,1-x)Sb(,x), with x (TURN) 0.6, has the lowest bandgap (=0.1 eV at 300(DEGREES)K) of any of the III-V ternary compounds. This bandgap is suitable for detectors in the 8-12 (mu)m wavelength region where an atmosphere window exists. So far, InAs(,1-x)Sb(,x) with 0.55 < x < 0.75 has not been achieved by LPE and molecular

  13. Application of semiconductor light sources for investigations of photochemical reactions

    NASA Astrophysics Data System (ADS)

    Landgraf, S.

    2001-09-01

    Semiconductor light sources, like laser diodes or ultrabright light emitting diodes, are widely used in optical spectroscopy. In this presentation an overview of applications in photochemistry is given. Since the beginning of the 1990s an increasing number of publications with the application of semiconductor light sources appeared. Three different techniques were used: single photon counting with short pulses, phase-modulation fluorometry using a conventional modulation spectrometer, or a lock-in amplifier. Using continuous wave laser diodes in the visible region, which are available from 690 to 630 nm (and, recently, down to 400 nm), a new compact fluorescence spectrometer was developed in our laboratory. Using the phase fluorometric method, measurements down to 100 ps are now possible. Values can be measured in steps of 10 ps with good reproducibility using a high-frequency signal generator and a GHz digital storage oscilloscope. Several investigations have been carried out applying this technique including time-resolved detection of crude oil as an example for possible practical applications.

  14. [Azoic color reaction of flavonoids and their analytical application].

    PubMed

    Yu, Qian; Chen, Xiao-Kang; Luo, Zong-Ming; Yang, Chi; Mai, Hua-Kun

    2004-08-01

    In NH4Cl-NH3 H2O buffer solution of pH 10.4, diazo salt of p-sulfodiazoben-zene chloride reacts with rutin, morin, genistin, quercetin, hesperidin, baicalin and daidzin to form color azo-compounds. These azo-compounds have an absorption maximum at 430 nm except for baicalin azo-compound, which has an absorption maximum at 380 nm. The sensitivity of azoic color reaction is reductive in the order of above flavonoids and the molar absorptivity is maximum for rutin and is minimal for daidzin among these azo-compounds, i. e. 3.28 x 10(4) and 8.3 x 10(2) L x mol(-1) x cm(-1) respectively. The proposed spectrophotometry has been applied to th determination of flavonoids in sophora seed and soybean cake. The RSDs of the method were found to be in the range of 0.75-4.48%, and the recoveries were in the range of 99.3%-105.0%.

  15. Ceramics Derived from Organo-Metallic Precursors

    DTIC Science & Technology

    1991-10-01

    of 4th International Conference on Ultrastructure Processing. 13. J.M. Boulton, S. Subramoney and D.R. Uhlmann: "Seeded Transformation of Aluminum ...evenly distributed throughout the bulk of the superconductor film; and, most importantly, the aluminum has diffused through almost the entire...present work was undertaken to explore the feasibility of such coating for application to both oxide ( aluminum oxide) and non-oxide (silicon carbide and

  16. The organometallic fluorine chemistry of palladium and rhodium: studies toward aromatic fluorination.

    PubMed

    Grushin, Vladimir V

    2010-01-19

    Although springing from two established fields, organometallic chemistry and fluorine chemistry, organometallic fluorine chemistry is still in its early stages. However, developments in this area are expected to provide new tools for the synthesis of selectively fluorinated organic compounds that have been in high demand. Selectively fluorinated organic molecules currently account for up to 40% of all agrochemicals and 20% of all pharmaceuticals on the market. Our research efforts have been focused on the development of new organometallic and catalytic methods for the selective introduction of fluorine and the CF(3) group into the aromatic ring. Monofluorinated and trifluoromethylated aromatic compounds are still made by the old technologies that employ stoichiometric quantities of hazardous and costly materials. In this Account, we describe our studies toward the development of safe, catalytic alternatives to these methods. We have synthesized, characterized, and studied the reactivity of the first aryl palladium(II) fluoride complexes. We have demonstrated for the first time that a Pd-F bond can be formed in a soluble and isolable molecular complex: this bond is more stable than previously thought. Toward the goal of fluoroarene formation via Ar-F reductive elimination, we have studied a number of sigma-aryl Pd(II) fluorides stabilized by various P, N, and S ligands. It has been established that numerous conventional tertiary phosphine ligands, most popular in Pd catalysis, are unlikely to be useful for the desired C-F bond formation at the metal center because of the competing, kinetically preferred P-F bond-forming reaction. A metallophosphorane mechanism has been demonstrated for the P-F bond-forming processes at Rh(I) and Pd(II), which rules out the possibility of controlling these reactions by varying the amount of phosphine in the system, a most common and often highly efficient technique in homogeneous catalysis. The novel F/Ph rearrangement of the fluoro

  17. Evaluation of the catalytic decomposition of H2O2 through use of organo-metallic complexes--a potential link to the luminol presumptive blood test.

    PubMed

    Soderquist, Thomas J; Chesniak, Olivia M; Witt, Matthew R; Paramo, Alan; Keeling, Victoria A; Keleher, Jason J

    2012-06-10

    Forensic scientists use several presumptive tests to detect latent blood stains at crime scenes; one of the most recognizable being the luminol reagent. Luminol, under basic conditions, reacts with an oxidizing species which, with the help of a transition metal catalyst facilitates a luminescent response. The typical oxidizing species used in the luminol reaction is hydrogen peroxide (H(2)O(2)). While the luminol reaction has been studied since its inception, the mechanistic pathway is still an area of great debate. Previous work suggests that the luminol reaction with latent blood stains possesses a correlation to the Fenton-Decomposition reaction mechanism, which decomposes H(2)O(2) into the strongly oxidizing hydroxyl radical (*OH) species. This work seeks to understand the luminol reaction on a mechanistic level and to determine if a synergy exists between the chemiluminescence observed in the reaction and the production of the hydroxyl radical via Fenton-like processes. Results indicate that organo-metallic complexes produce hydroxyl radicals at different rates and different concentrations. These findings appear to be related to structural differences in the organo-metallic complex, which conform to the 18 electron rule or are one electron rich/deficient. Furthermore, the production of *OH is controlled by the chemical environment which governs complex stability at high pH conditions, reflective of the luminol process. Model hemoglobin systems reveal a strong correlation between the rate of *OH production via the Fenton-like pathway and maximum chemiluminescent intensity.

  18. Atmospheric pressure synthesis of photoluminescent hybrid materials by sequential organometallic vapor infiltration into polyethylene terephthalate fibers

    SciTech Connect

    Akyildiz, Halil I.; Mousa, Moataz Bellah M.; Jur, Jesse S.

    2015-01-28

    Exposing a polymer to sequential organometallic vapor infiltration (SVI) under low pressure conditions can significantly modify the polymer's chemical, mechanical, and optical properties. We demonstrate that SVI of trimethylaluminum into polyethylene terephthalate (PET) can also proceed readily at atmospheric pressure, and at 60 °C the extent of reaction determined by mass uptake is independent of pressure between 2.5 Torr and 760 Torr. At 120 °C, however, the mass gain is 50% larger at 2.5 Torr relative to that at 760 Torr, indicating that the precursor diffusion in the chamber and fiber matrix decreases at higher source pressure. Mass gain decreases, in general, as the SVI process temperature increases both at 2.5 Torr and 760 Torr attributed to the faster reaction kinetics forming a barrier layer, which prevents further diffusion of the reactive species. The resulting PET/Al-O{sub x} product shows high photoluminescence compared to untreated fibers. A physical mask on the polymer during infiltration at 760 Torr is replicated in the underlying polymer, producing an image in the polymer that is visible under UV illumination. Because of the reduced precursor diffusivity during exposure at 760 Torr, the image shows improved resolution compared to SVI performed under typical 2.5 Torr conditions.

  19. Application of the Solid-Supported Glaser-Hay Reaction to Natural Product Synthesis.

    PubMed

    Lampkowski, Jessica S; Uthappa, Diya M; Halonski, John F; Maza, Johnathan C; Young, Douglas D

    2016-12-16

    The Glaser-Hay coupling of terminal alkynes is a useful synthetic reaction for the preparation of polyynes; however, chemoselectivity issues have precluded its widespread utilization. Conducting the reaction on a solid-support provides a mechanism to alleviate the chemoselectivity issues and provide products in high purities and yields. Moreover, the polyyne core is a key component to several natural products. Herein, we describe the application of a solid-supported Glaser-Hay reaction in the preparation of several natural products. These compounds were then screened for antibacterial activity, illustrating the utility of the methodology.

  20. The CCONE Code System and its Application to Nuclear Data Evaluation for Fission and Other Reactions

    SciTech Connect

    Iwamoto, O. Iwamoto, N.; Kunieda, S.; Minato, F.; Shibata, K.

    2016-01-15

    A computer code system, CCONE, was developed for nuclear data evaluation within the JENDL project. The CCONE code system integrates various nuclear reaction models needed to describe nucleon, light charged nuclei up to alpha-particle and photon induced reactions. The code is written in the C++ programming language using an object-oriented technology. At first, it was applied to neutron-induced reaction data on actinides, which were compiled into JENDL Actinide File 2008 and JENDL-4.0. It has been extensively used in various nuclear data evaluations for both actinide and non-actinide nuclei. The CCONE code has been upgraded to nuclear data evaluation at higher incident energies for neutron-, proton-, and photon-induced reactions. It was also used for estimating β-delayed neutron emission. This paper describes the CCONE code system indicating the concept and design of coding and inputs. Details of the formulation for modelings of the direct, pre-equilibrium and compound reactions are presented. Applications to the nuclear data evaluations such as neutron-induced reactions on actinides and medium-heavy nuclei, high-energy nucleon-induced reactions, photonuclear reaction and β-delayed neutron emission are mentioned.

  1. The CCONE Code System and its Application to Nuclear Data Evaluation for Fission and Other Reactions

    NASA Astrophysics Data System (ADS)

    Iwamoto, O.; Iwamoto, N.; Kunieda, S.; Minato, F.; Shibata, K.

    2016-01-01

    A computer code system, CCONE, was developed for nuclear data evaluation within the JENDL project. The CCONE code system integrates various nuclear reaction models needed to describe nucleon, light charged nuclei up to alpha-particle and photon induced reactions. The code is written in the C++ programming language using an object-oriented technology. At first, it was applied to neutron-induced reaction data on actinides, which were compiled into JENDL Actinide File 2008 and JENDL-4.0. It has been extensively used in various nuclear data evaluations for both actinide and non-actinide nuclei. The CCONE code has been upgraded to nuclear data evaluation at higher incident energies for neutron-, proton-, and photon-induced reactions. It was also used for estimating β-delayed neutron emission. This paper describes the CCONE code system indicating the concept and design of coding and inputs. Details of the formulation for modelings of the direct, pre-equilibrium and compound reactions are presented. Applications to the nuclear data evaluations such as neutron-induced reactions on actinides and medium-heavy nuclei, high-energy nucleon-induced reactions, photonuclear reaction and β-delayed neutron emission are mentioned.

  2. Second Generation Organometallic Materials for Non-Linear Optical Application

    DTIC Science & Technology

    2009-05-26

    University of Florida I . Project Objectives, Significance and Overview During the past several years in an AFOSR sponsored project our group has...Ar i PR3 rr\\3 PR 3 Pt—=— Ar- PRs n Pt-acetylide oligomer Pt-acetylide polymer Figure 1. Structure of platinum-acetylide materials. Work...Solvent - CH,C1 Energyu»» i /J Figure 9. Top: Structures of TPA-M complexes. Bottom: Nonlinear transmission for 10 and 20 mM, CH2C12 solutions of

  3. Organometallic Silicon-Containing Dendrimers and Their Electrochemical Applications

    NASA Astrophysics Data System (ADS)

    Cuadrado, Isabel

    Dendrimers constitute a unique class of macromolecular architectures that differs from all other synthetic macromolecules in its perfectly branched topology, which is constructed from a multifunctional central core and expands to the periphery that becomes denser with increasing generation number (see Chapter 1) [1-5]. Since the pioneering works published in the late 1970s and the mid-1980s [6-8], the design and synthesis of these tree-like, well-defined molecules, which exhibit a unique combination of chemical and physical properties, is a field which has sustained dramatic growth and has generated enthusiastic studies at the frontiers of organic, inorganic, supramolecular and polymer chemistry, and more recently in the fields of nanoscience, biotechnology and medicine [1-5, 9, 10]. Whereas the initial interest in dendrimers was focused on the synthetic and structural characterization challenges that pose their fractal geometries, nanometer sizes and monodisperse nature, in the last decade the emphasis has been placed mainly on modification of the properties of dendritic molecules by their functionalization

  4. Immediate systemic hypersensitivity reaction associated with topical application of Australian tea tree oil.

    PubMed

    Mozelsio, Nancy B; Harris, Kathleen E; McGrath, Kris G; Grammer, Leslie C

    2003-01-01

    Australian tea tree oil has been used as a veterinary antiseptic for many years and, more recently, has been extended into human use. There have been many reports of allergic contact dermatitis and toxicity reactions, but it has never been implicated in immediate systemic hypersensitivity reactions. A 38-year-old man experienced immediate flushing, pruritus, throat constriction, and lightheadedness after topical application of tea tree oil. Our purpose was to determine whether this represented an immunoglobulin E (IgE)--mediated reaction. Skin-prick and intradermal testing was performed, as well as enzyme-linked immunosorbent assays for specific IgG and IgE against tea tree oil. The patient had a positive wheal and flare reaction on intradermal testing with tea tree oil. All five patient controls were negative on skin testing. No specific IgG or IgE was detected. We present the first reported case of an immediate systemic hypersensitivity reaction occurring after topical application of Australian tea tree oil, confirmed by positive wheal and flare reaction on skin testing.

  5. MCNP6 Simulation of Reactions of Interest to FRIB, Medical, and Space Applications

    NASA Astrophysics Data System (ADS)

    Mashnik, Stepan G.

    The latest production-version of the Los Alamos Monte Carlo N-Particle transport code MCNP6 has been used to simulate a variety of particle-nucleus and nucleus-nucleus reactions of academic and applied interest to research subjects at the Facility for Rare Isotope Beams (FRIB), medical isotope production, space-radiation shielding, cosmic-ray propagation, and accelerator applications, including several reactions induced by radioactive isotopes, analyzing production of both stable and radioactive residual nuclei. Here, we discuss examples of validation and verification of MCNP6 by comparing with recent neutron spectra measured at the Heavy Ion Medical Accelerator in Chiba, Japan; spectra of light fragments from several reactions measured recently at GANIL, France; INFN Laboratori Nazionali del Sud, Catania, Italy; COSY of the Jülich Research Center, Germany; and cross sections of products from several reactions measured lately at GSI, Darmstadt, Germany; ITEP, Moscow, Russia; and, LANSCE, LANL, Los Alamos, U.S.A. As a rule, MCNP6 provides quite good predictions for most of the reactions we analyzed so far, allowing us to conclude that it can be used as a reliable and useful simulation tool for various applications for FRIB, medical, and space applications involving stable and radioactive isotopes.

  6. Chemical Reaction Rate Coefficients from Ring Polymer Molecular Dynamics: Theory and Practical Applications.

    PubMed

    Suleimanov, Yury V; Aoiz, F Javier; Guo, Hua

    2016-11-03

    This Feature Article presents an overview of the current status of ring polymer molecular dynamics (RPMD) rate theory. We first analyze the RPMD approach and its connection to quantum transition-state theory. We then focus on its practical applications to prototypical chemical reactions in the gas phase, which demonstrate how accurate and reliable RPMD is for calculating thermal chemical reaction rate coefficients in multifarious cases. This review serves as an important checkpoint in RPMD rate theory development, which shows that RPMD is shifting from being just one of recent novel ideas to a well-established and validated alternative to conventional techniques for calculating thermal chemical rate coefficients. We also hope it will motivate further applications of RPMD to various chemical reactions.

  7. Chemical Reaction Rate Coefficients from Ring Polymer Molecular Dynamics: Theory and Practical Applications

    DOE PAGES

    Suleimanov, Yury V.; Aoiz, F. Javier; Guo, Hua

    2016-11-03

    This Feature Article presents an overview of the current status of ring polymer molecular dynamics (RPMD) rate theory. We first analyze the RPMD approach and its connection to quantum transition-state theory. We then focus on its practical applications to prototypical chemical reactions in the gas phase, which demonstrate how accurate and reliable RPMD is for calculating thermal chemical reaction rate coefficients in multifarious cases. This review serves as an important checkpoint in RPMD rate theory development, which shows that RPMD is shifting from being just one of recent novel ideas to a well-established and validated alternative to conventional techniques formore » calculating thermal chemical rate coefficients. We also hope it will motivate further applications of RPMD to various chemical reactions.« less

  8. Literature information applicable to the reaction of uranium oxides with chlorine to prepare uranium tetrachloride

    SciTech Connect

    Haas, P.A.

    1992-02-01

    The reaction of uranium oxides and chlorine to prepare anhydrous uranium tetrachloride (UCl{sub 4}) are important to more economical preparation of uranium metal. The most practical reactions require carbon or carbon monoxide (CO) to give CO or carbon dioxide (CO{sub 2}) as waste gases. The chemistry of U-O-Cl compounds is very complex with valances of 3, 4, 5, and 6 and with stable oxychlorides. Literature was reviewed to collect thermochemical data, phase equilibrium information, and results of experimental studies. Calculations using thermodynamic data can identify the probable reactions, but the results are uncertain. All the U-O-Cl compounds have large free energies of formation and the calculations give uncertain small differences of large numbers. The phase diagram for UCl{sub 4}-UO{sub 2} shows a reaction to form uranium oxychloride (UOCl{sub 2}) that has a good solubility in molten UCl{sub 4}. This appears more favorable to good rates of reaction than reaction of solids and gases. There is limited information on U-O-Cl salt properties. Information on the preparation of titanium, zirconium, silicon, and thorium tetrachlorides (TiCl{sub 4}, ZrCl{sub 4}, SiCl{sub 4}, ThCl{sub 4}) by reaction of oxides with chlorine (Cl{sub 2}) and carbon has application to the preparation of UCl{sub 4}.

  9. A Review of the Tissue Residue Approach for Organic and Organometallic Compounds in Aquatic Organisms

    EPA Science Inventory

    This paper reviews the tissue residue approach (TRA) for toxicity assessment as it applies to organic chemicals and some organometallic compounds (tin, mercury, and lead). Specific emphasis was placed on evaluating key factors that influence interpretation of critical body resid...

  10. Organometallic Rhenium Complexes Divert Doxorubicin to the Mitochondria.

    PubMed

    Imstepf, Sebastian; Pierroz, Vanessa; Rubbiani, Riccardo; Felber, Michael; Fox, Thomas; Gasser, Gilles; Alberto, Roger

    2016-02-18

    Doxorubicin, a well-established chemotherapeutic agent, is known to accumulate in the cell nucleus. By using ICP-MS, we show that the conjugation of two small organometallic rhenium complexes to this structural motif results in a significant redirection of the conjugates from the nucleus to the mitochondria. Despite this relocation, the two bioconjugates display excellent toxicity toward HeLa cells. In addition, we carried out a preliminarily investigation of aspects of cytotoxicity and present evidence that the conjugates disrupt the mitochondrial membrane potential, are strong inhibitors of human Topoisomerase II, and induce apoptosis. Such derivatives may enhance the therapeutic index of the aggressive parent drug and overcome drug resistance by influencing nuclear and mitochondrial homeostasis.

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

    NASA Astrophysics Data System (ADS)

    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.

  12. Flat Chern Band in a Two-Dimensional Organometallic Framework

    NASA Astrophysics Data System (ADS)

    Liu, Zheng; Wang, Zheng-Fei; Mei, Jia-Wei; Wu, Yong-Shi; Liu, Feng

    2013-03-01

    By combining exotic band dispersion with nontrivial band topology, an interesting type of band, namely the flat chern band (FCB), has recently been proposed, in which carriers experience strong Coulomb interaction as well as topological frustration that in together spawn unprecedented topological strongly-correlated electronic states, such as high-temperature fractional quantum hall state. Despite the proposal of several theoretical lattice models, however, it remains a doubt whether such a ``romance of flatland'' could exist in a real material. Here, we present a first-principles design to realize a nearly FCB right around the Fermi level in a two-dimensional (2D) Indium-Phenylene Organometallic Framework (IPOF). Our design in addition provides a general strategy to synthesize topologically nontrivial materials in virtue of organic chemistry and nanotechnology. Supported by DOE-BES and ARL

  13. Flat Chern Band in a Two-Dimensional Organometallic Framework

    NASA Astrophysics Data System (ADS)

    Liu, Zheng; Wang, Zheng-Fei; Mei, Jia-Wei; Wu, Yong-Shi; Liu, Feng

    2013-03-01

    By combining exotic band dispersion with nontrivial band topology, an interesting type of band structure, namely, the flat Chern band, has recently been proposed to spawn high-temperature fractional quantum Hall states. Despite the proposal of several theoretical lattice models, however, it remains doubtful whether such a “romance of flatland” could exist in a real material. Here, we present a first-principles design of a two-dimensional indium-phenylene organometallic framework that realizes a nearly flat Chern band right around the Fermi level by combining lattice geometry, spin-orbit coupling, and ferromagnetism. An effective four-band model is constructed to reproduce the first-principles results. Our design, in addition, provides a general strategy to synthesize topologically nontrivial materials by virtue of organic chemistry and nanotechnology.

  14. Analysis of trace impurities in organometallic semiconductor grade reagent materials using electrothermal vaporization - inductively coupled plasma spectrometry

    SciTech Connect

    Argentine, M.D.

    1993-12-31

    Trace impurity determinations in volatile, pyrophoric organometallic materials is complicated owing to its chemical nature. Furthermore, trends toward high semiconductor circuit density demand that impurity determinations are performed at increasingly low levels. Volatility of the impurities is also desired as it plays a significant role in impurity incorporation in semiconductor products. Determination of both volatile and nonvolatile impurities in semiconductor-grade organometallic reagent materials has been accomplished using electrothermal vaporization-inductively coupled plasma spectrometry. Solid or liquid materials can be dispensed directly onto a graphite microboat, and application of an appropriate time-temperature ramp allows separation of impurities based on volatility. Temporal separation allows quantitative capabilities on both volatile and nonvolatile signals in a single ETV run. Calibration efforts for volatile impurities have been compared with results from exponential dilution and direct vapor sampling techniques. Nonvolatile impurity determinations can be reasonably performed with aqueous external standard calibration. Inductively coupled plasma-mass spectrometry provides an alternate and more sensitive, multielement detection method. Several spectroscopic and non-spectroscopic difficulties with volatile impurity detection remain. Nonetheless, qualitative and semiquantitative (<50% RSD) determination of most impurities may be performed in a single ETV run.

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

    NASA Astrophysics Data System (ADS)

    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

  16. Organometallic catalysts for primary phosphoric acid fuel cells

    NASA Technical Reports Server (NTRS)

    Walsh, Fraser

    1987-01-01

    A continuing effort by the U.S. Department of Energy to improve the competitiveness of the phosphoric acid fuel cell by improving cell performance and/or reducing cell cost is discussed. Cathode improvement, both in performance and cost, available through the use of a class of organometallic cathode catalysts, the tetraazaannulenes (TAAs), was investigated. A new mixed catalyst was identified which provides improved cathode performance without the need for the use of a noble metal. This mixed catalyst was tested under load for 1000 hr. in full cell at 160 to 200 C in phosphoric acid H3PO4, and was shown to provide stable performance. The mixed catalyst contains an organometallic to catalyze electroreduction of oxygen to hydrogen peroxide and a metal to catalyze further electroreduction of the hydrogen peroxide to water. Cathodes containing an exemplar mixed catalyst (e.g., Co bisphenyl TAA/Mn) operate at approximately 650 mV vs DHE in 160 C, 85% H3PO4 with oxygen as reactant. In developing this mixed catalyst, a broad spectrum of TAAs were prepared, tested in half-cell and in a rotating ring-disk electrode system. TAAs found to facilitate the production of hydrogen peroxide in electroreduction were shown to be preferred TAAs for use in the mixed catalyst. Manganese (Mn) was identified as a preferred metal because it is capable of catalyzing hydrogen peroxide electroreduction, is lower in cost and is of less strategic importance than platinum, the cathode catalyst normally used in the fuel cell.

  17. Organometallic catalysts for primary phosphoric acid fuel cells

    NASA Astrophysics Data System (ADS)

    Walsh, Fraser

    1987-03-01

    A continuing effort by the U.S. Department of Energy to improve the competitiveness of the phosphoric acid fuel cell by improving cell performance and/or reducing cell cost is discussed. Cathode improvement, both in performance and cost, available through the use of a class of organometallic cathode catalysts, the tetraazaannulenes (TAAs), was investigated. A new mixed catalyst was identified which provides improved cathode performance without the need for the use of a noble metal. This mixed catalyst was tested under load for 1000 hr. in full cell at 160 to 200 C in phosphoric acid H3PO4, and was shown to provide stable performance. The mixed catalyst contains an organometallic to catalyze electroreduction of oxygen to hydrogen peroxide and a metal to catalyze further electroreduction of the hydrogen peroxide to water. Cathodes containing an exemplar mixed catalyst (e.g., Co bisphenyl TAA/Mn) operate at approximately 650 mV vs DHE in 160 C, 85% H3PO4 with oxygen as reactant. In developing this mixed catalyst, a broad spectrum of TAAs were prepared, tested in half-cell and in a rotating ring-disk electrode system. TAAs found to facilitate the production of hydrogen peroxide in electroreduction were shown to be preferred TAAs for use in the mixed catalyst. Manganese (Mn) was identified as a preferred metal because it is capable of catalyzing hydrogen peroxide electroreduction, is lower in cost and is of less strategic importance than platinum, the cathode catalyst normally used in the fuel cell.

  18. Kinetics of the hydrogen abstraction OH + alkane --> H2O + alkyl reaction class: an application of the reaction class transition state theory.

    PubMed

    Huynh, Lam K; Ratkiewicz, Artur; Truong, Thanh N

    2006-01-19

    This paper presents an application of the reaction class transition state theory (RC-TST) to predict thermal rate constants for hydrogen abstraction reactions of the type OH + alkane --> HOH + alkyl. We have derived all parameters for the RC-TST method for this reaction class from rate constants of 19 representative reactions, coupling with linear energy relationships (LERs), so that rate constants for any reaction in this class can be predicted from its reaction energy calculated at either the AM1 semiempirical or BH&HLYP/cc-pVDZ level of theory. The RC-TST/LER thermal rate constants for selected reactions are in good agreement with those available in the literature. Detailed analyses of the results show that the RC-TST/LER method is an efficient method for accurately estimating rate constants for a large number of reactions in this class. Analysis of the LERs leads to the discovery of the beta-carbon radical stabilization effect that stabilizes the transition state of any reaction in this class that yields products having one or more beta-carbons, and thus leads to the lower barrier for such a reaction.

  19. Time resolved infrared studies of C-H bond activation by organometallics

    SciTech Connect

    Asplund, M.C. |

    1998-06-01

    This work describes how step-scan Fourier Transform Infrared spectroscopy and visible and near infrared ultrafast lasers have been applied to the study of the photochemical activation of C-H bonds in organometallic systems, which allow for the selective breaking of C-H bonds in alkanes. The author has established the photochemical mechanism of C-H activation by Tp{sup *}Rh(CO){sub 2}(Tp{sup *} = HB-Pz{sup *}{sub 3}, Pz = 3,5-dimethylpyrazolyl) in alkane solution. The initially formed monocarbonyl forms a weak solvent complex, which undergoes a change in Tp{sup *} ligand connectivity. The final C-H bond breaking step occurs at different time scales depending on the structure of the alkane. In linear solvents, the time scale is <50 ns and cyclic alkanes is {approximately}200 ps. The reactivity of the Tp{sup *}Rh(CO){sub 2} system has also been studied in aromatic solvents. Here the reaction proceeds through two different pathways, with very different time scales. The first proceeds in a manner analogous to alkanes and takes <50 ns. The second proceeds through a Rh-C-C complex, and takes place on a time scale of 1.8 {micro}s.

  20. Formation of Organometallic Intermediate States in On-Surface Ullmann Couplings.

    PubMed

    Barton, Dennis; Gao, Hong-Ying; Held, Philipp Alexander; Studer, Armido; Fuchs, Harald; Doltsinis, Nikos L; Neugebauer, Johannes

    2017-02-17

    Possible origins of the formation of organometallic intermediates in on-surface Ullmann couplings have been investigated by surface tunneling microscopy (STM) and density functional theory (DFT) calculations. We consider the case of iodobenzenes on the coinage metals Au, Ag and Cu. We found experimental evidence for the formation of surface vacancies and the presence of metal adatoms in these coupling reactions, which are taken as a hint for the reactive extraction of surface atoms by adsorbates. In a second step, we demonstrate by ab initio molecular dynamics calculations for aryl-iodides on copper that metal atoms can be pulled out of the surface to form metalorganic species. By contrast, a thermally activated provision of a metal atom from the surface to form an adatom is energetically unfavourable. Finally, we investigate the mechanism and energetics of the reactive extraction of surface metal atoms by means of (climbing-image) nudged-elastic-band density-functional theory calculations for iodobenzene on copper, silver and gold, and analyze our results in the light of the experimental findings.

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

    PubMed

    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.

  2. Interpretation and application of reaction class transition state theory for accurate calculation of thermokinetic parameters using isodesmic reaction method.

    PubMed

    Wang, Bi-Yao; Li, Ze-Rong; Tan, Ning-Xin; Yao, Qian; Li, Xiang-Yuan

    2013-04-25

    We present a further interpretation of reaction class transition state theory (RC-TST) proposed by Truong et al. for the accurate calculation of rate coefficients for reactions in a class. It is found that the RC-TST can be interpreted through the isodesmic reaction method, which is usually used to calculate reaction enthalpy or enthalpy of formation for a species, and the theory can also be used for the calculation of the reaction barriers and reaction enthalpies for reactions in a class. A correction scheme based on this theory is proposed for the calculation of the reaction barriers and reaction enthalpies for reactions in a class. To validate the scheme, 16 combinations of various ab initio levels with various basis sets are used as the approximate methods and CCSD(T)/CBS method is used as the benchmarking method in this study to calculate the reaction energies and energy barriers for a representative set of five reactions from the reaction class: R(c)CH(R(b))CR(a)CH2 + OH(•) → R(c)C(•)(R(b))CR(a)CH2 + H2O (R(a), R(b), and R(c) in the reaction formula represent the alkyl or hydrogen). Then the results of the approximate methods are corrected by the theory. The maximum values of the average deviations of the energy barrier and the reaction enthalpy are 99.97 kJ/mol and 70.35 kJ/mol, respectively, before correction and are reduced to 4.02 kJ/mol and 8.19 kJ/mol, respectively, after correction, indicating that after correction the results are not sensitive to the level of the ab initio method and the size of the basis set, as they are in the case before correction. Therefore, reaction energies and energy barriers for reactions in a class can be calculated accurately at a relatively low level of ab initio method using our scheme. It is also shown that the rate coefficients for the five representative reactions calculated at the BHandHLYP/6-31G(d,p) level of theory via our scheme are very close to the values calculated at CCSD(T)/CBS level. Finally, reaction

  3. Synthesis of polystyrene microspheres and functionalization with Pd(0) nanoparticles to perform bioorthogonal organometallic chemistry in living cells.

    PubMed

    Unciti-Broceta, Asier; Johansson, Emma M V; Yusop, Rahimi M; Sánchez-Martín, Rosario M; Bradley, Mark

    2012-05-31

    We have developed miniaturized heterogeneous Pd(0)-catalysts (Pd(0)-microspheres) with the ability to enter cells, stay harmlessly within the cytosol and mediate efficient bioorthogonal organometallic chemistries (e.g., allylcarbamate cleavage and Suzuki-Miyaura cross-coupling). This approach is a major addition to the toolbox available for performing chemical reactions within cells. Here we describe a full protocol for the synthesis of the Pd(0)-microspheres from readily available starting materials (by the synthesis of size-controlled amino-functionalized polystyrene microspheres), as well as for their characterization (electron microscopy and palladium quantitation) and functional validation ('in solution' and 'in cytoplasm' conversions). From the beginning of the synthesis to functional evaluation of the catalytic device requires 5 d of work.

  4. Tribromobenzene on Cu(111): Temperature-dependent formation of halogen-bonded, organometallic, and covalent nanostructures

    SciTech Connect

    Fan, Qitang; Wang, Tao; Zhu, Junfa; Liu, Liming; Zhao, Jin; Gottfried, J. Michael

    2015-03-14

    The temperature-controlled surface-assisted synthesis of halogen bonded, organometallic, and covalent nanostructures based on 1,3,5-tribromo-benzene (TriBB) was studied with scanning tunneling microscopy and X-ray photoemission spectroscopy in ultrahigh vacuum. Vapor deposition of TriBB onto a Cu(111) surface held at 90 K leads to the formation of large domains of a honeycomb-like organic monolayer structure stabilized by triangular nodes with Br⋯Br intermolecular bonds. Upon annealing the organic monolayer to ∼140 K, a new hexagonal close-packed structure with intact TriBB molecules connected by Cu adatoms is formed. Further warming up the sample to 300 K gives rise to the scission of C–Br bonds and formation of C–Cu–C bonds between phenyl fragments such that stable dendritic organometallic networks are formed. Larger islands of organometallic networks are obtained by maintaining the temperature of Cu(111) at 420 K during deposition of TriBB. Simultaneously, large islands of Br atoms are formed around the organometallic networks. Annealing the more extended organometallic network (prepared at 420 K) to 520 K leads to the formation of a branched covalent organic framework (COF) which comprises structural elements of porous graphene and is surrounded by Br islands. These organometallic networks and COFs appear as small dendritic and branched domains, most likely due to the steric influence exerted by the Br islands.

  5. Tribromobenzene on Cu(111): Temperature-dependent formation of halogen-bonded, organometallic, and covalent nanostructures

    NASA Astrophysics Data System (ADS)

    Fan, Qitang; Wang, Tao; Liu, Liming; Zhao, Jin; Zhu, Junfa; Gottfried, J. Michael

    2015-03-01

    The temperature-controlled surface-assisted synthesis of halogen bonded, organometallic, and covalent nanostructures based on 1,3,5-tribromo-benzene (TriBB) was studied with scanning tunneling microscopy and X-ray photoemission spectroscopy in ultrahigh vacuum. Vapor deposition of TriBB onto a Cu(111) surface held at 90 K leads to the formation of large domains of a honeycomb-like organic monolayer structure stabilized by triangular nodes with Br⋯Br intermolecular bonds. Upon annealing the organic monolayer to ˜140 K, a new hexagonal close-packed structure with intact TriBB molecules connected by Cu adatoms is formed. Further warming up the sample to 300 K gives rise to the scission of C-Br bonds and formation of C-Cu-C bonds between phenyl fragments such that stable dendritic organometallic networks are formed. Larger islands of organometallic networks are obtained by maintaining the temperature of Cu(111) at 420 K during deposition of TriBB. Simultaneously, large islands of Br atoms are formed around the organometallic networks. Annealing the more extended organometallic network (prepared at 420 K) to 520 K leads to the formation of a branched covalent organic framework (COF) which comprises structural elements of porous graphene and is surrounded by Br islands. These organometallic networks and COFs appear as small dendritic and branched domains, most likely due to the steric influence exerted by the Br islands.

  6. The state and catalytic properties of (Ni + Pd)/SiO{sub 2} systems obtained by grafting organometallic complexes on the surface of SiO{sub 2}

    SciTech Connect

    Koval`chuk, V.I.; Chesnokov, N.V.; Naimushina, L.V.

    1995-05-01

    The adsorption and catalytic properties of Pd/SiO{sub 2}, Ni/SiO{sub 2}, and (Pd + Ni)/SiO{sub 2} samples obtained by grafting organometallic Pd and Ni compounds on the support surface are studied. Bimetallic Pd-Ni catalysts are shown to have an additive catalytic action in the hydrogenation of benzene. Synergistic effects are detected in the reactions of ethane hydrogenolysis, CO hydrogenation, and propylene hydroformylation. The obtained data show that the surface of bimetallic cluster particles becomes enriched with palladium atoms.

  7. [Co(η5-P5){η2-P2H(mes)}]2-: a phospha-organometallic complex obtained by the transition-metal-mediated activation of the heptaphosphide trianion.

    PubMed

    Knapp, Caroline M; Westcott, Bethan H; Raybould, Melissa A C; McGrady, John E; Goicoechea, Jose M

    2012-09-03

    A carbon copy: The chemical activation of the heptaphosphide trianion with [Co(PEt(2)Ph)(2)(mes)(2)] (see picture; 1) yields the novel phospha-organometallic complex [Co(η(5)-P(5)){η(2)-P(2)H(mes)}](2-) (2). The reaction product maintains the nuclearity of the parent cluster, but extensive cage fragmentation takes place to yield a diamagnetic "inorganometallic" cobalt complex.

  8. Applications of quantum chemistry to gas and solid phase reaction kinetics

    NASA Astrophysics Data System (ADS)

    Senosiain, Juan Pablo

    Chemical kinetics has nourished from the achievements of computational quantum chemistry as perhaps no other field. This thesis illustrates the application of first-principles calculations to elucidate complex reaction mechanisms, and to quantitatively simulate reaction rates. The work embodied in this dissertation encompasses several projects with very diverse applications. In some cases, quantum chemistry calculations have been used for predicting reaction rates, while in others they are used in a semi-qualitative manner to elucidate complex reaction mechanisms. The first two chapters of this dissertation explain some key theoretical concepts of quantum chemistry and chemical kinetics. They are not intended to be exhaustive or detailed, but rather to illustrate general principles that are applied in the subsequent chapters. Chapter three reviews the disperse literature on the statistical treatment of internal rotors and provides a comparison of commonly used approximations. Chapters four through six cover three areas of special interest to gas-phase kinetics: bond dissociation energies, transition state theory and unimolecular reactions, with particular emphasis on combustion and atmospheric chemistry applications. A critical assessment of reaction barriers and bond dissociation energies calculated with several ab initio methods in common use is provided in chapters four and five, respectively. Chapters seven and eight illustrate how quantum chemistry can be used to decipher complex reaction mechanisms, with applications to current and future problems in semiconductor processing. The former studies the mechanisms of boron diffusion through thin gate oxide layers in metal oxide field effect transistors (MOSFETs). The latter investigates the details of atomic layer deposition (ALD) reactions on germanium and silicon-germanium alloys. Both of these studies are motivated by the miniaturization trend in gate oxide layers in MOSFET devices. As the device feature size

  9. Model for the Vaporization of Mixed Organometallic Compounds in the Metalorganic Chemical Vapor Deposition of High Temperature Superconducting Films

    NASA Technical Reports Server (NTRS)

    Meng, Guangyao; Zhou, Gang; Schneider, Roger L.; Sarma, Bimal K.; Levy, Moises

    1993-01-01

    A model of the vaporization and mass transport of mixed organometallics from a single source for thin film metalorganic chemical vapor deposition is presented. A stoichiometric gas phase can be obtained from a mixture of the organometallics in the desired mole ratios, in spite of differences in the volatilities of the individual compounds. Proper film composition and growth rates are obtained by controlling the velocity of a carriage containing the organometallics through the heating zone of a vaporizer.

  10. General chemical kinetics computer program for static and flow reactions, with application to combustion and shock-tube kinetics

    NASA Technical Reports Server (NTRS)

    Bittker, D. A.; Scullin, V. J.

    1972-01-01

    A general chemical kinetics program is described for complex, homogeneous ideal-gas reactions in any chemical system. Its main features are flexibility and convenience in treating many different reaction conditions. The program solves numerically the differential equations describing complex reaction in either a static system or one-dimensional inviscid flow. Applications include ignition and combustion, shock wave reactions, and general reactions in a flowing or static system. An implicit numerical solution method is used which works efficiently for the extreme conditions of a very slow or a very fast reaction. The theory is described, and the computer program and users' manual are included.

  11. Application of Fenton's reaction to steam explosion prehydrolysates from poplar biomass.

    PubMed

    Oliva, J M; Manzanares, P; Ballesteros, I; Negro, M J; González, A; Ballesteros, M

    2005-01-01

    The application of Fenton's reaction to enhance the fermentability of prehydrolysates obtained from steam explosion pretreatment of poplar biomass was studied. Reaction conditions of temperature and H2O2 and Fe(II) concentrations were studied. The fermentability of prehydrolysate treated by Fenton's reaction was tested by using different inoculum sizes of thermotolerant strain Kluyveromyces marxianus CECT 10875. The highest percentages of toxic compound degradation (ranging from 71 to 93% removal) were obtained at the highest H2O2 concentration tested (50 mM). However, a negative effect on fermentability was observed at this H2O2 concentration at the lower inoculum loading. An increase in inoculum size to 0.6 g/L resulted in an enhanced ethanol fermentation yield of 95% relative to control.

  12. Preparation of bifunctional mesoporous silica nanoparticles by orthogonal click reactions and their application in cooperative catalysis.

    PubMed

    Dickschat, Arne T; Behrends, Frederik; Bühner, Martin; Ren, Jinjun; Weiss, Mark; Eckert, Hellmut; Studer, Armido

    2012-12-21

    The synthesis of bifunctional mesoporous silica nanoparticles is described. Two chemically orthogonal functionalities are incorporated into mesoporous silica by co-condensation of tetraethoxysilane with two orthogonally functionalized triethoxyalkylsilanes. Post-functionalization is achieved by orthogonal surface chemistry. A thiol-ene reaction, Cu-catalyzed 1,3-dipolar alkyne/azide cycloaddition, and a radical nitroxide exchange reaction are used as orthogonal processes to install two functionalities at the surface that differ in reactivity. Preparation of mesoporous silica nanoparticles bearing acidic and basic sites by this approach is discussed. Particles are analyzed by solid state NMR spectroscopy, elemental analysis, infrared-spectroscopy, and scanning electron microscopy. As a first application, these particles are successfully used as cooperative catalysts in the Henry reaction.

  13. A QSAR for the hydroxyl radical reaction rate constant: validation, domain of application, and prediction

    NASA Astrophysics Data System (ADS)

    Öberg, Tomas

    A large number of anthropogenic organic chemicals are emitted into the troposphere. Reactions with the hydroxyl radical are a dominant removal pathway for most organic compounds, but experimentally determined gas-phase reaction rate constants are only available for about 750 compounds. The lack of experimental data increases the importance of applying quantitative structure-activity relationships (QSAR) to evaluate and predict reactivities. It is generally acknowledged that these empirical relationships are valid only within the same domain for which they were developed. However, model validation is sometimes neglected and the application domain is not always well defined. The purpose of this paper is to outline how validation and domain definition can facilitate the modeling and prediction of the hydroxyl radical reaction rates for a large database. A substantial number of theoretical descriptors (867) were generated from 2D molecular structures for compounds present in the Syracuse Research Corporation's PhysProp Database. A QSAR model was developed for the hydroxyl radical reaction rate constant using a projection-based regression technique, partial least squares regression (PLSR). The PLSR model was subsequently validated with an external test set. The main factors of variation could be attributed to two reaction pathways, hydrogen atom abstraction and addition to double bonds or aromatic systems. A set of 17 293 compounds, drawn from the PhysProp Database, was projected onto the PLSR model and 74% were inside the applicability domain. The predicted hydroxyl reaction rates for 25% of these compounds were slow or negligible, with atmospheric half-lives in the range from days to years. Finally, the list of persistent organic compounds was matched against the OECD list of high production volume chemicals (HPVC). Together with the experimental data, nearly three hundred compounds were identified as both persistent and in high volume production.

  14. Gas-Phase Oxidation via Ion/Ion Reactions: Pathways and Applications

    NASA Astrophysics Data System (ADS)

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

    2017-01-01

    Here, we provide an overview of pathways available upon the gas-phase oxidation of peptides and DNA via ion/ion reactions and explore potential applications of these chemistries. The oxidation of thioethers (i.e., methionine residues and S-alkyl cysteine residues), disulfide bonds, S-nitrosylated cysteine residues, and DNA to the [M+H+O]+ derivative via ion/ion reactions with periodate and peroxymono-sulfate anions is demonstrated. The oxidation of neutral basic sites to various oxidized structures, including the [M+H+O]+, [M-H]+, and [M-H-NH3]+ species, via ion/ion reactions is illustrated and the oxidation characteristics of two different oxidizing reagents, periodate and persulfate anions, are compared. Lastly, the highly efficient generation of molecular radical cations via ion/ion reactions with sulfate radical anion is summarized. Activation of the newly generated molecular radical peptide cations results in losses of various neutral side chains, several of which generate dehydroalanine residues that can be used to localize the amino acid from which the dehydroalanine was generated. The chemistries presented herein result in a diverse range of structures that can be used for a variety of applications, including the identification and localization of S-alkyl cysteine residues, the oxidative cleavage of disulfide bonds, and the generation of molecular radical cations from even-electron doubly protonated peptides.

  15. The use of low energy, ion induced nuclear reactions for proton radiotherapy applications

    SciTech Connect

    Horn, K.M.; Doyle, B.; Segal, M.N.; Hamm, R.W.; Adler, R.J.; Glatstein, E.

    1995-04-01

    Medical radiotherapy has traditionally relied upon the use of external photon beams and internally implanted radioisotopes as the chief means of irradiating tumors. However, advances in accelerator technology and the exploitation of novel means of producing radiation may provide useful alternatives to some current modes of medical radiation delivery with reduced total dose to surrounding healthy tissue, reduced expense, or increased treatment accessibility. This paper will briefly overview currently established modes of radiation therapy, techniques still considered experimental but in clinical use, innovative concepts under study that may enable new forms of treatment or enhance existing ones. The potential role of low energy, ion-induced nuclear reactions in radiotherapy applications is examined specifically for the 650 keV d({sup 3}He,p){sup 4}He nuclear reaction. This examination will describe the basic physics associated with this reaction`s production of 17.4 MeV protons and the processes used to fabricate the necessary materials used in the technique. Calculations of the delivered radiation dose, heat generation, and required exposure times are presented. Experimental data are also presented validating the dose calculations. The design of small, lower cost ion accelerators, as embodied in `nested`-tandem and radio frequency quadrupole accelerators is examined, as is the potential use of high-output {sup 3}He and deuterium ion sources. Finally, potential clinical applications are discussed in terms of the advantages and disadvantages of this technique with respect to current radiotherapy methods and equipment.

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

    SciTech Connect

    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

  17. Development of chiral thiourea catalysts and its application to asymmetric catalytic reactions.

    PubMed

    Takemoto, Yoshiji

    2010-05-01

    We have developed several multifunctional thiourea catalysts bearing a tertiary amine or an 1,2-amino alcohol in expectation of their synchronous activation of a nucleophile and an electrophile through both acid-base and hydrogen-bonding interactions. From these studies, it was revealed that the weak acidity of thioureas compared with metallic Lewis acids could be overcome by this modification. The bifunctional aminothiourea could be used efficiently for a wide range of diastereoselective and enantioselective nucleophilic reactions such as Michael addition of 1,3-dicarbonyl compounds to nitroolefines, aza-Henry reaction of nitroalkanes to N-Boc imines, and hydrazination of cyclic beta-keto esters. We also discovered that multifunctional thiourea catalyst, bearing an 1,2-amino alcohol moiety, significantly accelerated the Petasis-type reaction of alkenylboronic acids to N-phenoxycarbonyl quinolinium salts, prepared from quinolines and phenyl chloroformate, to afford 1,2-addition products with high enantioselectivity (up to 97% ee). Furthermore, to expand the synthetic applicability of the thiourea-catalyzed asymmetric reactions, tandem organocatalyzed reactions were explored to establish the concise one-pot synthesis of chiral densely functionalized three-, five-, and six-membered compounds.

  18. Applications of nuclear reaction analysis for determining hydrogen and deuterium distribution in metals

    SciTech Connect

    Altstetter, C.J.

    1981-01-01

    The use of ion beams for materials analysis has made a successful transition from the domain of the particle physicist to that of the materials scientist. The subcategory of this field, nuclear reaction analysis, is just now undergoing the transition, particularly in applications to hydrogen in materials. The materials scientist must locate the nearest accelerator, because now he will find that using it can solve mysteries that do not yield to other techniques. 9 figures

  19. Manned Evaluation of a Diver Heater for SDV Applications Using Hydrogen Catalytic Reactions

    DTIC Science & Technology

    2005-06-01

    DIVER HEATER FOR SDV APPLICATIONS USING HYDROGEN CATALYTIC REACTIONS GAS CIRCUIT The basic heater design uses a gas ejector pump to recirculate the gas...entrance of the gas ejector pump. In this manner the hydrogen is mixed inside the pressure vessel with the recirculated gas and the fresh incoming air to...recirculatory flow then passes through a gas-to-water heat exchanger where the heat is removed and some of the water vapor condenses . The recirculatory flow then

  20. Organometallic complexes with terminal imidazolato ligands and their use as metalloligands.

    PubMed

    Gómez, Eva; Huertos, Miguel A; Pérez, Julio; Riera, Lucía; Menéndez-Velázquez, Amador

    2010-10-18

    Compounds [Re(bipy)(CO)(3)(HIm)]OTf (1) and [Mo(η(3)-C(3)H(4)-R-2)(CO)(2)(HIm)(phen)]BAr'(4) [R = Me (2a), H (2b); Ar' = 3,5-bis(trifluoromethyl)phenyl; HIm = 1H-imidazole] were prepared from 1H-imidazole and either [Re(OTf)(bipy)(CO)(3)] or [MoCl(η(3)-C(3)H(4)-R-2)(CO)(2)(phen)]. Compounds 1, 2a, and 2b were deprotonated to afford the terminal κ-N-imidazolate complexes [Re(bipy)(CO)(3)(Im)] (3) and [Mo(η(3)-C(3)H(4)-R-2)(CO)(2)(Im)(phen)] [R = Me (4a), H (4b)], which were fully characterized, including an X-ray structural determination of 3. The topological analysis of the electron density (obtained from the X-ray diffraction study) and its Laplacian were used to characterize the differences in the electron density at the five-membered ring ligand between the imidazole and imidazolate complexes 1 and 3. The reaction of complexes 3, 4a, and 4b with the appropriate organometallic complexes afforded the bimetallic imidazolate-bridged compounds [{Re(bipy)(CO)(3)}(2)(μ-Im)]OTf (5), [{Mo(η(3)-C(4)H(7))(CO)(2)(phen)}(2)(μ-Im)]OTf (6), and [{Mo(η(3)-C(3)H(5))(CO)(2)(phen)}(μ-Im){Re(phen)(CO)(3)}]OTf (7). The reaction of [Mo(η(3)-C(4)H(7))(CO)(2)(Im)(phen)] (4a) with SnClPh(3) led to the formation of the trinuclear complex [{Mo(η(3)-C(4)H(7))(CO)(2)(phen)(μ-Im)}(2){SnPh(3)}]BAr'(4) (8).

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

    PubMed

    Polakovič, Milan; Švitel, Juraj; Bučko, Marek; Filip, Jaroslav; Neděla, Vilém; Ansorge-Schumacher, Marion B; Gemeiner, Peter

    2017-02-08

    Viable microbial cells are important biocatalysts in the production of fine chemicals and biofuels, in environmental applications and also in emerging applications such as biosensors or medicine. Their increasing significance is driven mainly by the intensive development of high performance recombinant strains supplying multienzyme cascade reaction pathways, and by advances in preservation of the native state and stability of whole-cell biocatalysts throughout their application. In many cases, the stability and performance of whole-cell biocatalysts can be highly improved by controlled immobilization techniques. This review summarizes the current progress in the development of immobilized whole-cell biocatalysts, the immobilization methods as well as in the bioreaction engineering aspects and economical aspects of their biocatalytic applications.

  2. Lower limb ice application alters ground reaction force during gait initiation

    PubMed Central

    Muniz, Thiago B.; Moraes, Renato; Guirro, Rinaldo R. J.

    2015-01-01

    BACKGROUND: Cryotherapy is a widely used technique in physical therapy clinics and sports. However, the effects of cryotherapy on dynamic neuromuscular control are incompletely explained. OBJECTIVES: To evaluate the effects of cryotherapy applied to the calf, ankle and sole of the foot in healthy young adults on ground reaction forces during gait initiation. METHOD: This study evaluated the gait initiation forces, maximum propulsion, braking forces and impulses of 21 women volunteers through a force platform, which provided maximum and minimum ground reaction force values. To assess the effects of cooling, the task - gait initiation - was performed before ice application, immediately after and 30 minutes after removal of the ice pack. Ice was randomly applied on separate days to the calf, ankle and sole of the foot of the participants. RESULTS: It was demonstrated that ice application for 30 minutes to the sole of the foot and calf resulted in significant changes in the vertical force variables, which returned to their pre-application values 30 minutes after the removal of the ice pack. Ice application to the ankle only reduced propulsion impulse. CONCLUSIONS: These results suggest that although caution is necessary when performing activities that require good gait control, the application of ice to the ankle, sole of the foot or calf in 30-minute intervals may be safe even preceding such activities. PMID:25993625

  3. The influence of topical steroid application on tuberculin skin reactions in healthy persons.

    PubMed

    Thestrup-Pedersen, K; Ahlburg, H; Hansen, P; Larsen, P O

    1982-01-01

    Thirty-seven healthy persons were studied in order to evaluate the influence of topical steroid application on tuberculin skin reactions. Four areas measuring 4 cm in diameter were each treated with 50 micrograms of hydrocortisone cream 1%, or 50% micrograms of halcinonide (Halog) cream 0.1%, or 50 micrograms of unguentum cetacei simplex (cold cream), or not treated. The creams were applied once daily for 3 days before and one day after a tuberculin skin test. After 24 and 48 hours the area of induration were measured. We observed that application of unguentum cetacei simplex increased the size of the induration at the 24-hour reading, but not after 48 hours. Hydrocortisone cream 1% gave the same effect, whereas halcinonide cream (Halog) 0.1% caused ischaemia of the skin and reduced the induration of the skin test after 24 hours, but not after 48 hours. In 12 persons we found that simple rubbing of the skin with halcinonide cream base did not affect the size of the tuberculin skin reaction. In the present study we found that even very potent local steroid application on intact skin could only delay the development of tuberculin skin reactions, but could not diminish their size.

  4. The first organometallic selective estrogen receptor modulators (SERMs) and their relevance to breast cancer.

    PubMed

    Jaouen, Gérard; Top, Siden; Vessières, Anne; Leclercq, G; McGlinchey, Michael J

    2004-09-01

    In the overall scheme of the future development of new drugs for the treatment of breast cancer, specially tamoxifen resistant tumours, we have explored the unprecedented use of organometallic SERMs. The initial idea is to enhance the efficacy of the current standard, i.e. tamoxifen, by modifying the structure through judicious incorporation of an organometallic moiety possessing novel properties. Results have been varied, justifying a systematic approach that has proved to be full of surprised. The following differing situations were observed (a) the anti-proliferative effect is due to the vector and the organometallic moiety does not improve the effects of the SERM, no matter what concentration is used. In particular, this is the case for the hydroxytamoxifen derivative bearing a CpRe(CO)3 group, which behaves almost identically to hydroxytamoxifen. These stable species have future promise for use with radionucleides of Re and Tc (b) the effect of the organometallic moiety counteracts the anti-estrogenic behaviour of the vector and leads to species with proliferative activity; this is the case with Cp2TiCl2 entity, which when attached to tamoxifen behaves as a powerful estrogen, probably due to in situ release of Ti(IV) (c) a synergy exists between the cytotoxic organometallic moiety and its organic vector, leading to unique anti-proliferative effects on breast cancer cells classed ER+ and ER-. This result opens a new window on organometallic oncology. It is also clear that the range of possibilities is broad, varied and currently unpredictable. A systematic study combining organometallic chemistry and biology is the only option in the search for new SERMs with novel properties.

  5. Sample treatment in chromatography-based speciation of organometallic pollutants.

    PubMed

    Gómez-Riza, J L; Morales, E; Giráldez, I; Sánchez-Rodas, D; Velasco, A

    2001-12-14

    Speciation analysis is nowadays performed routinely in many laboratories to control the quality of the environment, food and health. Chemical speciation analyses generally include the study of different oxidation state of elements or individual organometallic compounds. The determination of the different chemical forms of elements is still an analytical challenge, since they are often unstable and concentrations in different matrices of interest are in the microg l(-1) or even in the ng l(-1) range (e.g., estuarine waters) or ng g(-1) in sediments and biological tissues. For this reason, sensitive and selective analytical atomic techniques are being used as available detectors for speciation, generally coupled with chromatography for the time-resolved introduction of analytes into the atomic spectrometer. The complexity of these instrumental couplings has a straightforward consequence on the duration of the analysis, but sample preparation to separate and transfer the chemical species present in the sample into a solution to be accepted readily by a chromatographic column is the more critical step of total analysis, and demands considerable operator skills and time cost. Traditionally, liquid-liquid extraction has been employed for sample treatment with serious disadvantages, such as consumption, disposal and long-term exposure to organic solvent. In addition, they are usually cumbersome and time-consuming. Therefore, the introduction of new reagents such as sodium tetraethylborate for the simultaneous derivatization of several elements has been proposed. Other possibilities are based in the implementation of techniques for efficient and accelerated isolation of species from the sample matrix. This is the case for microwave-assisted extraction, solid-phase extraction and microextraction, supercritical fluid extraction or pressurized liquid extraction, which offer new possibilities in species treatment, and the advantages of a drastic reduction of the extraction

  6. Active photonic devices based on colloidal semiconductor nanocrystals and organometallic halide perovskites

    NASA Astrophysics Data System (ADS)

    Suárez Alvarez, Isaac

    2016-10-01

    Semiconductor nanocrystals have arisen as outstanding materials to develop a new generation of optoelectronic devices. Their fabrication under simple and low cost colloidal chemistry methods results in cheap nanostructures able to provide a wide range of optical functionalities. Their attractive optical properties include a high absorption cross section below the band gap, a high quantum yield emission at room temperature, or the capability of tuning the band-gap with the size or the base material. In addition, their solution process nature enables an easy integration on several substrates and photonic structures. As a consequence, these nanoparticles have been extensively proposed to develop several photonic applications, such as detection of light, optical gain, generation of light or sensing. This manuscript reviews the great effort undertaken by the scientific community to construct active photonic devices based on these nanoparticles. The conditions to demonstrate stimulated emission are carefully studied by comparing the dependence of the optical properties of the nanocrystals with their size, shape and composition. In addition, this paper describes the design of different photonic architectures (waveguides and cavities) to enhance the generation of photoluminescence, and hence to reduce the threshold of optical gain. Finally, semiconductor nanocrystals are compared to organometallic halide perovskites, as this novel material has emerged as an alternative to colloidal nanoparticles.

  7. Study of surface relief gratings on azo organometallic films in picosecond regime.

    PubMed

    Luc, J; Bouchouit, K; Czaplicki, R; Fillaut, J-L; Sahraoui, B

    2008-09-29

    Materials for optical data storage and optical information processing must exhibit good holographic properties. Many materials for these applications have been already proposed. Here we describe a grating inscription process characterized by short inscription time and long-time stability. A series of ruthenium-acetylide organometallic complexes containing an azobenzene fragment were synthesized. Photo-induced gratings were produced by short pulse (16 ps, 532 nm) laser irradiation. The surface relief gratings formed at the same time were observed by atomic force microscope. In this work, we highlight the short inscription times brought into play as well as the good temporal stability of these gratings stored at room temperature. We study the influence of the polarization states and the light intensity of writing beams on the dynamics of the surface relief gratings formation and we compare these results with those of a known representative of azobenzene derivative (Disperse Red 1). Lastly, we show that it is possible to write two-dimensional surface relief gratings.

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

    PubMed

    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.

  9. Statistical rate theory and kinetic energy-resolved ion chemistry: theory and applications.

    PubMed

    Armentrout, P B; Ervin, Kent M; Rodgers, M T

    2008-10-16

    Ion chemistry, first discovered 100 years ago, has profitably been coupled with statistical rate theories, developed about 80 years ago and refined since. In this overview, the application of statistical rate theory to the analysis of kinetic-energy-dependent collision-induced dissociation (CID) reactions is reviewed. This procedure accounts for and quantifies the kinetic shifts that are observed as systems increase in size. The statistical approach developed allows straightforward extension to systems undergoing competitive or sequential dissociations. Such methods can also be applied to the reverse of the CID process, association reactions, as well as to quantitative analysis of ligand exchange processes. Examples of each of these types of reactions are provided and the literature surveyed for successful applications of this statistical approach to provide quantitative thermochemical information. Such applications include metal-ligand complexes, metal clusters, proton-bound complexes, organic intermediates, biological systems, saturated organometallic complexes, and hydrated and solvated species.

  10. Deciphering Halogen Competition in Organometallic Halide Perovskite Growth

    DOE PAGES

    Keum, Jong Kahk; Ovchinnikova, Olga S.; Chen, Shiyou; ...

    2016-03-01

    Organometallic halide perovskites (OHPs) hold great promise for next-generation, low-cost optoelectronic devices. During the chemical synthesis and crystallization of OHP thin films a major unresolved question is the competition between multiple halide species (e.g. I-, Cl-, Br-) in the formation of the mixed halide perovskite crystals. Whether Cl- ions are successfully incorporated into the perovskite crystal structure or alternatively, where they are located, is not yet fully understood. Here, in situ X-ray diffraction measurements of crystallization dynamics are combined with ex situ TOF-SIMS chemical analysis to reveal that Br- or Cl- ions can promote crystal growth, yet reactive I- ionsmore » prevent them from incorporating into the lattice of the final perovskite crystal structure. The Cl- ions are located in the grain boundaries of the perovskite films. These findings significantly advance our understanding of the role of halogens during synthesis of hybrid perovskites, and provide an insightful guidance to the engineering of high-quality perovskite films, essential for exploring superior-performance and cost-effective optoelectronic devices.« less

  11. Deciphering Halogen Competition in Organometallic Halide Perovskite Growth

    SciTech Connect

    Keum, Jong Kahk; Ovchinnikova, Olga S.; Chen, Shiyou; Du, Mao-Hua; Ivanov, Ilia N; Rouleau, Christopher; Geohegan, David B.; Xiao, Kai

    2016-03-01

    Organometallic halide perovskites (OHPs) hold great promise for next-generation, low-cost optoelectronic devices. During the chemical synthesis and crystallization of OHP thin films a major unresolved question is the competition between multiple halide species (e.g. I-, Cl-, Br-) in the formation of the mixed halide perovskite crystals. Whether Cl- ions are successfully incorporated into the perovskite crystal structure or alternatively, where they are located, is not yet fully understood. Here, in situ X-ray diffraction measurements of crystallization dynamics are combined with ex situ TOF-SIMS chemical analysis to reveal that Br- or Cl- ions can promote crystal growth, yet reactive I- ions prevent them from incorporating into the lattice of the final perovskite crystal structure. The Cl- ions are located in the grain boundaries of the perovskite films. These findings significantly advance our understanding of the role of halogens during synthesis of hybrid perovskites, and provide an insightful guidance to the engineering of high-quality perovskite films, essential for exploring superior-performance and cost-effective optoelectronic devices.

  12. High-sensitivity molecular organometallic resist for EUV (MORE)

    NASA Astrophysics Data System (ADS)

    Passarelli, James; Murphy, Michael; Del Re, Ryan; Sortland, Miriam; Dousharm, Levi; Vockenhuber, Michaela; Ekinci, Yasin; Neisser, Mark; Freedman, Daniel A.; Brainard, Robert L.

    2015-03-01

    We have developed organometallic carboxylate compounds [RnM(O2CR')2] capable of acting as negativetone EUV resists. Overall, the best and fastest resists contain antimony, are pentavalent and the carboxylate group contains a polymerizable olefin (e.g. acrylate, methacrylate or styrenecarboxylate). Evidence suggests that high sensitivity is achieved through the polymerization of olefins in the exposed region. We have performed a systematic sensitivity study of molecules of the type RnM(O2CR')2 where we have studied seven R groups, four main group metals (M), and three polymerizable carboxylate groups (O2CR'). We found that the greatest predictor of sensitivity of the RnSb(O2CR')2 resists is their level of polymerizable olefins. We mathematically define the polymerizable olefin loading (POL) as the ratio of the number of olefins vs. the number of non-hydrogen atoms. Linear and log plots of Emax vs. POL for a variety of molecules of the type R3Sb(O2CR')2 lend insight into the behaviour of these resists.

  13. Organometallic carboxylate resists for extreme ultraviolet with high sensitivity

    NASA Astrophysics Data System (ADS)

    Passarelli, James; Murphy, Michael; Re, Ryan Del; Sortland, Miriam; Hotalen, Jodi; Dousharm, Levi; Fallica, Roberto; Ekinci, Yasin; Neisser, Mark; Freedman, Daniel A.; Brainard, Robert L.

    2015-10-01

    We have developed organometallic carboxylate compounds [RnM)] capable of acting as negative-tone extreme ultraviolet (EUV) resists. The most sensitive of these resists contain antimony, three R-groups and two carboxylate groups, and carboxylate groups with polymerizable olefins (e.g., acrylate, methacrylate, or styrenecarboxylate). Evidence suggests that high sensitivity is achieved through the polymerization of olefins in the exposed region. We have performed a systematic sensitivity study of the molecules of the type RnM) where we have studied seven R groups, four main group metals (M), and three polymerizable carboxylate groups (O2CR‧). The sensitivity of these resists was evaluated using Emax or dose to maximum resist thickness after exposure and development. We found that the greatest predictor of sensitivity of the RnSb) resists is their level of polymerizable olefins. We mathematically define the polymerizable olefin loading (POL) as the ratio of the number of olefins versus the number of nonhydrogen atoms. Linear and log plots of Emax versus POL for a variety of molecules of the type R3Sb) lend insight into the behavior of these resists.

  14. Coordination of dibensothiophenes and corannulenes to organometallic ruthenium (II) fragments

    SciTech Connect

    Vecchi, Paul Anthony

    2005-01-01

    This dissertation contains five papers in the format required for journal publication which describe (in part) my research accomplishments as a graduate student at Iowa State University. This work can be broadly categorized as the binding of weakly-coordinating ligands to cationic organometallic ruthenium fragments, and consists of two main areas of study. Chapters 2-4 are investigations into factors that influence the binding of dibenzothiophenes to [Cp'Ru(CO)2(+ fragments, where Cp' = η5-C5H5 (Cp) and η5-C5Me5 (Cp*). Chapters 5 and 6 present the synthesis and structural characterization of complexes containing corannulene buckybowls that are η6-coordinated to [Cp*Ru(+ fragments. The first chapter contains a brief description of the difficulty in lowering sulfur levels in diesel fuel along with a review of corannulene derivatives and their metal complexes. After the final paper is a short summary of the work herein (Chapter 7). Each chapter is independent, and all equations, schemes, figures, tables, references, and appendices in this dissertation pertain only to the chapter in which they appear.

  15. MALDI-TOFMS analysis of coordination and organometallic complexes: a nic(h)e area to work in.

    PubMed

    Wyatt, Mark F

    2011-07-01

    A mini-review of the characterisation of metal-containing compounds by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOFMS) is presented. Organometallic and coordination compounds have many varied applications, most notably in industrial catalytic processes and also in the electronics and healthcare sectors. In general, the compounds discussed, be they small or large molecules, have a high percentage metal content, rather than simply containing 'a metal atom'. A brief history of the field is given, but the main scope over the last 5 years is covered in some detail. How MALDI-TOFMS compliments electrospray for metal-containing compounds is highlighted. Perspectives on recent advances, such as solvent-free and air/moisture-sensitive sample preparation, and potential future challenges and developments, such as nanomaterials and metallodrug/metallometabolite imaging, are given.

  16. Square-micrometer-sized, free-standing organometallic sheets and their square-centimeter-sized multilayers on solid substrates.

    PubMed

    Zheng, Zhikun; Ruiz-Vargas, Carlos S; Bauer, Thomas; Rossi, Antonella; Payamyar, Payam; Schütz, Andri; Stemmer, Andreas; Sakamoto, Junji; Schlüter, A Dieter

    2013-11-01

    Oligofunctional terpyridine-based monomers are spread at an air/water interface, where they are connected with transition metal salts such as Fe(II) into mechanically coherent monolayer sheets of macroscopic dimension. The conversions of these processes are determined by XPS for several monomer/metal ion combinations. The sheets are transferred onto TEM grids, the 20 × 20 square micrometer sized holes of which can be spanned. AFM indentation experiments provide in-plane elastic moduli which are compared with naturally occurring sheets such as graphene. The new organometallic sheets are also used to create multilayer assemblies on square centimeter length scales on solid substrates. Finally some directions are provided where this research can lead to in future and where its application potential lies.

  17. Application of a Particle Method to the Advection-Diffusion-Reaction Equation

    NASA Astrophysics Data System (ADS)

    Paster, A.; Bolster, D.; Benson, D. A.

    2012-12-01

    -known phenomena of incomplete mixing (Ovchinnikov-Zeldovich segregation). The numerical results of the particle-tracking simulations are compared to an approximate analytical solution and the late time discrepancy is explained. We also study, for a two dimensional system, how shear flow effects the reaction rate. We do so since shear flow is the simplest form of a spatially variable advection. For the shear flow system, we find that shear flow leads to better mixing of the system on one hand, and a surprising one dimensional segregation at late times, on the other hand. This is in contrast with zero-advection two-dimensional system, where the late time behavior is characterized by the formation of two-dimensional islands. References (Manuscripts in submission): Paster A., D. Bolster and D.A. Benson. Connecting the dots: application of a particle method to the diffusion-reaction equation. Submitted to Advances in Water Resources. Paster A., D. Bolster and D.A. Benson. Particle Tracking and the Diffusion-Reaction Equation. Submitted to Water Resources Research.

  18. Synthesis and reactivity of [penta(4-halogenophenyl)cyclopentadienyl][hydrotris(indazolyl)borato]ruthenium(II) complexes: rotation-induced Fosbury flop in an organometallic molecular turnstile.

    PubMed

    Carella, Alexandre; Launay, Jean-Pierre; Poteau, Romuald; Rapenne, Gwénaël

    2008-01-01

    The preparation of ruthenium(II) complexes coordinated to a penta(4-halogeno)phenylcyclopentadienyl ligand and to the hydrotris(indazolyl)borate ligand are detailed. Our strategy involves first the coordination of the penta(4-bromo)phenylcyclopentadienyl ligand by reaction with the ruthenium-carbonyl cluster followed by the coordination of the tripodal ligand. The pentabrominated precursor was successfully converted to the pentaiodinated derivative by using the Klapars-Buchwald methodology, applied for the first time on organometallic substrates. Cross-coupling reactions were performed on both pentabromo and pentaiodo complexes to introduce in a single step the five peripheric ferrocenyl fragments required to obtain a potential molecular motor. The two ligands present in the ruthenium complexes undergo a correlated rotation that was established both experimentally by NMR experiments and an X-ray diffraction study, and theoretically by DFT calculations. The potential-energy curve obtained by DFT revealed the energy barrier of the gearing mechanism to be only 4.5 kcal mol(-1). These sterically highly constrained complexes can be regarded as organometallic molecular turnstiles.

  19. A particle-mesh algorithm for advection-reaction-diffusion equations with applications to plankton modeling

    NASA Astrophysics Data System (ADS)

    Paparella, F.; Oliveri, F.

    2009-04-01

    The interplay of advection, reaction and diffusion terms in ADR equations is a rather difficult one to be modeled numerically. The kind of spurious oscillations that is usually harmless for non-reacting scalars is often amplified without bounds by reaction terms. Furthermore, in most biogeochimical applications, such as mesoscale or global-scale plankton modeling, the diffusive fluxes may be smaller than the numerical ones. Inspired by the particle-mesh methods used by cosmologists, we propose to discretize on a grid only the diffusive term of the equation, and solve the advection-reaction terms as ordinary differential equations along the characteristic lines. Diffusion happens by letting the concentration field carried by each particle to relax towards the diffusive field known on the grid, without redistributing the particles. This method, in the limit of vanishing diffusivity and for a fixed mesh size, recovers the advection-reaction solution with no numerical diffusion. We show some example numerical solutions of the ADR equations stemming from a simple predator-prey model.

  20. Kinetic study of irreversible inhibition of an enzyme consumed in the reaction it catalyses. Application to the inhibition of the puromycin reaction by spiramycin and hydroxylamine.

    PubMed

    Dinos, G P; Coutsogeorgopoulos, C

    1997-06-01

    A systematic procedure for the kinetic study of irreversible inhibition when the enzyme is consumed in the reaction which it catalyses, has been developed and analysed. Whereas in most reactions the enzymes are regenerated after each catalytic event and serve as reusable transacting effectors, in the consumed enzymes each catalytic center participates only once and there is no enzyme turnover. A systematic kinetic analysis of irreversible inhibition of these enzyme reactions is presented. Based on the algebraic criteria proposed in this work, it should be possible to evaluate either the mechanism of inhibition (complexing or non-complexing), or the type of inhibition (competitive, non-competitive, uncompetitive, mixed non-competitive). In addition, all kinetic constants involved in each case could be calculated. An experimental application of this analysis is also presented, concerning peptide bond formation in vitro. Using the puromycin reaction, which is a model reaction for the study of peptide bond formation in vitro and which follows the same kinetic law as the enzymes under study, we have found that: (i) the antibiotic spiramycin inhibits the puromycin reaction as a competitive irreversible inhibitor in a one step mechanism with an association rate constant equal to 1.3 x 10(4) M-1 s-1 and, (ii) hydroxylamine inhibits the same reaction as an irreversible non-competitive inhibitor also in a one step mechanism with a rate constant equal to 1.6 x 10(-3) M-1 s-1.

  1. Conjugate addition-enantioselective protonation reactions.

    PubMed

    Phelan, James P; Ellman, Jonathan A

    2016-01-01

    The addition of nucleophiles to electron-deficient alkenes represents one of the more general and commonly used strategies for the convergent assembly of more complex structures from simple precursors. In this review the addition of diverse protic and organometallic nucleophiles to electron-deficient alkenes followed by enantioselective protonation is summarized. Reactions are first categorized by the type of electron-deficient alkene and then are further classified according to whether catalysis is achieved with chiral Lewis acids, organocatalysts, or transition metals.

  2. A broadly applicable and practical oligomeric (salen) Co catalyst for enantioselective epoxide ring-opening reactions

    PubMed Central

    White, David E.; Tadross, Pamela M.; Lu, Zhe

    2014-01-01

    The (salen) Co catalyst (4a) can be prepared as a mixture of cyclic oligomers in a short, chromatography-free synthesis from inexpensive, commercially available precursors. This catalyst displays remarkable enhancements in reactivity and enantioselectivity relative to monomeric and other multimeric (salen) Co catalysts in a wide variety of enantioselective epoxide ring-opening reactions. The application of catalyst 4a is illustrated in the kinetic resolution of terminal epoxides by nucleophilic ring-opening with water, phenols, and primary alcohols; the desymmetrization of meso epoxides by addition of water and carbamates; and the desymmetrization of oxetanes by intramolecular ring opening with alcohols and phenols. The favorable solubility properties of complex 4a under the catalytic conditions facilitated mechanistic studies, allowing elucidation of the basis for the beneficial effect of oligomerization. Finally, a catalyst selection guide is provided to delineate the specific advantages of oligomeric catalyst 4a relative to (salen) Co monomer 1 for each reaction class. PMID:25045188

  3. A broadly applicable and practical oligomeric (salen) Co catalyst for enantioselective epoxide ring-opening reactions.

    PubMed

    White, David E; Tadross, Pamela M; Lu, Zhe; Jacobsen, Eric N

    2014-07-08

    The (salen) Co catalyst (4a) can be prepared as a mixture of cyclic oligomers in a short, chromatography-free synthesis from inexpensive, commercially available precursors. This catalyst displays remarkable enhancements in reactivity and enantioselectivity relative to monomeric and other multimeric (salen) Co catalysts in a wide variety of enantioselective epoxide ring-opening reactions. The application of catalyst 4a is illustrated in the kinetic resolution of terminal epoxides by nucleophilic ring-opening with water, phenols, and primary alcohols; the desymmetrization of meso epoxides by addition of water and carbamates; and the desymmetrization of oxetanes by intramolecular ring opening with alcohols and phenols. The favorable solubility properties of complex 4a under the catalytic conditions facilitated mechanistic studies, allowing elucidation of the basis for the beneficial effect of oligomerization. Finally, a catalyst selection guide is provided to delineate the specific advantages of oligomeric catalyst 4a relative to (salen) Co monomer 1 for each reaction class.

  4. Catalytically active polymers obtained by molecular imprinting and their application in chemical reaction engineering.

    PubMed

    Brüggemann, O

    2001-08-01

    Molecular imprinting is a way of creating polymers bearing artificial receptors. It allows the fabrication of highly selective plastics by polymerizing monomers in the presence of a template. This technique primarily had been developed for the generation of biomimetic materials to be used in chromatographic separation, in extraction approaches and in sensors and assays. Beyond these applications, in the past few years molecular imprinting has become a tool for producing new kinds of catalysts. For catalytic applications, the template must be chosen, so that it is structurally comparable with the transition state (a transition state analogue, TSA) of a reaction, or with the product or substrate. The advantage of using these polymeric catalysts is obvious: the backbone withstands more aggressive conditions than a bio material could ever survive. Results are presented showing the applicability of a molecularly imprinted catalyst in different kinds of chemical reactors. It is demonstrated that the catalysts can be utilized not only in batch but also in continuously driven reactors and that their performance can be improved by means of chemical reaction engineering.

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

    NASA Technical Reports Server (NTRS)

    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.

  6. Pd-N-Heterocyclic Carbene (NHC) Organic Silica: Synthesis and Application in Carbon-Carbon Coupling Reactions

    EPA Science Inventory

    The first Pd-N-heterocyclic carbene (NHC) complex in the form of organic silica was prepared using sol-gel method and its application in Heck and Suzuki reaction were demonstrated. These C-C coupling reactions proceeded efficiently under the influence of microwave irradiation, wi...

  7. [Color reaction of cationic surfactants on bromphenol red and its analytical applications].

    PubMed

    Huang, C

    2000-04-01

    The suitable conditions, mechanism, characteristics and analytical applications of bromphenol red (BPR) reacting on cationic surfactants (CSAA) such as cetylpyridinium bromide (CPB) or cetyltrimetryl ammonium bromide (CTAB) were investigated. The results show that the single molecular CSAA reacts on BPR to form an ion-associate complex at pH 5.0-6.0, and its molar ratio (CSAA:BPR) is 3:2. Based on this color reaction, the critical micelle concentration (CMC) of CTAB and CPB was determined, and the possibility for the determination of trace CTAB and CPB were proposed.

  8. Shadow masked organometallic vapor phase epitaxy for advanced micro-optical structures

    NASA Astrophysics Data System (ADS)

    Peake, Gregory Merwin

    2000-12-01

    This thesis presents novel techniques and applications of nonplanar chemical vapor deposition (CVD) for optoelectronic materials and devices. Specifically, nonplanar organometallic vapor phase epitaxy (OMVPE) employing a shadow mask has been developed for the fabrication of integrated optoelectronic structures. Shadow masked OMVPE (SM-OMVPE) is currently the only technique known to produce thick, nonplanar layers of single crystal material without macroscopic faceting. By the use of SM-OMVPE, various microlenses, micromirrors and novel devices have been designed fabricated and tested. Shadow masked microlenses with record short focal lengths have been produced. High quality microlens arrays with accurate control of lens diameter, sagitta, focal length, astigmatism and position have been designed, fabricated and tested. The author has shown that precise three-dimensional control during crystal growth can be employed to construct useful optoelectronic structures in a reproducible manner. This work also presents novel techniques for the fabrication of shadow masks. A high aluminum- concentration spacer layer and chemical recipes for the removal of epitaxial shadow masks are reported. In addition, the first reusable shadow mask constructed by reactive ion etching has been utilized for the growth of shadow masked structures. Direct fusion wafer bonding of silicon shadow masks was first developed by the author and has proven to be a robust, clean and reliable technique for mask placement. The application of shadow masked growth to vertical cavity semiconductor lasers (VCSELs) was initiated in this work. Microlenses were designed for top-emitting VCSELs to provide focusing of the output beam and these designs are currently being fabricated at Sandia National Laboratories. Furthermore, by introducing curvature to the distributed Bragg reflector (DBR) mirrors, a high power single mode VCSEL has been designed. The author has grown the first concentrically

  9. Application of proton boron fusion reaction to radiation therapy: A Monte Carlo simulation study

    NASA Astrophysics Data System (ADS)

    Yoon, Do-Kun; Jung, Joo-Young; Suh, Tae Suk

    2014-12-01

    Three alpha particles are emitted from the point of reaction between a proton and boron. The alpha particles are effective in inducing the death of a tumor cell. After boron is accumulated in the tumor region, the emitted from outside the body proton can react with the boron in the tumor region. An increase of the proton's maximum dose level is caused by the boron and only the tumor cell is damaged more critically. In addition, a prompt gamma ray is emitted from the proton boron reaction point. Here, we show that the effectiveness of the proton boron fusion therapy was verified using Monte Carlo simulations. We found that a dramatic increase by more than half of the proton's maximum dose level was induced by the boron in the tumor region. This increase occurred only when the proton's maximum dose point was located within the boron uptake region. In addition, the 719 keV prompt gamma ray peak produced by the proton boron fusion reaction was positively detected. This therapy method features the advantages such as the application of Bragg-peak to the therapy, the accurate targeting of tumor, improved therapy effects, and the monitoring of the therapy region during treatment.

  10. Application of proton boron fusion reaction to radiation therapy: A Monte Carlo simulation study

    SciTech Connect

    Yoon, Do-Kun; Jung, Joo-Young; Suh, Tae Suk

    2014-12-01

    Three alpha particles are emitted from the point of reaction between a proton and boron. The alpha particles are effective in inducing the death of a tumor cell. After boron is accumulated in the tumor region, the emitted from outside the body proton can react with the boron in the tumor region. An increase of the proton's maximum dose level is caused by the boron and only the tumor cell is damaged more critically. In addition, a prompt gamma ray is emitted from the proton boron reaction point. Here, we show that the effectiveness of the proton boron fusion therapy was verified using Monte Carlo simulations. We found that a dramatic increase by more than half of the proton's maximum dose level was induced by the boron in the tumor region. This increase occurred only when the proton's maximum dose point was located within the boron uptake region. In addition, the 719 keV prompt gamma ray peak produced by the proton boron fusion reaction was positively detected. This therapy method features the advantages such as the application of Bragg-peak to the therapy, the accurate targeting of tumor, improved therapy effects, and the monitoring of the therapy region during treatment.

  11. SU-D-304-07: Application of Proton Boron Fusion Reaction to Radiation Therapy

    SciTech Connect

    Jung, J; Yoon, D; Shin, H; Kim, M; Suh, T

    2015-06-15

    Purpose: we present the introduction of a therapy method using the proton boron fusion reaction. The purpose of this study is to verify the theoretical validity of proton boron fusion therapy using Monte Carlo simulations. Methods: After boron is accumulated in the tumor region, the emitted from outside the body proton can react with the boron in the tumor region. An increase of the proton’s maximum dose level is caused by the boron and only the tumor cell is damaged more critically. In addition, a prompt gamma ray is emitted from the proton boron reaction point. Here we show that the effectiveness of the proton boron fusion therapy (PBFT) was verified using Monte Carlo simulations. Results: We found that a dramatic increase by more than half of the proton’s maximum dose level was induced by the boron in the tumor region. This increase occurred only when the proton’s maximum dose point was located within the boron uptake region (BUR). In addition, the 719 keV prompt gamma ray peak produced by the proton boron fusion reaction was positively detected. Conclusion: This therapy method features the advantages such as the application of Bragg-peak to the therapy, the accurate targeting of tumor, improved therapy effects, and the monitoring of the therapy region during treatment.

  12. Synthesis of Diverse Heterocyclic Scaffolds via Tandem Additions to Imine Derivatives and Ring-Forming Reactions

    PubMed Central

    Sunderhaus, James D.; Dockendorff, Chris; Martin, Stephen F.

    2009-01-01

    A novel strategy has been developed for the efficient syntheses of diverse arrays of heterocyclic compounds. The key elements of the approach comprise a Mannich-type, multicomponent coupling reaction in which functionalized amines, aromatic aldehydes, acylating agents, and π- and organometallic nucleophiles are combined to generate intermediates that are then further transformed into diverse heterocyclic scaffolds via a variety of cyclization manifolds. Significantly, many of these scaffolds bear functionality that may be exploited by further manipulation to create diverse collections of compounds having substructures found in biologically active natural products and clinically useful drugs. The practical utility of this strategy was exemplified by its application to the first, and extraordinarily concise synthesis of the isopavine alkaloid roelactamine. PMID:20625454

  13. Reaction Rate Theory in Coordination Number Space: An Application to Ion Solvation

    SciTech Connect

    Roy, Santanu; Baer, Marcel D.; Mundy, Christopher J.; Schenter, Gregory K.

    2016-04-14

    Understanding reaction mechanisms in many chemical and biological processes require application of rare event theories. In these theories, an effective choice of a reaction coordinate to describe a reaction pathway is essential. To this end, we study ion solvation in water using molecular dynamics simulations and explore the utility of coordination number (n = number of water molecules in the first solvation shell) as the reaction coordinate. Here we compute the potential of mean force (W(n)) using umbrella sampling, predicting multiple metastable n-states for both cations and anions. We find with increasing ionic size, these states become more stable and structured for cations when compared to anions. We have extended transition state theory (TST) to calculate transition rates between n-states. TST overestimates the rate constant due to solvent-induced barrier recrossings that are not accounted for. We correct the TST rates by calculating transmission coefficients using the reactive flux method. This approach enables a new way of understanding rare events involving coordination complexes. We gratefully acknowledge Liem Dang and Panos Stinis for useful discussion. This research used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. SR, CJM, and GKS were supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. MDB was supported by MS3 (Materials Synthesis and Simulation Across Scales) Initiative, a Laboratory Directed Research and Development Program at Pacific Northwest National Laboratory (PNNL). PNNL is a multiprogram national laboratory operated by Battelle for the U.S. Department of Energy.

  14. Genipin diffusion and reaction into a gelatin matrix for tissue engineering applications.

    PubMed

    Montemurro, Francesca; De Maria, Carmelo; Orsi, Gianni; Ghezzi, Lisa; Tinè, Maria Rosaria; Vozzi, Giovanni

    2017-04-01

    Genipin is a natural low-toxic cross-linker for molecules with primary amino groups, and its use with collagen and gelatin has shown a great potential in tissue engineering applications. The fabrication of scaffolds with a well-organized micro and macro topology using additive manufacturing systems requires an accurate control of working parameters, such as reaction rate, gelling time, and diffusion constant. A polymeric system of 5% w/v gelatin in PBS with 2 mg/mL collagen solutions in a 1:1 weight ratio was used as template to perform measurements varying genipin concentration in a range of 0.1-1.5% w/w with respect to gelatin. In the first part of this work, the reaction rate of the polymeric system was estimated using a new colorimetric analysis of the reaction. Then its workability time, closely related to the gelling time, was evaluated thanks to rheological analysis: finally, the quantification of static and dynamic diffusion constants of genipin across nonreacting and reacting membranes, made respectively by agarose and gelatin, was performed. It was shown that the colorimetric analysis is a good indicator of the reaction progress. The gelling time depends on the genipin concentration, but a workability window of 40 min guaranteed up to 0.5% w/w genipin. The dynamic diffusion constant of genipin in the proposed polymeric system is in the order of magnitude of 10(-7) . The obtained results indicated the possibility to use the genipin, gelatin, and collagen, in the proposed concentrations, to build well-defined hydrogel scaffolds with both extrusion-based and 3D ink-jet system. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 105B: 473-480, 2017.

  15. Towards cancer cell-specific phototoxic organometallic rhenium(I) complexes.

    PubMed

    Leonidova, Anna; Pierroz, Vanessa; Rubbiani, Riccardo; Heier, Jakob; Ferrari, Stefano; Gasser, Gilles

    2014-03-21

    Over the recent years, several Re(I) organometallic compounds have been shown to be toxic to various cancer cell lines. However, these compounds lacked sufficient selectivity towards cancer tissues to be used as novel chemotherapeutic agents. In this study, we probe the potential of two known N,N-bis(quinolinoyl) Re(I) tricarbonyl complex derivatives, namely Re(I) tricarbonyl [N,N-bis(quinolin-2-ylmethyl)amino]-4-butane-1-amine (Re-NH₂) and Re(I) tricarbonyl [N,N-bis(quinolin-2-ylmethyl)amino]-5-valeric acid (Re-COOH), as photodynamic therapy (PDT) photosensitizers. Re-NH₂ and Re-COOH proved to be excellent singlet oxygen generators in a lipophilic environment with quantum yields of about 75%. Furthermore, we envisaged to improve the selectivity of Re-COOH via conjugation to two types of peptides, namely a nuclear localization signal (NLS) and a derivative of the neuropeptide bombesin, to form Re-NLS and Re-Bombesin, respectively. Fluorescent microscopy on cervical cancer cells (HeLa) showed that the conjugation of Re-COOH to NLS significantly enhanced the compound's accumulation into the cell nucleus and more specifically into its nucleoli. Importantly, in view of PDT applications, the cytotoxicity of the Re complexes and their bioconjugates increased significantly upon light irradiation. In particular, Re-Bombesin was found to be at least 20-fold more toxic after light irradiation. DNA photo-cleavage studies demonstrated that all compounds damaged DNA via singlet oxygen and, to a minor extent, superoxide production.

  16. Molecular tectonics: heterometallic coordination networks based on a Pt(II) organometallic metallatecton.

    PubMed

    Zigon, Nicolas; Kyritsakas, Nathalie; Hosseini, Mir Wais

    2015-08-28

    Combinations of a neutral organometallic tecton based on a square planar Pt(ii) complex bearing two triphenylphosphine groups and two 4-ethynylpyridyl coordinating moieties in trans positions, with various metal halides (MX2, M = Co(ii), Ni(ii), Cd(ii), X = Cl(-) or Br(-)) lead to the formation of 2D grid type heterobimetallic coordination networks in the crystalline phase.

  17. 40 CFR 721.10414 - Polycyclic polyamine diester organometallic compound (generic) (P-10-358).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Polycyclic polyamine diester organometallic compound (generic) (P-10-358). 721.10414 Section 721.10414 Protection of Environment ENVIRONMENTAL... compound (generic) (P-10-358). (a) Chemical substance and significant new uses subject to reporting....

  18. 40 CFR 721.10414 - Polycyclic polyamine diester organometallic compound (generic) (P-10-358).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Polycyclic polyamine diester organometallic compound (generic) (P-10-358). 721.10414 Section 721.10414 Protection of Environment ENVIRONMENTAL... compound (generic) (P-10-358). (a) Chemical substance and significant new uses subject to reporting....

  19. 40 CFR 721.10414 - Polycyclic polyamine diester organometallic compound (generic) (P-10-358).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Polycyclic polyamine diester organometallic compound (generic) (P-10-358). 721.10414 Section 721.10414 Protection of Environment ENVIRONMENTAL... compound (generic) (P-10-358). (a) Chemical substance and significant new uses subject to reporting....

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

    ERIC Educational Resources Information Center

    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…

  1. Facile synthesis of PdSx/C porous nanospheres and their applications for ethanol oxidation reaction

    NASA Astrophysics Data System (ADS)

    Zhang, Qiang; Zhang, Fuhua; Ma, Xuemei; Zheng, Yiqun; Hou, Shifeng

    2016-12-01

    We report a facile approach for the synthesis of carbon-supported palladium polysulphide porous nanospheres (PdSx/C) and their applications for ethanol oxidation reaction. Typical synthesis started with generation of palladium/poly (3,4-ethylenedioxythiophene)(Pd/PEDOT) nanospheres, followed by a calcination process at an optimized temperature to form PdSx/C, with an average size of 2.47 ± 0.60 and 50 nm of PdSx nanoparticles and carbon porous nanospheres, respectively. Various techniques, such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and electrochemical techniques were performed to characterize their morphologies, compositions and structures. In contrary to most Pd-based electrochemical catalysts that could be easily poised with trace sulfur during the catalytic oxidation process, the as-prepared PdSx/C porous nanospheres exhibited high electrocatalytic activities and stabilities for the electrochemical catalytic oxidation of ethanol in alkaline medium. In particular, the forward peak current intensity achieved 162.1 mA mg-1 and still maintained at 46.7 mA mg-1 even after 1000 cycles. This current work not only offers a novel type of fuel-cell catalyst for ethanol oxidation reaction, but also provides a possible route for solving the sulfur-poisoning problem in catalysis.

  2. Advances in digital polymerase chain reaction (dPCR) and its emerging biomedical applications.

    PubMed

    Cao, Lei; Cui, Xingye; Hu, Jie; Li, Zedong; Choi, Jane Ru; Yang, Qingzhen; Lin, Min; Ying Hui, Li; Xu, Feng

    2017-04-15

    Since the invention of polymerase chain reaction (PCR) in 1985, PCR has played a significant role in molecular diagnostics for genetic diseases, pathogens, oncogenes and forensic identification. In the past three decades, PCR has evolved from end-point PCR, through real-time PCR, to its current version, which is the absolute quantitive digital PCR (dPCR). In this review, we first discuss the principles of all key steps of dPCR, i.e., sample dispersion, amplification, and quantification, covering commercialized apparatuses and other devices still under lab development. We highlight the advantages and disadvantages of different technologies based on these steps, and discuss the emerging biomedical applications of dPCR. Finally, we provide a glimpse of the existing challenges and future perspectives for dPCR.

  3. Alkene Cleavage Catalysed by Heme and Nonheme Enzymes: Reaction Mechanisms and Biocatalytic Applications

    PubMed Central

    Mutti, Francesco G.

    2012-01-01

    The oxidative cleavage of alkenes is classically performed by chemical methods, although they display several drawbacks. Ozonolysis requires harsh conditions (−78°C, for a safe process) and reducing reagents in a molar amount, whereas the use of poisonous heavy metals such as Cr, Os, or Ru as catalysts is additionally plagued by low yield and selectivity. Conversely, heme and nonheme enzymes can catalyse the oxidative alkene cleavage at ambient temperature and atmospheric pressure in an aqueous buffer, showing excellent chemo- and regioselectivities in certain cases. This paper focuses on the alkene cleavage catalysed by iron cofactor-dependent enzymes encompassing the reaction mechanisms (in case where it is known) and the application of these enzymes in biocatalysis. PMID:22811656

  4. Application of click chemistry conditions for 5-bromo-2'-deoxyuridine determination through Fenton and related reactions.

    PubMed

    Cappella, Paolo; Pulici, Maurizio; Gasparri, Fabio

    2015-01-05

    Mixtures of ascorbate and copper used in certain click chemistry experimental conditions act as oxidizing agents, catalyzing the formation of reactive oxygen species through Fenton and related reactions. Hydroxyl radicals act as chemical nucleases, introducing DNA strand breaks that can be exploited for BrdU immunostaining in place of acid denaturation. This procedure is readily applicable to high content analysis and flow cytometry assays, and provides results comparable to click chemistry EdU cycloaddition and classical BrdU immunodetection. Importantly, this approach allows preservation of labile epitopes such as phosphoproteins. This unit describes an optimized method that successfully employs Fenton chemistry for simultaneous detection of phosphoproteins and BrdU in intact cells.

  5. Coriolis coupling effects in the dynamics of deep well reactions: application to the H(+) + D2 reaction.

    PubMed

    Hankel, M

    2011-05-07

    We present exact and estimated quantum differential and integral cross sections as well as product state distributions for the title reaction. We employ a time-dependent wavepacket method including all Coriolis couplings and also an adapted code where the helicity quantum number and with this the Coriolis couplings have been truncated. Results from helicity truncated as well as helicity conserving (HC) calculation are presented. The HC calculations fail to reproduce the exact results due to the influence of the centrifugal barrier. While the truncated calculation overestimate the exact integral cross sections they reproduce the features of the integral cross section very well. We also find that the product rotational state distributions are well reproduced if the maximum helicity state is chosen carefully. The helicity truncated calculations fail to give a good approximation of differential cross sections.

  6. Application of a reaction model to improve calculation of the sugar recovery standard for sugar analysis.

    PubMed

    Shen, Jiacheng; Wyman, Charles E

    2012-01-01

    A kinetic model was applied to improve determination of the sugar recovery standard (SRS) for biomass analysis. Three sets of xylose (0.10-1.00 g/L and 0.999-19.995 g/L) and glucose (0.206-1.602 g/L) concentrations were measured by HPLC following reaction of each for 1 h. Then, parameters in a kinetic model were fit to the resulting sugar concentration data, and the model was applied to predict the initial sugar concentrations and the best SRS value (SRS(p)). The initial sugar concentrations predicted by the model agreed with the actual initial sugar concentrations. Although the SRS(e) calculated directly from experimental data oscillated considerably with sugar concentration, the SRS(p) trend was smooth. Statistical analysis of errors and application of the F-test confirmed that application of the model reduced experimental errors in SRS(e). Reference SRS(e) values are reported for the three series of concentrations.

  7. [Application of the polymerase chain reaction to the diagnosis of sickle cell anemia in Venezuela].

    PubMed

    Martínez, J; Blanco, Z; Hakshaw, P; Moreno, N

    1998-02-01

    Application of polymerase chain reaction technology to detect sickle cell patients and heterozygous carriers in a group of patients suspect for sickle cell disease was carried out. The sample was composed of 102 normal individuals, and 102 unrelated out patients who were attending in the Hematology Service at the Maracay Central Hospital in the State of Aragua in Venezuela. All patients were interviewed. Results of their medical histories and the physical examination, made during the clinical visit, were recorded. The blood samples were collected in EDTA by venopuncture and genomic DNA was extracted from leucocytes. An amplified 536 base pairs fragment of the beta-globin gene containing codon 6, was digested with an isoschizomer of Mst II, Bsu36 I and electrophoresed in 3% agarose. We have established the technical conditions in our laboratory for the detection of sickle cell disease using a PCR assay. 32 patients having haemoglobin SS (HbSS) and 70 patients in the heterozygous state (HbAS) were identified. We confirm that the normal controls have the HbAA genotype. The standardization of a highly sensitive and specific diagnostic test for sickle cell disease permited us to identify the normal controls, the homozygotes and heterozygotes. This methodology is one of the fundamental technical bases for establishing a newborn screening programme in the Central Region of Venezuela and also has application in research related with other genetic diseases that affect the Venezuelan people.

  8. The Effect of Fuel Types on Porous Alumina Produced via Soft Combustion Reaction for Implant Applications

    NASA Astrophysics Data System (ADS)

    Jamil, Radin Shafinaz; Abdul Razak, Khairunisak; Ahmad, Nurfateen Fakhariah; Mohamad, Hasmaliza

    2012-03-01

    This article describes the effects of fuel types on the porous structure of alumina produced using a soft combustion reaction. There are several combustion parameters that could affect the porous structure of the alumina produced such as fuel-to-oxidizer ratios, ignition temperature, and type of fuels. In this study, the effect of fuel types on alumina properties was studied. Citric acid, glycine, and urea were used as fuels along with aluminum nitrate as an oxidizer. The properties of porous alumina produced using three different fuels were compared to determine the optimum fuel that could produce the best properties for implant applications. X-ray diffraction analysis showed that single-phase alumina powder was obtained in all samples. Morphology observation using scanning electron microscope (SEM) on sintered bodies showed open pores which had potential to be used in implant applications. Porous alumina produced using glycine as fuel (AG) showed the best properties; high surface area of 8.7 m2/g, porosity of 70% and sintered density 1.37 g/cm3.

  9. Plasmonic Properties of Bimetallic Nanostructures and Their Applications in Hydrogen Sensing and Chemical Reactions

    NASA Astrophysics Data System (ADS)

    Jiang, Ruibin

    Noble metal nanocrystals have attracted great interest from a wide range of research fields because of their intriguing properties endowed by their localized surface plasmon resonances, which are the collective oscillations of free electrons. Under resonant excitation, metal nanostructures exhibit very large scattering and absorption cross sections and large near-field enhancement. These extraordinary properties can be used in different applications, such as plasmonic sensing and imaging, plasmon-controlled optics, photothermal therapy, photocatalysis, solar cells, and so on. Gold and Silver nanocrystals have plasmon resonances in the visible and near-infrared regions. However, gold and silver are not suitable for some applications. For example, they are generally inactive for catalyzing chemical reactions. The integration of plasmonic metals with other metals can offer superior or new physical/chemical properties. In this thesis, I prepared Au/Ag and Au/Pd bimetallic nanostructures and studied their plasmonic properties and applications in hydrogen sensing and photocatalysis. Seeds have a crucial importance in the synthesis of bimetallic nanostructures. I therefore first studied the roles of the crystalline structure and shape of seeds on the overgrowth of bimetallic nanostructures. The overgrowth of silver and palladium on single crystalline Au nanorods, multicrystalline Au nanorods, and nanobipyramids were studied under the same conditions for each metal. The growths of silver and palladium on single crystalline Au nanorods gave cuboidal nanostructures, while rod-shaped nanostructures were obtained from the growths of silver and palladium on multicrystalline Au nanorods and nanobipyramids. Moreover, the growths of silver and palladium on multicrystalline Au nanobipyramids started at the stepped side facets, while the growths started at the twin boundaries on multicrystalline Au nanorods. These results unambiguously indicate that the crystalline structure of

  10. Alumina-supported bimetallics of palladium alloyed with germanium, tin, lead, or antimony from organometallic precursors I. Preparation and characterization

    SciTech Connect

    Aduriz, H.R.; Bodnariuk, P. , Bahia Blanca ); Coq, B.; Figueras, F. )

    1989-09-01

    Bimetallic PdSn, PdSb, PdPb, and PdGe on alumina catalysts with a low metal content have been prepared using either chloride or organometallic precursors. For the catalysts obtained from chloride precursors no interaction was observed between the two metals, and the catalysts behaved like pure Pd/Al{sub 2}O{sub 3}. In contrast, the reactions of (C{sub 4}H{sub 9}){sub 4}Sn, (C{sub 4}H{sub 9}){sub 4}Pb, (C{sub 4}H{sub 9}){sub 4}Ge, or (C{sub 4}H{sub 9}){sub 3}Sb in n-heptane solution with reduced Pd/Al{sub 2}O{sub 3} catalyst yielded a supported alloy. The interaction between metallic palladium and the organic modifier is highly selective and leads to the formation of a well-tailored bimetallic catalyst. When these final solids are reduced at 573 or 773 K, the second metal locates preferentially at the outer layer of the bimetallic aggregates. After reduction at 773 K large metallic aggregates are obtained (particle size 15 nm), and the formation of {beta}-palladium hydride, which can be formed with pure palladium catalysts, is suppressed by the addition of a small amount of the second metal. The specific activity of the palladium surface atoms for isoprene hydrogenation is then lowered, and the selectivity increased.

  11. The Copper-nicotinamide complex: sustainable applications in coupling and cycloaddition reactions

    EPA Science Inventory

    Crystalline copper (II)-nicotinamide complex, synthesized via simple mixing of copper chloride and nicotinamide solution at room temperature, catalyzes the C-S, C-N bond forming and cycloaddition reactions under a variety of sustainable reaction conditions.

  12. Organometallic ruthenium(II) complexes: synthesis, structure and influence of substitution at azomethine carbon towards DNA/BSA binding, radical scavenging and cytotoxicity.

    PubMed

    Sathyadevi, Palanisamy; Krishnamoorthy, Paramasivam; Bhuvanesh, Nattamai S P; Kalaiselvi, Palaniswamy; Vijaya Padma, Viswanadha; Dharmaraj, Nallasamy

    2012-09-01

    Bivalent, ruthenium organometallics containing hydrazone ligands with the composition [RuH(CO)(PPh(3))(2)(L(1-3))] (4-6) have been synthesised from the reactions of [RuH(2)(CO)(PPh(3))(3)] and benzoic acid pyridine-2-ylmethylene-hydrazide (HL(1)) (1) /benzoic acid (1-pyridin-2-yl-ethylidene)-hydrazide (HL(2)) (2)/benzoic acid (phenyl-pyridin-2-yl-methylene)-hydrazide (HL(3)) (3) and characterised by various physico-chemical techniques. The X-ray crystal structure of one of the above complexes, [RuH(CO)(PPh(3))(2)(L(3))] (6) demonstrated a distorted octahedral coordination geometry around the metal centre. Results of our investigation on the effect of substitution (H or CH(3) or C(6)H(5)) at the azomethine carbon of coordinated hydrazone in these ruthenium chelates on the potential binding with DNA/BSA, free radical scavenging and cytotoxicity is presented.

  13. Combining Organometallic Reagents, the Sulfur Dioxide Surrogate DABSO, and Amines: A One-Pot Preparation of Sulfonamides, Amenable to Array Synthesis**

    PubMed Central

    Deeming, Alex S; Russell, Claire J; Willis, Michael C

    2015-01-01

    We describe a method for the synthesis of sulfonamides through the combination of an organometallic reagent, a sulfur dioxide equivalent, and an aqueous solution of an amine under oxidative conditions (bleach). This simple reaction protocol avoids the need to employ sulfonyl chloride substrates, thus removing the limitation imposed by the commercial availability of these reagents. The resultant method allows access to new chemical space, and is also tolerant of the polar functional groups needed to impart favorable physiochemical properties required for medicinal chemistry and agrochemistry. The developed chemistry is employed in the synthesis of a targeted 70 compound array, prepared using automated methods. The array achieved a 93 % success rate for compounds prepared. Calculated molecular weights, lipophilicities, and polar surface areas are presented, demonstrating the utility of the method for delivering sulfonamides with drug-like properties. PMID:25431118

  14. Cross-coupling of C(sp)-H Bonds with Organometallic Reagents via Pd(II)/Pd(0) Catalysis**

    PubMed

    Wasa, Masayuki; Engle, Keary M; Yu, Jin-Quan

    2010-12-01

    Palladium-catalyzed C-H activation/C-C bond-forming reactions have emerged as a promising class of synthetic tools in organic chemistry. Among the many different means of forging C-C bonds using Pd-mediated C-H activation, a new horizon in this field is Pd(II)-catalyzed cross-coupling of C-H bonds with organometallic reagents via a Pd(II)/Pd(0) catalytic cycle. While this type of reaction has proven to be effective for the selective functionalization of aryl C(sp(2))-H bonds, the focus of this review is on Pd(II)-catalyzed C(sp(3))-H activation/C-C cross-coupling, a topic of particular importance because reactions of this type enable fundamentally new methods for bond construction. Since our laboratory's initial report on cross-coupling of C-H bonds in 2006, this area has expanded rapidly, and the unique ability of Pd(II) catalysts to cleave and functionalize alkyl C(sp(3))-H bonds has been exploited to develop protocols for forming an array of C(sp(3))-C(sp(2)) and C(sp(3))-C(sp(3)) bonds. Furthermore, enantioselective C(sp(3))-H activation/C-C cross-coupling has been achieved through the use of chiral amino acid-derived ligands, offering a novel technique for producing enantioenriched molecules. Although this nascent field remains at an early stage of development, further investigations hold the potential to revolutionalize the way in which chiral molecules are synthesized in industrial and academic laboratories.

  15. Carbon–heteroatom bond formation catalysed by organometallic complexes

    PubMed Central

    Hartwig, John F.

    2010-01-01

    At one time the synthetic chemist’s last resort, reactions catalysed by transition metals are now the preferred method for synthesizing many types of organic molecule. A recent success in this type of catalysis is the discovery of reactions that form bonds between carbon and heteroatoms (such as nitrogen, oxygen, sulphur, silicon and boron) via complexes of transition metals with amides, alkoxides, thiolates, silyl groups or boryl groups. The development of these catalytic processes has been supported by the discovery of new elementary reactions that occur at metal–heteroatom bonds and by the identification of factors that control these reactions. Together, these findings have led to new synthetic processes that are in daily use and have formed a foundation for the development of processes that are likely to be central to synthetic chemistry in the future. PMID:18800130

  16. Applicability of fiber-optic-based Raman probes for on-line reaction monitoring of high-pressure catalytic hydrogenation reactions.

    PubMed

    Hamminga, Gerben M; Mul, Guido; Moulijn, Jacob A

    2007-05-01

    This study evaluates the applicability of fiber-optic-based Raman probes for on-line reaction monitoring of high-pressure catalytic hydrogenation reactions in batch autoclaves. First, based on trends in the strong intensity of the 945 cm(-1) C-O-C vibration of 1,3-dioxolane, the effect of various experimental parameters on sensitivity was evaluated and can be summarized as follows: (1) above 500 rpm a linear increase in stirring speed induces a linear decrease in Raman intensity; (2) a linear increase in hydrogen pressure also leads to a linear decrease of the Raman signal; (3) linear temperature elevation exponentially decreases the Raman intensity; and (4) increasing the catalyst particle concentration results in a steep nonlinear decrease of the Raman signal. Light scattering by gas bubbles, or combined scattering and absorption by (black) catalyst particles, reducing the amount of light collected by the optical fiber probe, explain the observed experimental trends. Second, the sensitivity of Raman spectroscopy was directly compared with attenuated total reflection-Fourier transform infrared (ATR-FT-IR) spectroscopy in the analysis of three different hydrogenation reactions over a Cu-ZnO catalyst. From the applied target molecules, diethyl maleate hydrogenation could be very well analyzed by Raman spectroscopy due to the high Raman scattering efficiency of the C=C bond, while for analysis of the hydrogenation of gamma-butyrolactone or 1-butanal, ATR-FT-IR is the technique of choice.

  17. Role of prostaglandin E2 and leukotriene B4 in skin reaction induced by transdermal application of propranolol.

    PubMed

    Kobayashi, I; Hosaka, K; Maruo, H; Saeki, Y; Kamiyama, M; Konno, C; Gemba, M

    2000-02-01

    Dermal application of propranolol (PRL) induced formation of erythema and edema, and pseudoeosinophil infiltration in epidermis and dermis at the application site in guinea pigs. We investigated the production of prostaglandin E2 (PGE2) and leukotriene B4 (LTB4) at the application site of PRL and the role of these inflammatory chemical mediators in the occurrence of the skin reactions. PGE2 was found to be produced at the application site slightly after the accumulation of PRL released from the adhesive bandage in the patch test, and the amount of PGE2 increased continuously, with a peak value obtained at 24 h after application. The time-course changes resembled those of delta a* value, the index of erythema formation determined by colorimetric measurement, and edema formation. The production of PGE2 by dermal application of PRL was suppressed by local pretreatment with dexamethasone or indomethacin. However, no notable production of LTB4 was observed at the application site of PRL.

  18. Scalable graphene synthesised by plasma-assisted selective reaction on silicon carbide for device applications

    NASA Astrophysics Data System (ADS)

    Tsai, Hsu-Sheng; Lai, Chih-Chung; Medina, Henry; Lin, Shih-Ming; Shih, Yu-Chuan; Chen, Yu-Ze; Liang, Jenq-Horng; Chueh, Yu-Lun

    2014-10-01

    Graphene, a two-dimensional material with honeycomb arrays of carbon atoms, has shown outstanding physical properties that make it a promising candidate material for a variety of electronic applications. To date, several issues related to the material synthesis and device fabrication need to be overcome. Despite the fact that large-area graphene films synthesised by chemical vapour deposition (CVD) can be grown with relatively few defects, the required transfer process creates wrinkles and polymer residues that greatly reduce its performance in device applications. Graphene synthesised on silicon carbide (SiC) has shown outstanding mobility and has been successfully used to develop ultra-high frequency transistors; however, this fabrication method is limited due to the use of costly ultra-high vacuum (UHV) equipment that can reach temperatures over 1500 °C. Here, we show a simple and novel approach to synthesise graphene on SiC substrates that greatly reduces the temperature and vacuum requirements and allows the use of equipment commonly used in the semiconductor processing industry. In this work, we used plasma treatment followed by annealing in order to obtain large-scale graphene films from bulk SiC. After exposure to N2 plasma, the annealing process promotes the reaction of nitrogen ions with Si and the simultaneous condensation of C on the surface of SiC. Eventually, a uniform, large-scale, n-type graphene film with remarkable transport behaviour on the SiC wafer is achieved. Furthermore, graphene field effect transistors (FETs) with high carrier mobilities on SiC were also demonstrated in this study.Graphene, a two-dimensional material with honeycomb arrays of carbon atoms, has shown outstanding physical properties that make it a promising candidate material for a variety of electronic applications. To date, several issues related to the material synthesis and device fabrication need to be overcome. Despite the fact that large-area graphene films

  19. Cytotoxicity of iron oxide nanoparticles made from the thermal decomposition of organometallics and aqueous phase transfer with Pluronic F127

    PubMed Central

    Gonzales, Marcela; Mitsumori, Lee M.; Kushleika, John V.; Rosenfeld, Michael E.; Krishnan, Kannan M.

    2010-01-01

    Magnetic nanoparticles are promising molecular imaging agents due to their relative high relaxivity and the potential to modify surface functionality to tailor biodistribution. In this work we describe the synthesis of magnetic nanoparticles using organic solvents with organometallic precursors. This method results in nanoparticles that are highly crystalline, and have uniform size and shape. The ability to create a monodispersion of particles of the same size and shape results in unique magnetic properties that can be useful for biomedical applications with MR imaging. Before these nanoparticles can be used in biological applications, however, means are needed to make the nanoparticles soluble in aqueous solutions and the toxicity of these nanoparticles needs to be studied. We have developed two methods to surface modify and transfer these nanoparticles to the aqueous phase using the biocompatible co-polymer, Pluronic F127. Cytotoxicity was found to be dependent on the coating procedure used. Nanoparticle effects on a cell-culture model was quantified using concurrent assaying; a LDH assay to determine cytotoxicity and an MTS assay to determine viability for a 24 hour incubation period. Concurrent assaying was done to insure that nanoparticles did not interfere with the colorimetric assay results. This report demonstrates that a monodispersion of nanoparticles of uniform size and shape can be manufactured. Initial cytotoxicity testing of new molecular imaging agents need to be carefully constructed to avoid interference and erroneous results. PMID:20623517

  20. APPLICATION OF NONINVASIVE PREGNANCY DIAGNOSIS IN BACTRIAN CAMELS (CAMELUS BACTRIANUS) USING CUBONI REACTION AND BARIUM CHLORIDE TEST.

    PubMed

    Fedorova, Tamara; Brandlová, Karolína; Lukešová, Daniela

    2015-06-01

    Pregnancy diagnoses in half-tamed animals are often very complicated. This study aimed to examine the alternative noninvasive and cheap methods of pregnancy diagnosis from urine in domestic Bactrian camels (Camelus bactrianus). Urine from 14 female camels kept in four European zoologic gardens was collected and tested by two chemical tests--Cuboni reaction and barium chloride test. The Cuboni reaction was significantly (P<0.01) affected by the pregnancy status of female camels. The total accuracy of the Cuboni reaction was 70.5% but it increased significantly (P<0.05) in the time leading up to parturition. The accuracy was 100% in the 3rd third of pregnancy. Urine of nonpregnant females did not react with a solution of barium chloride while, contrary to other studies, white precipitates formed mostly (80 to 100%) in urine of pregnant females. This study concluded that the Cuboni reaction is applicable for pregnancy diagnosis in camels.

  1. Cation coordination reactions on nanocrystals: surface/interface, doping control and advanced photocatalysis applications (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Zhang, Jiatao

    2016-10-01

    Abstract: Including the shape and size effect, the controllable doping, hetero-composite and surface/interface are the prerequisite of colloidal nanocrystals for exploring their optoelectronic properties, such as fluorescence, plasmon-exciton coupling, efficient electron/hole separation, and enhanced photocatalysis applications. By controlling soft acid-base coordination reactions between cation molecular complexes and colloidal nanocrystals, we showed that chemical thermodynamics could drive nanoscale monocrystalline growth of the semiconductor shell on metal nano-substrates and the substitutional heterovalent doping in semiconductor nanocrystals. We have demonstrated evolution of relative position of Au and II-VI semiconductor in Au-Semi from symmetric to asymmetric configuration, different phosphines initiated morphology engineering, oriented attachment of quantum dots into micrometer nanosheets with synergistic control of surface/interface and doing, which can further lead to fine tuning of plasmon-exciton coupling. Therefore, different hydrogen photocatalytic performance, Plasmon enhanced photocatalysis properties have been achieved further which lead to the fine tuning of plasmon-exciton coupling. Substitutional heterovalent doping here enables the tailoring of optical, electronic properties and photocatalysis applications of semiconductor nanocrystals because of electronic impurities (p-, n-type doping) control. References: (1) J. Gui, J. Zhang*, et al. Angew. Chem. Int. Ed. 2015, 54, 3683. (2) Q. Zhao, J. Zhang*, etc., Adv. Mater. 2014, 26, 1387. (3) J. Liu, Q. Zhao, S. G. Wang*, J. Zhang*, etc., Adv. Mater. 2015, 27-2753-2761. (4) H. Qian, J. Zhang*, etc., NPG Asia Mater. (2015) 7, e152. (5) M. Ji, M. Xu, etc., J. Zhang*, Adv. Mater. 2016, in proof. (6) S. Yu, J. T. Zhang, Y. Tang, M. Ouyang*, Nano Lett. 2015, 15, 6282-6288. (7) J. Zhang, Y. Tang, K. Lee and M. Ouyang*, Science 2010, 327, 1634. (8) J. Zhang, Y. Tang, K. Lee, M. Ouyang*, Nature 2010, 466

  2. Oxygen-Incorporated MoS2 Nanosheets with Expanded Interlayers for Hydrogen Evolution Reaction and Pseudocapacitor Applications.

    PubMed

    Zhou, Jiang; Fang, Guozhao; Pan, Anqiang; Liang, Shuquan

    2016-12-14

    Two-dimensional transition-metal dichalcogenides (TMDs) nanosheets have attracted tremendous research interest. Engineering the structure of MoS2 may result in desirable performance for energy applications. In this work, oxygen-incorporated MoS2 nanosheets with expanded interlayers have been synthesized by a solvothermal reaction. The oxygen-incorporated MoS2 nanosheets with rich defects demonstrate excellent hydrogen evolution reaction activity with a small Tafel slope of 42 mV decade(-1) as well as excellent long-term stability. Interestingly, a large expanded ∼8.40 Å interlayer of (002) faces can be achieved by controlling the reaction time. This material also shows excellent long-term cycling stability (up to 20 000 cycles) as well as high specific capacitance for pseudocapacitors. We believe that the structural modification strategy can be applied for other TMDs to further optimize the performance for various applications.

  3. Bimolecular reaction rates from ring polymer molecular dynamics: Application to H + CH4→ H2 + CH3

    NASA Astrophysics Data System (ADS)

    Suleimanov, Yury V.; Collepardo-Guevara, Rosana; Manolopoulos, David E.

    2011-01-01

    In a recent paper, we have developed an efficient implementation of the ring polymer molecular dynamics (RPMD) method for calculating bimolecular chemical reaction rates in the gas phase, and illustrated it with applications to some benchmark atom-diatom reactions. In this paper, we show that the same methodology can readily be used to treat more complex polyatomic reactions in their full dimensionality, such as the hydrogen abstraction reaction from methane, H + CH_4 rArr H_2 + CH_3. The present calculations were carried out using a modified and recalibrated version of the Jordan-Gilbert potential energy surface. The thermal rate coefficients obtained between 200 and 2000 K are presented and compared with previous results for the same potential energy surface. Throughout the temperature range that is available for comparison, the RPMD approximation gives better agreement with accurate quantum mechanical (multiconfigurational time-dependent Hartree) calculations than do either the centroid density version of quantum transition state theory (QTST) or the quantum instanton (QI) model. The RPMD rate coefficients are within a factor of 2 of the exact quantum mechanical rate coefficients at temperatures in the deep tunneling regime. These results indicate that our previous assessment of the accuracy of the RPMD approximation for atom-diatom reactions remains valid for more complex polyatomic reactions. They also suggest that the sensitivity of the QTST and QI rate coefficients to the choice of the transition state dividing surface becomes more of an issue as the dimensionality of the reaction increases.

  4. Systematic exploration of the mechanism of chemical reactions: the global reaction route mapping (GRRM) strategy using the ADDF and AFIR methods.

    PubMed

    Maeda, Satoshi; Ohno, Koichi; Morokuma, Keiji

    2013-03-21

    Global reaction route mapping (GRRM), a fully-automated search for all important reaction pathways relevant to a given purpose, on the basis of quantum chemical calculations enables systematic elucidation of complex chemical reaction mechanisms. However, GRRM had previously been limited to very simple systems. This is mainly because such calculations are highly demanding even in small systems when a brute-force sampling is considered. Hence, we have developed two independent but complementary methods: anharmonic downward distortion following (ADDF) and artificial force induced reaction (AFIR) methods. ADDF can follow reaction pathways starting from local minima on the potential energy surface (PES) toward transition structures (TSs) and dissociation channels. AFIR can find pathways starting from two or more reactants toward TSs for their associative reactions. In other words, ADDF searches for A → X type isomerization and A → X + Y type dissociation pathways, whereas AFIR finds A + B → X (+ Y) type associative pathways. Both follow special paths called the ADDF path and the AFIR path, and these tend to pass through near TSs of corresponding reaction pathways, giving approximate TSs. Such approximate TSs can easily be re-optimized to corresponding true TSs by standard geometry optimizations. On the basis of these two methods, we have proposed practical strategies of GRRM. The GRRM strategies have been applied to a variety of chemical systems ranging from thermal- and photochemical-reactions in small systems to organometallic- and enzyme-catalysis, on the basis of quantum chemical calculations. In this perspective, we present an overview of the GRRM strategies and some results of applications. Their practical usage for systematic prediction is also discussed.

  5. A target-triggered strand displacement reaction cycle: the design and application in adenosine triphosphate sensing.

    PubMed

    Cheng, Sheng; Zheng, Bin; Wang, Mozhen; Lam, Michael Hon-Wah; Ge, Xuewu

    2014-02-01

    A strand displacement reaction (SDR) system that runs solely on oligonucleotides has been developed for the amplification detection of adenosine triphosphate (ATP). It involves a target-induced SDR and an entropy-driven catalytic cycle of two SDRs with five oligonucleotides, denoted as substrate, fuel, catalyst, C-1, and C-2. Catalyst, released from the ATP aptamer-catalyst duplex by ATP molecule, catalyzes the SDRs to finally form the substrate-fuel duplex. All of the intermediates in the catalytic SDR processes have been identified by polyacrylamide gel electrophoresis (PAGE) analysis. The introduction of ATP into the SDR system will induce the ATP aptamer to form G-quadruplex conformation so as to release catalyst and trigger the SDR cycle. When the substrate and C-2 oligonucleotides were labeled with a carboxyfluorescein (FAM) fluorophore and a 4-([4-(dimethylamino)phenyl]azo)benzoic acid (DABCYL) quencher, this SDR catalytic system exhibited a "turn-on" response for ATP. The condition for detecting ATP, such as Mg²⁺ concentration, has been optimized to afford a detection limit of 20 nM. This work provides an enzyme-free biosensing strategy and has potential application in aptamer-based biosensing.

  6. Variance-reduced simulation of lattice discrete-time Markov chains with applications in reaction networks

    NASA Astrophysics Data System (ADS)

    Maginnis, P. A.; West, M.; Dullerud, G. E.

    2016-10-01

    We propose an algorithm to accelerate Monte Carlo simulation for a broad class of stochastic processes. Specifically, the class of countable-state, discrete-time Markov chains driven by additive Poisson noise, or lattice discrete-time Markov chains. In particular, this class includes simulation of reaction networks via the tau-leaping algorithm. To produce the speedup, we simulate pairs of fair-draw trajectories that are negatively correlated. Thus, when averaged, these paths produce an unbiased Monte Carlo estimator that has reduced variance and, therefore, reduced error. Numerical results for three example systems included in this work demonstrate two to four orders of magnitude reduction of mean-square error. The numerical examples were chosen to illustrate different application areas and levels of system complexity. The areas are: gene expression (affine state-dependent rates), aerosol particle coagulation with emission and human immunodeficiency virus infection (both with nonlinear state-dependent rates). Our algorithm views the system dynamics as a "black-box", i.e., we only require control of pseudorandom number generator inputs. As a result, typical codes can be retrofitted with our algorithm using only minor changes. We prove several analytical results. Among these, we characterize the relationship of covariances between paths in the general nonlinear state-dependent intensity rates case, and we prove variance reduction of mean estimators in the special case of affine intensity rates.

  7. Tuning graphene for energy and environmental applications: Oxygen reduction reaction and greenhouse gas mitigation

    NASA Astrophysics Data System (ADS)

    Haque, Enamul; Sarkar, Shuranjan; Hassan, Mahbub; Hossain, Md. Shahriar; Minett, Andrew I.; Dou, Shi Xue; Gomes, Vincent G.

    2016-10-01

    Porous nitrogen-doped graphene samples were synthesized and tuned via pyrolysis of solid nitrogen precursor dimethyl-aminoterephthalate with graphene oxide as template. Our investigations show that the extent of thermal treatment, total concentration of nitrogen and the nature of nitrogen moieties play important roles in enhancing oxygen reduction reaction (ORR) and CO2 uptake. N-doped graphene synthesized at 650 °C (NG-650) with specific BET surface area of 278 m2/g, exhibits enhanced CO2 sorption capacity of 4.43 mmol/g (at 298 K, 1 bar) with exceptional selectivity (CO2:N2 = 42) and cyclic regeneration stability. In contrast, nitrogen-doped graphene synthesized at 750 °C (NG-750) demonstrated excellent catalytic activity for ORR via favourable 4e- transfer, performance stability with tests conducted up to 5000 cycles, and is unaffected by methanol cross-over effect. Thus, NG-750 shows potential to replace metal-based electrodes for fuel cell application. The comparative results for ORR with non-doped and nitrogen-doped graphene electrodes showed that graphitic nitrogen sites play vital role in enhancing catalytic activity.

  8. Mechanisms of Propidium Monoazide Inhibition of Polymerase Chain Reaction and implications for Propidium Monoazide Applications

    NASA Astrophysics Data System (ADS)

    Lee, C. M.; Darrach, H.; Ponce, A.; McFarland, E.; Laymon, C.; Fingland, N. K.

    2015-12-01

    PMA-qPCR is a laboratory technique that can be used to identify viable microbes by employing the use of propidium monoazide (PMA), a DNA-intercalating dye, and quantitative polymerase chain reaction (qPCR). The current model of PMA-qPCR operates under the assumption that PMA is only capable of entering membrane-compromised cells, where it irreversibly cross-links to DNA and makes it unavailable for amplification via qPCR. However, the exact mechanism behind PMA's entry into the cell and its interaction with genetic material is not well understood. To better understand PMA's capabilities, we have examined the effect PMA has on enzyme binding and processivity using endonucleases and exonucleases. Our results suggest that the current model behind PMA-qPCR inhibition is incomplete, in that rather than precipitating the entirety of the DNA, PMA also inhibits enzyme binding and/or processivity in soluble DNA. These results have important implications for studying the viable community of microorganisms in various applications, such as environmental monitoring, planetary protection and bioburden assessment, and biohazard detection.

  9. Application of Theories, Principles and Methods of Adult Learning for Managers to Improve Workplace Reactions to Learning, Knowledge and Performance

    ERIC Educational Resources Information Center

    Steier, E. Joseph, III

    2010-01-01

    The objective of this dissertation was to explore the concept that knowledge and application of theories, principles and methods of adult learning to teaching may be a core management competency needed for companies to improve employee reaction to learning, knowledge transfer and behavior as well as engagement, retention and profitability.…

  10. Development and Application of α-Heteroatom Ketones in Asymmetric Michael Reaction with β-trans-Nitroalkenes.

    PubMed

    Yang, Dongxu; Li, Dan; Wang, Linqing; Zhao, Depeng; Wang, Rui

    2015-05-01

    The successful design and application of a new type of N-phenyl-imidazole-modified α-heteroatom ketones in asymmetric anti-selective Michael reactions with β-trans-nitroalkenes is reported. High yields and enantioselectivities could be obtained, and the corresponding conjugate adducts could be further transformed into related chiral esters and cyclopropane derivatives with excellent enantioselectivities.

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

    PubMed

    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.

  12. Organometallic Chemistry and catalysis on gold metal surfaces

    SciTech Connect

    Angelici, Robert J.

    2007-11-21

    As in transition metal complexes, C{triple_bond}N-R ligands adsorbed on powdered gold undergo attack by amines to give putative diaminocarbene groups on the gold surface. This reaction forms the basis for the discovery of a gold metal-catalyzed reaction of C{triple_bond}N-R, primary amines (R{prime}NH{sub 2}) and O{sub 2} to give carbodiimides (R{prime}-N{double_bond}C{double_bond}N-R). An analogous reaction of C{triple_bond}O, RNH{sub 2}, and O{sub 2} gives isocyanates (R-N{double_bond}C{double_bond}O), which react with additional amine to give urea (RNH){sub 2}C{double_bond}O products. The gold-catalyzed reaction of C{triple_bond}N-R with secondary amines (HNR{prime}{sub 2}) and O{sub 2} gives mixed ureas RNH(CO)NR{prime}{sub 2}. In another type of gold-catalyzed reaction, secondary amines HN(CH{sub 2}R){sub 2} react with O{sub 2} to undergo dehydrogenation to the imine product, RCH{double_bond}N(CH{sub 2}R). Of special interest is the high catalytic activity of gold powder, which is otherwise well-known for its poor catalytic properties.

  13. Microsolvated transition state models for improved insight into chemical properties and reaction mechanisms.

    PubMed

    Sunoj, Raghavan B; Anand, Megha

    2012-10-05

    Over the years, several methods have been developed to effectively represent the chemical behavior of solutes in solvents. The environmental effects arising due to solvation can generally be achieved either through inclusion of discrete solvent molecules or by inscribing into a cavity in a homogeneous and continuum dielectric medium. In both these approaches of computational origin, the perturbations on the solute induced by the surrounding solvent are at the focus of the problem. While the rigor and method of inclusion of solvent effects vary, such solvation models have found widespread applications, as evident from modern chemical literature. A hybrid method, commonly referred to as cluster-continuum model (CCM), brings together the key advantages of discrete and continuum models. In this perspective, we intend to highlight the latent potential of CCM toward obtaining accurate estimates on a number of properties as well as reactions of contemporary significance. The objective has generally been achieved by choosing illustrative examples from the literature, besides expending efforts to bring out the complementary advantages of CCM as compared to continuum or discrete solvation models. The majority of examples emanate from the prevalent applications of CCM to organic reactions, although a handful of interesting organometallic reactions have also been discussed. In addition, increasingly accurate computations of properties like pK(a) and solvation of ions obtained using the CCM protocol are also presented.

  14. The solid-state synthesis of metal nanoparticles from organometallic precursors.

    PubMed

    Wostek-Wojciechowska, Dorota; Jeszka, Jeremiasz K; Amiens, Catherine; Chaudret, Bruno; Lecante, Pierre

    2005-07-01

    Nanoparticles (NPs), average size of 2-5 nm, of ruthenium, cobalt, and rhodium have been prepared by an original method, namely the solid-state decomposition under dihydrogen of an organometallic precursor either dispersed in polymer films or directly as nanocrystals. The NPs dispersion, size, and morphology are investigated by transmission electron microscopy, and their structure by wide angle X-ray scattering. Infrared spectroscopy, after adsorption of carbon monoxide on the metal NPs surfaces, evidences a nonoxidized surface of high reactivity.

  15. Progress toward cascade cells made by OM-VPE. [organometallic vapor phase epitaxy

    NASA Technical Reports Server (NTRS)

    Borden, P. G.; Larue, R. A.; Ludowise, M. J.

    1982-01-01

    Organometallic Vapor Phase Epitaxy (COM-VPE) was used to make a sophisticated monolithic cascade cell, with a peak AMO efficiency of 16.6%, not corrected for 14% grid coverage. The cell has 9 epitaxial layers. The top cell is 1.35 microns thick with a 0.1 micron thich emitter. Both cells are heteroface n-p structures. The cascade cell uses metal interconnects. Details of growth and processing are described.

  16. Organometallic Compounds and Polymers with Second and Third Order Nonlinear Optical Properties

    DTIC Science & Technology

    1993-05-06

    Nonlinear Optical Properties of Inorganic Coordination Polymers . William Chiang, Mark E. Thompson, Donna Van Engen , "Organic Materials for Nonlinear...Organometallic Compounds and Polymers with Second and Third Order Nonlinear Optical Pro. -c.AUTHOR(S) 61102F 2303 All Mark E. Thompson, PI 7. PERFORMING...scale Sc -Cr $5 Fe > Co. Polar coordination polymers were prepared in which excellent polar order was found in the polyermic chains. however, the

  17. Application of the aza-Diels-Alder reaction in the synthesis of natural products.

    PubMed

    Cao, Min-Hui; Green, Nicholas J; Xu, Sheng-Zhen

    2017-03-22

    The Diels-Alder reaction that involves a nitrogen atom in the diene or dienophile is termed the aza-Diels-Alder reaction. As well as the powerful all-carbon Diels-Alder reaction, the aza-Diels-Alder reaction has also played an important role in the total synthesis of natural products. Herein, we review various natural products using an aza-Diels-Alder reaction as a key step to their total synthesis, and divide the syntheses into inter- and intra-molecular aza-Diels-Alder reactions and a retro-aza-Diels-Alder reaction. Inter- and intra-molecular aza-Diels-Alder reactions involve an imine as an electron deficient dienophile and an imine as an electron deficient azadiene. The significance of the aza-Diels-Alder reaction for the construction of a six-membered ring containing nitrogen is tremendous, but the development of asymmetric, in particular catalytic enantioselective intramolecular aza-Diels-Alder reaction in the total synthesis of natural products remains highly challenging, and will no doubt see enormous advances in the future.

  18. Aza-crown ether complex cation ionic liquids: preparation and applications in organic reactions.

    PubMed

    Song, Yingying; Cheng, Chen; Jing, Huanwang

    2014-09-26

    Aza-crown ether complex cation ionic liquids (aCECILs) were devised, fabricated, and characterized by using NMR spectroscopy, MS, thermogravimetric differential thermal analysis (TG-DTA), elemental analysis and physical properties. These new and room-temperature ILs were utilized as catalysts in various organic reactions, such as the cycloaddition reaction of CO2 to epoxides, esterification of acetic acid and alcohols, the condensation reaction of aniline and propylene carbonate, and Friedel-Crafts alkylation of indole with aldehydes were investigated carefully. In these reactions, the ionic liquid exhibited cooperative catalytic activity between the anion and cation. In addition, the aza-[18-C-6HK][HSO4]2 was the best acidic catalyst in the reactions of esterification and Friedel-Crafts alkylation under mild reaction conditions.

  19. Effective reaction at a fluid–solid interface: Applications to biotransformation in porous media

    SciTech Connect

    Wood, Brian D.; Radakovich, Karen; Golfier, Fabrice

    2007-06-01

    In this work we develop, via volume averaging, the macroscale transport equation for a reactive chemical species undergoing a heterogeneous reaction with Michaelis–Menton type kinetics. We describe the closure problem required to predict the effective macroscale reaction rate from the microscale geometry and the chemical, physical, and microbial properties. The effective rate of reaction predicted from the closure problem is compared with the reaction rate with that is obtained by direct numerical simulation at the microscale. This comparison shows that the macroscale description of the reaction process is generally valid when the coefficient of variation of the concentration field is small compared with unity. Our results are subsequently used to interpret laboratory data for the enzymatic transformation of p-nitrophenyl phosphate hexahydrate. In particular, we provide some interpretation of the observed effect of porewater velocity on the effective reaction rate.

  20. Effective reaction at a fluid solid interface: Applications to biotransformation in porous media

    NASA Astrophysics Data System (ADS)

    Wood, Brian D.; Radakovich, Karen; Golfier, Fabrice

    2007-06-01

    In this work we develop, via volume averaging, the macroscale transport equation for a reactive chemical species undergoing a heterogeneous reaction with Michaelis-Menton type kinetics. We describe the closure problem required to predict the effective macroscale reaction rate from the microscale geometry and the chemical, physical, and microbial properties. The effective rate of reaction predicted from the closure problem is compared with the reaction rate that is obtained by direct numerical simulation at the microscale. This comparison shows that the macroscale description of the reaction process is generally valid when the coefficient of variation of the concentration field is small compared with unity. Our results are subsequently used to interpret laboratory data for the enzymatic transformation of p-nitrophenyl phosphate hexahydrate. In particular, we provide some interpretation of the observed effect of porewater velocity on the effective reaction rate.

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

    PubMed

    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

  2. Molecular Simulation of Shocked Materials Using Reaction Ensemble Monte Carlo: Part 1. Application to Nitrogen Dissociation

    DTIC Science & Technology

    2006-11-01

    constituting the chemically reacting species is conserved. Thermochemical software such as the chemical equilibrium code (12) and Cheetah (13) are...stoichiometric coefficient of species i in reaction j; ξj is the molecular extent of reaction for reaction j; qint,i is the quantum partition function for the...Detonation Properties of PETN. J. Chem. Phys. 1984, 81, 1251. 13. Fried, L. E. Cheetah 3.0 User’s Manual; Lawrence Livermore National Laboratory

  3. Molecular Models of Ruthenium(II) Organometallic Complexes

    ERIC Educational Resources Information Center

    Coleman, William F.

    2007-01-01

    This article presents the featured molecules for the month of March, which appear in the paper by Ozerov, Fafard, and Hoffman, and which are related to the study of the reactions of a number of "piano stool" complexes of ruthenium(II). The synthesis of compound 2a offers students an alternative to the preparation of ferrocene if they are only…

  4. Applications of Skyrme energy-density functional to fusion reactions for synthesis of superheavy nuclei

    SciTech Connect

    Wang Ning; Scheid, Werner; Wu Xizhen; Liu Min; Li Zhuxia

    2006-10-15

    The Skyrme energy-density functional approach has been extended to study massive heavy-ion fusion reactions. Based on the potential barrier obtained and the parametrized barrier distribution the fusion (capture) excitation functions of a lot of heavy-ion fusion reactions are studied systematically. The average deviations of fusion cross sections at energies near and above the barriers from experimental data are less than 0.05 for 92% of 76 fusion reactions with Z{sub 1}Z{sub 2}<1200. For the massive fusion reactions, for example, the {sup 238}U-induced reactions and {sup 48}Ca+{sup 208}Pb, the capture excitation functions have been reproduced remarkably well. The influence of structure effects in the reaction partners on the capture cross sections is studied with our parametrized barrier distribution. By comparing the reactions induced by double-magic nucleus {sup 48}Ca and by {sup 32}S and {sup 35}Cl, the ''threshold-like'' behavior in the capture excitation function for {sup 48}Ca-induced reactions is explored and an optimal balance between the capture cross section and the excitation energy of the compound nucleus is studied. Finally, the fusion reactions with {sup 36}S, {sup 37}Cl, {sup 48}Ca, and {sup 50}Ti bombarding {sup 248}Cm, {sup 247,249}Bk, {sup 250,252,254}Cf, and {sup 252,254}Es, as well as the reactions leading to the same compound nucleus with Z=120 and N=182, are studied further. The calculation results for these reactions are useful for searching for the optimal fusion configuration and suitable incident energy in the synthesis of superheavy nuclei.

  5. Application of the balancing holes on the turbine stage discs with higher root reaction

    NASA Astrophysics Data System (ADS)

    Mrózek, Lukáš; Tajč, Ladislav; Hoznedl, Michal; Miczán, Martin

    2016-03-01

    The influence of the flow area of balancing holes in the discs of a steam turbine on its thermodynamic efficiency is examined for turbine stages operating in the increased root reaction regime. The interstage seal flooding with steam is modelled. The impact is given on stage reaction changes, on mass flow adjustments, and on overpressure operating in the rotor disc.

  6. Nuclear Reactions: Studying Peaceful Applications in the Middle and Secondary School.

    ERIC Educational Resources Information Center

    Szymanski Sunal, Cynthia; Sunal, Dennis W.

    1999-01-01

    Asserts that students must learn about nuclear fission and fusion in the social studies curriculum to help them develop a foundation for considering the social issues associated with the everyday use of nuclear reactions. Gives background on the two types of reactions and provides three lessons for middle and secondary classrooms. (CMK)

  7. Scanning electrochemical microscopy #54. Application to the study of heterogeneous catalytic reactions-hydrogen peroxide decomposition.

    PubMed

    Fernández, José L; Hurth, Cedric; Bard, Allen J

    2005-05-19

    A scanning electrochemical microscopy (SECM) approach for the analysis of heterogeneous catalytic reactions at solid-liquid interfaces is described and applied. In this scheme, reactant, generated at a tip, undergoes a reaction (e.g., disproportionation) at the substrate. The theoretical background for this study, performed by digital simulations using a finite difference method, considers a chemical reaction at the substrate with general stoichiometry. In this case, the fraction of regenerated mediator (nu(S)) may differ with respect to a substrate reaction that is the reverse of the tip reaction, resulting in an asymmetric mediator loop. Simulated tip current transients and approach curves at different values of the kinetic rate constant for reactions where nu(S) < 1 were used to analyze this new SECM situation. This approach was used to study the catalytic decomposition of hydrogen peroxide (HO2- --> 1/2O2 + OH-), where nu(S) = 0.5, on supported catalysts. A gold-mercury amalgam tip was used to quantitatively reduce dissolved O2 (mediator) to HO2-, which was decomposed back to oxygen at the catalyst substrate. Rate constants for the decomposition reaction on immobilized catalase and Pt particles were measured at different pH values by the correlation of experimental approach curves with the theoretical dependencies.

  8. Predicting rare events in chemical reactions: Application to skin cell proliferation.

    PubMed

    Lee, Chiu Fan

    2010-08-01

    In a well-stirred system undergoing chemical reactions, fluctuations in the reaction propensities are approximately captured by the corresponding chemical Langevin equation. Within this context, we discuss in this work how the Kramers escape theory can be used to predict rare events in chemical reactions. As an example, we apply our approach to a recently proposed model on cell proliferation with relevance to skin cancer [P. B. Warren, Phys. Rev. E 80, 030903 (2009)]. In particular, we provide an analytical explanation for the form of the exponential exponent observed in the onset rate of uncontrolled cell proliferation.

  9. 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

    NASA Astrophysics Data System (ADS)

    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.

  10. Conjugate addition–enantioselective protonation reactions

    PubMed Central

    Phelan, James P

    2016-01-01

    Summary The addition of nucleophiles to electron-deficient alkenes represents one of the more general and commonly used strategies for the convergent assembly of more complex structures from simple precursors. In this review the addition of diverse protic and organometallic nucleophiles to electron-deficient alkenes followed by enantioselective protonation is summarized. Reactions are first categorized by the type of electron-deficient alkene and then are further classified according to whether catalysis is achieved with chiral Lewis acids, organocatalysts, or transition metals. PMID:27559372

  11. Time resolved studies of bond activation by organometallic complexes

    SciTech Connect

    Wilkens, Matthew J.

    1998-05-01

    In 1971, Jetz and Graham discovered that the silicon-hydrogen bond in silanes could be broken under mild photochemical conditions in the presence of certain transition metal carbonyls. Such reactions fall within the class of oxidative addition. A decade later, similar reactivity was discovered in alkanes. In these cases a C-H bond in non-functionalized alkanes was broken through the oxidative addition of Cp*Ir(H)2L (Cp* = (CH3)5C5, L = PPh3, Ph = C6H5) to form Cp*ML(R)(H) or of Cp*Ir(CO)2 to form Cp*Ir(CO)(R)(H). These discoveries opened an entirely new field of research, one which naturally included mechanistic studies aimed at elucidating the various paths involved in these and related reactions. Much was learned from these experiments but they shared the disadvantage of studying under highly non-standard conditions a system which is of interest largely because of its characteristics under standard conditions. Ultrafast time-resolved IR spectroscopy provides an ideal solution to this problem; because it allows the resolution of chemical events taking place on the femto-through picosecond time scale, it is possible to study this important class of reactions under the ambient conditions which are most of interest to the practicing synthetic chemist. Certain of the molecules in question are particularly well-suited to study using the ultrafast IR spectrophotometer described in the experimental section because they contain one or more carbonyl ligands.

  12. Carbon-coated magnetic palladium: applications in partial oxidation of alcohols and coupling reactions.

    EPA Science Inventory

    Magnetic carbon supported Pd catalyst has been synthesized via in situ generation of nanoferrites and incorporation of carbon from renewable cellulose via calcination; catalyst can be used for oxidation of alcohols, amination reaction and arylation of aryl halides (cross coupli...

  13. Organo-niobate Ionic Liquids: Synthesis, Characterization and Application as Acid Catalyst in Pechmann Reactions

    PubMed Central

    Soares, Valerio C. D.; Alves, Melquizedeque B.; Souza, Ernesto R.; Pinto, Ivana O.; Rubim, Joel C.; Andrade, Carlos Kleber Z.; Suarez, Paulo A. Z.

    2007-01-01

    The combinations of 1-butyl-3-methylimidazolium chloride with NbCl5 yielded ionic mixtures with different melting point temperatures and acidity depending on the niobium molar fraction. The mixtures were characterized by thermal (DSC) and spectroscopic (FT-IR and 1H NMR) analysis. The Pechmann reactions of different phenols with ethylacetoacetate, producing coumarins, was used as model to evaluate the catalytic behavior of these mixtures as acid Lewis catalyst. These reactions were carried out using acidic mixtures of 60 mol%.

  14. A biocompatible in vivo ligation reaction and its application for noninvasive bioluminescent imaging of protease activity in living mice.

    PubMed

    Godinat, Aurélien; Park, Hyo Min; Miller, Stephen C; Cheng, Ke; Hanahan, Douglas; Sanman, Laura E; Bogyo, Matthew; Yu, Allen; Nikitin, Gennady F; Stahl, Andreas; Dubikovskaya, Elena A

    2013-05-17

    The discovery of biocompatible reactions had a tremendous impact on chemical biology, allowing the study of numerous biological processes directly in complex systems. However, despite the fact that multiple biocompatible reactions have been developed in the past decade, very few work well in living mice. Here we report that D-cysteine and 2-cyanobenzothiazoles can selectively react with each other in vivo to generate a luciferin substrate for firefly luciferase. The success of this "split luciferin" ligation reaction has important implications for both in vivo imaging and biocompatible labeling strategies. First, the production of a luciferin substrate can be visualized in a live mouse by bioluminescence imaging (BLI) and furthermore allows interrogation of targeted tissues using a "caged" luciferin approach. We therefore applied this reaction to the real-time noninvasive imaging of apoptosis associated with caspase 3/7. Caspase-dependent release of free D-cysteine from the caspase 3/7 peptide substrate Asp-Glu-Val-Asp-D-Cys (DEVD-(D-Cys)) allowed selective reaction with 6-amino-2-cyanobenzothiazole (NH(2)-CBT) in vivo to form 6-amino-D-luciferin with subsequent light emission from luciferase. Importantly, this strategy was found to be superior to the commercially available DEVD-aminoluciferin substrate for imaging of caspase 3/7 activity. Moreover, the split luciferin approach enables the modular construction of bioluminogenic sensors, where either or both reaction partners could be caged to report on multiple biological events. Lastly, the luciferin ligation reaction is 3 orders of magnitude faster than Staudinger ligation, suggesting further applications for both bioluminescence and specific molecular targeting in vivo.

  15. Deuteron-induced nucleon transfer reactions within an ab initio framework: First application to p-shell nuclei

    DOE PAGES

    Raimondi, Francesco; Hupin, Guillaume; Navratil, Petr; ...

    2016-05-10

    Low-energy transfer reactions in which a proton is stripped from a deuteron projectile and dropped into a target play a crucial role in the formation of nuclei in both primordial and stellar nucleosynthesis, as well as in the study of exotic nuclei using radioactive beam facilities and inverse kinematics. Here, ab initio approaches have been successfully applied to describe the 3H(d,n)4He and 3He(d,p)4He fusion processes. An ab initio treatment of transfer reactions would also be desirable for heavier targets. In this work, we extend the ab initio description of (d,p) reactions to processes with light p-shell nuclei. As a firstmore » application, we study the elastic scattering of deuterium on 7Li and the 7Li(d,p)8Li transfer reaction based on a two-body Hamiltonian. We use the no-core shell model to compute the wave functions of the nuclei involved in the reaction, and describe the dynamics between targets and projectiles with the help of microscopic-cluster states in the spirit of the resonating group method. The shapes of the excitation functions for deuterons impinging on 7Li are qualitatively reproduced up to the deuteron breakup energy. The interplay between d–7Li and p–8Li particle-decay channels determines some features of the 9Be spectrum above the d+7Li threshold. Our prediction for the parity of the 17.298 MeV resonance is at odds with the experimental assignment. Deuteron stripping reactions with p-shell targets can now be computed ab initio, but calculations are very demanding. Finally, a quantitative description of the 7Li(d,p)8Li reaction will require further work to include the effect of three-nucleon forces and additional decay channels and to improve the convergence rate of our calculations.« less

  16. Application of an electrochemical hydrogen meter for studying reactions in liquid sodium

    NASA Astrophysics Data System (ADS)

    Gnanasekaran, T.; Ganesan, V.; Periaswami, G.; Mathews, C. K.; Borgstedt, H. U.

    1990-05-01

    An electrochemical hydrogen meter based on a CaCl2- CaH2 solid electrolyte was used to study the reactions of rust (FeOOH) and hydrocarbon based oil with liquid sodium in the temperature range of 623 to 748 K. The results indicated that the reaction between FeOOH and sodium is slow at 623 K and fast at 723 K. The hydrogen concentration in sodium is increased due to the reaction. Similarly, the reaction between oil and sodium proceeds slowly at 623 K whereas above 673 K, it takes place rapidly. The gaseous products released during sodium-oil reactions were analysed by means of the gas Chromatographie technique. It was found that methane was the major gaseous product formed and its formation obeyed a parabolic rate law. The response of the meter for the liberation of hydrogen in both reactions was found to be fast, qualifying the meter for detecting the ingress of hydrogen bearing compounds into sodium.

  17. Applicability of PM3 to transphosphorylation reaction path: Toward designing a minimal ribozyme

    NASA Technical Reports Server (NTRS)

    Manchester, John I.; Shibata, Masayuki; Setlik, Robert F.; Ornstein, Rick L.; Rein, Robert

    1993-01-01

    A growing body of evidence shows that RNA can catalyze many of the reactions necessary both for replication of genetic material and the possible transition into the modern protein-based world. However, contemporary ribozymes are too large to have self-assembled from a prebiotic oligonucleotide pool. Still, it is likely that the major features of the earliest ribozymes have been preserved as molecular fossils in the catalytic RNA of today. Therefore, the search for a minimal ribozyme has been aimed at finding the necessary structural features of a modern ribozyme (Beaudry and Joyce, 1990). Both a three-dimensional model and quantum chemical calculations are required to quantitatively determine the effects of structural features of the ribozyme on the reaction it catalyzes. Using this model, quantum chemical calculations must be performed to determine quantitatively the effects of structural features on catalysis. Previous studies of the reaction path have been conducted at the ab initio level, but these methods are limited to small models due to enormous computational requirements. Semiempirical methods have been applied to large systems in the past; however, the accuracy of these methods depends largely on a simple model of the ribozyme-catalyzed reaction, or hydrolysis of phosphoric acid. We find that the results are qualitatively similar to ab initio results using large basis sets. Therefore, PM3 is suitable for studying the reaction path of the ribozyme-catalyzed reaction.

  18. An Advanced Organometallic Lab Experiment with Biological Implications: Synthesis and Characterization of Fe[subscript 2](µ-S[subscript 2])(C0)[subscript 6

    ERIC Educational Resources Information Center

    Barrett, Jacob; Spentzos, Ariana; Works, Carmen

    2015-01-01

    The organometallic complex Fe[subscript 2](µ-S[subscript 2])(CO)[subscript 6] has interesting biological implications. The concepts of bio-organometallic chemistry are rarely discussed at the undergraduate level, but this experiment can start such a conversation and, in addition, teach valuable synthetic techniques. The lab experiment takes a…

  19. Chiral GAP catalysts of phosphonylated imidazolidinones and their applications in asymmetric Diels-Alder and Friedel-Crafts reactions.

    PubMed

    Qiao, Shuo; Mo, Junming; Wilcox, Cody B; Jiang, Bo; Li, Guigen

    2017-02-21

    The design and synthesis of recyclable imidazolidinone catalysts using GAP chemistry/technique was described. Their applications in asymmetric Diels-Alder and Friedel-Crafts reactions with α,β-unsaturated aldehydes resulted in excellent yields and higher enantioselectivities than previous processes. As recyclable small molecular catalysts, phosphonylated imidazolidinones can be recovered and reused for up to three runs without costing significant decrease in catalytic activity.

  20. Glucansucrases: three-dimensional structures, reactions, mechanism, α-glucan analysis and their implications in biotechnology and food applications.

    PubMed

    Leemhuis, Hans; Pijning, Tjaard; Dobruchowska, Justyna M; van Leeuwen, Sander S; Kralj, Slavko; Dijkstra, Bauke W; Dijkhuizen, Lubbert

    2013-01-20

    Glucansucrases are extracellular enzymes that synthesize a wide variety of α-glucan polymers and oligosaccharides, such as dextran. These carbohydrates have found numerous applications in food and health industries, and can be used as pure compounds or even be produced in situ by generally regarded as safe (GRAS) lactic acid bacteria in food applications. Research in the recent years has resulted in big steps forward in the understanding and exploitation of the biocatalytic potential of glucansucrases. This paper provides an overview of glucansucrase enzymes, their recently elucidated crystal structures, their reaction and product specificity, and the structural analysis and applications of α-glucan polymers. Furthermore, we discuss key developments in the understanding of α-glucan polymer formation based on the recently elucidated three-dimensional structures of glucansucrase proteins. Finally we discuss the (potential) applications of α-glucans produced by lactic acid bacteria in food and health related industries.

  1. Development and application of a numerical model of kinetic and equilibrium microbiological and geochemical reactions (BIOKEMOD)

    NASA Astrophysics Data System (ADS)

    Salvage, Karen M.; Yeh, Gour-Tsyh

    1998-08-01

    This paper presents the conceptual and mathematical development of the numerical model titled BIOKEMOD, and verification simulations performed using the model. BIOKEMOD is a general computer model for simulation of geochemical and microbiological reactions in batch aqueous solutions. BIOKEMOD may be coupled with hydrologic transport codes for simulation of chemically and biologically reactive transport. The chemical systems simulated may include any mixture of kinetic and equilibrium reactions. The pH, pe, and ionic strength may be specified or simulated. Chemical processes included are aqueous complexation, adsorption, ion-exchange and precipitation/dissolution. Microbiological reactions address growth of biomass and degradation of chemicals by microbial metabolism of substrates, nutrients, and electron acceptors. Inhibition or facilitation of growth due to the presence of specific chemicals and a lag period for microbial acclimation to new substrates may be simulated if significant in the system of interest. Chemical reactions controlled by equilibrium are solved using the law of mass action relating the thermodynamic equilibrium constant to the activities of the products and reactants. Kinetic chemical reactions are solved using reaction rate equations based on collision theory. Microbiologically mediated reactions for substrate removal and biomass growth are assumed to follow Monod kinetics modified for the potentially limiting effects of substrate, nutrient, and electron acceptor availability. BIOKEMOD solves the ordinary differential and algebraic equations of mixed geochemical and biogeochemical reactions using the Newton-Raphson method with full matrix pivoting. Simulations may be either steady state or transient. Input to the program includes the stoichiometry and parameters describing the relevant chemical and microbiological reactions, initial conditions, and sources/sinks for each chemical species. Output includes the chemical and biomass concentrations

  2. Solution phase and membrane immobilized iron-based free radical reactions: Fundamentals and applications for water treatment

    NASA Astrophysics Data System (ADS)

    Lewis, Scott Romak

    Membrane-based separation processes have been used extensively for drinking water purification, wastewater treatment, and numerous other applications. Reactive membranes synthesized through functionalization of the membrane pores offer enhanced reactivity due to increased surface area at the polymer-solution interface and low diffusion limitations. Oxidative techniques utilizing free radicals have proven effective for both the destruction of toxic organics and non-environmental applications. Most previous work focuses on reactions in the homogeneous phase; however, the immobilization of reactants in membrane pores offers several advantages. The use of polyanions immobilized in a membrane or chelates in solution prevents ferric hydroxide precipitation at near-neutral pH, a common limitation of iron(Fe(II/III))-catalyzed hydrogen peroxide (H 2O2) decomposition. The objectives of this research are to develop a membrane-based platform for the generation of free radicals, degrade toxic organic compounds using this and similar solution-based reactions, degrade toxic organic compounds in droplet form, quantify hydroxyl radical production in these reactions, and develop kinetic models for both processes. In this study, a functionalized membrane containing poly(acrylic acid) (PAA) was used to immobilize iron ions and conduct free radical reactions by permeating H2O2 through the membrane. The membrane's responsive behavior to pH and divalent cations was investigated and modeled. The conversion of Fe(II) to Fe(III) in the membrane and its effect on the decomposition of hydrogen peroxide were monitored and used to develop kinetic models for predicting H2O2 decomposition in these systems. The rate of hydroxyl radical production, and hence contaminant degradation can be varied by changing the residence time, H2O2 concentration, and/or iron loading. Using these membrane-immobilized systems, successful removal of toxic organic compounds, such as pentachlorophenol (PCP), from water

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

    DOEpatents

    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.

  4. Organometallics for Conducting Polymer Synthesis and Starburst Polymer Synthesis

    DTIC Science & Technology

    1991-05-16

    Polymers for Electronic and Photonic Applications. (B) Metal(0) Deposition in Sol-Gel Materials for Heterogeneous Catalysis . Dow Coming Corporation...Deposition in Sol-Gel Materials for Heterogeneous Catalysis . Shell Development Company, Westhollow Research Center, Houston, Texas, March 16, 1991

  5. 'Dynamic Distance' Reaction Coordinate for Competing Bonds:  Applications in Classical and Ab Initio Simulations.

    PubMed

    Burisch, Christian; Markwick, Phineus R L; Doltsinis, Nikos L; Schlitter, Jürgen

    2008-01-01

    A versatile reaction coordinate, the "dynamic distance", is introduced for the study of reactions involving the rupture and formation of a series of chemical bonds or contacts. The dynamic distance is a mass-weighted mean of selected distances. When implemented as a generalized constraint, the dynamic distance is particularly suited for driving activated processes by controlled increase during a simulation. As a single constraint acting upon multiple degrees of freedom, the sequence of events along the resulting reaction pathway is determined unambiguously by the underlying energy landscape. Free energy profiles can be readily obtained from the mean constraint force. In this paper both theoretical aspects and numerical implementation are discussed, and the unique and diverse properties of this reaction coordinate are demonstrated using three examples:  In the framework of Car-Parrinello molecular dynamics, we present results for the prototypical double proton-transfer reaction in formic acid dimer and the photocycle of the guanine-cytosine DNA base pair. As a classical mechanical example, the opening of the binding pocket of the enzyme rubisco is analyzed.

  6. Thiol-ene click reaction as a general route to functional trialkoxysilanes for surface coating applications.

    PubMed

    Tucker-Schwartz, Alexander K; Farrell, Richard A; Garrell, Robin L

    2011-07-27

    Functionalized trialkoxysilanes are widely used to modify the surface properties of materials and devices. It will be shown that the photoinitiated radical-based thiol-ene "click" reaction provides a simple and efficient route to diverse trialkoxysilanes. A total of 15 trialkoxysilanes were synthesized by reacting either alkenes with 3-mercaptopropyltrialkoxysilane or thiols with allyltrialkoxysilanes in the presence of a photoinitiator. The functionalized trialkoxysilanes were obtained in quantitative to near-quantitative yields with high purity. The photochemical reactions can be run neat in standard borosilicate glassware using a low power 15-W blacklight. A wide range of functional groups is tolerated in this approach, and even complex alkenes click with the silane precursors. To demonstrate that these silanes can be used as surface coating agents, several were reacted with iron oxide superparamagnetic nanoparticles and the loadings quantified. The photoinitiated thiol-ene reaction thus offers a facile and efficient method for preparing surface-active functional trialkoxysilanes.

  7. Dynamic modeling of biochemical reactions with application to signal transduction: principles and tools using Mathematica.

    PubMed

    Tóth, János; Rospars, Jean-Pierre

    2005-01-01

    Modeling of biochemical phenomena is based on formal reaction kinetics. This requires the translation of the original reaction systems into sets of differential equations expressing the effects of the various reaction steps. The temporal behavior of the system is obtained by solving the differential equations. We present the main concepts on which the formal approach of these two problems is based and we show how the amount of work needed to treat them can be significantly reduced by using a mathematical program package (Mathematica). Symbolic and numerical calculations can be performed with the programs presented and graphic presentations of the behavior of the system be obtained. The basic ideas are illustrated with three examples taken from the area of signal transduction and ion signaling.

  8. Investigation and application of multiple reactions between molybdoniobium heteropoly acid and di- or trimethylthionines

    SciTech Connect

    Mirzoyam, F.B.; Karapetyan, A.A.

    1986-03-01

    This paper presents the results of the study and use of reactions of molybdoniobic acid (MNA) with di- and trimethylthiones (DMT and TMT, respectively). It was found that light absorption of acetone solutions of the products of outer-sphere interaction between MNA and DMT or TMT enabled the determination of optimum acidity for MNA formation. Reaction between TMT and MNA gives two different compounds containing two and five associated dye cations, different in molar extinction coefficient and optimum reaction acidity (pH 0.05-0.25 and 0.35-0.90). Formation of the 6th and 8th molybdenum series with an identical composition of the outer sphere is shown. A highly sensitive photometric method for determining niobium has been developed.

  9. Recent progress in the preparation and application of carbon nanocapsules

    NASA Astrophysics Data System (ADS)

    Hwang, Kuo Chu

    2010-09-01

    In this review paper, the processes for the fabrication of carbon nanoparticles, carbon nanospheres, carbon onions, onion-like carbons and metal-filled carbon nanocapsules are reviewed. These processes include carbon arc discharge, metal catalysed chemical vapour deposition, thermal pyrolysis of organometallics and nanodiamonds, electric arc in liquid (e.g. liquid N2, H2O and organic solvents), and microwave arcing. The applications of both hollow and metal-filled carbon nanocapsules/nanoparticles as x-ray target materials, nanolubricants, broadband electromagnetic wave absorbers, catalysts for organic reactions, electrode materials for batteries and electrochemical immunoassays, biomedical gene/drug transporters, etc are also reviewed. The future prospects are also discussed.

  10. Application of an atmospheric pressure sampling mass spectrometer to chlorination reactions

    NASA Technical Reports Server (NTRS)

    Jacobson, N. S.

    1986-01-01

    An atmospheric pressure mass spectrometric sampling system, based on a free jet expansion was used to study certain M-Cl-O reactions at high temperatures. The apparatus enables the volatile species from a 1-atm chemical process to be directly identified with a mass spectrometer which operates at approx. 10 to the minus 8th power torr. Studies for both pure metals and alloys are discussed. It is shown that this mass spectrometer system aids in identifying the volatile species, and provides fundamental information on the reaction mechanism.

  11. Diffusion and reaction of pollutants in stratus clouds: application to nocturnal acid formation in plumes

    SciTech Connect

    Seigneur, C.; Saxena, P.; Mirabella, V.A.

    1985-09-01

    A mathematical model is presented that describes the transport, turbulent diffusion, and chemical reactions of air pollutants in stratus clouds. The chemical kinetic mechanism treats 97 gaseous, heterogeneous, and aqueous reactions between 54 species. The dispersion and night-time chemistry of a power plant plume in a stratus cloud is simulated. The contributions of various chemical pathways to the formation of sulfate and nitrate, the differences between plume and background concentrations, and the effect of reduced primary emissions on secondary pollutants are discussed. Calculated sulfate and nitrate concentrations are commensurate with measured atmospheric concentrations.

  12. Benzannulation via the Reaction of Ynamides and Vinylketenes. Application to the Synthesis of Highly Substituted Indoles

    PubMed Central

    Lam, Tin Yiu; Wang, Yu-Pu

    2013-01-01

    A two-stage “tandem strategy” for the synthesis of indoles with a high level of substitution on the six-membered ring is described. Benzannulation based on the reaction of cyclobutenones with ynamides proceeds via a cascade of four pericyclic reactions to produce multiply substituted aniline derivatives in which the position ortho to the nitrogen can bear a wide range of functionalized substituents. In the second stage of the tandem strategy, highly substituted indoles are generated via acid-, base-, and palladium-catalyzed cyclization and annulation processes. PMID:23952525

  13. Engineered Organometallic Polymer and Hybrid Systems Containing Nanoparticles and/or Poly(ferrocenylsilanes)

    NASA Astrophysics Data System (ADS)

    Roskov, Kristen Ekiert

    electrospun fibers, and the fibers have likewise been aligned to permit longrange orientation order at both the nanoscale and macroscale. This is an important consideration in the fabrication of devices spanning multiple size scales. The GNRs within nano/microfibers exhibit excellent alignment with their longitudinal axis parallel to the fiber axis. Optical absorbance spectroscopy measurements reveal that the longitudinal surface plasmon resonance bands of the aligned GNRs are highly anisotropic, depending on polarization angle, and that maximum absorption occurs when polarization is parallel to the fiber axis. Lastly, blends of hydrophobic and hydrophilic polymers have been prepared to control the spatial position of SPIONs within electrospun fibers on the basis of thermodynamic compatibility. In this case, TEM confirms that a core-sheath nanostructure naturally forms due to polymer-polymer phase separation and that the hydrophobic nanoparticles are sequestered in one preferred phase. Lastly, a nanocomposite fiber is created using only one entity, the organometallic polymer poly(ferrocenylsilane) (PFS)and its crystalline structure is probed alone and in the presence of SPIONs. Block copolymer cylindrical micelles of PFS-b-poly(isoprene) (PI) are crosslinked within an elastomeric matrix of poly (vinylmethoxysilane) (PVMS) and found to maintain their crystalline structure with the target application being nanowires in soft electronics.

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

    SciTech Connect

    Bursten, B.E.

    1992-12-04

    The upgrade to the DECstation 3100 (and other workstations underway) has enabled the use of more sophisticated electronic structure methods. Research were done in the following fields: tris(cyclopentadienyl) actinide complexes; actinide-containing molecules with metal-metal bonds (U dimer, Th-Ru, Zr-Ru); and applications of fully relativistic DV-X[alpha] method to trivalent actinide chemistry (MCl[sub 3]).

  15. Modular self-assembly, characterization, and host-guest chemistry of nanoscale organometallic architectures

    SciTech Connect

    Manna, J.; Kuehl, C.J.; Stang, P.J.; Muddiman, D.C.; Smith, R.D.

    1997-12-31

    The supramolecular synthesis and chemistry of organic macrocycles has been the focus of considerable study for over thirty years. In contrast, the chemistry of analogous inorganic and organometallic macrocycles is in it infancy; little is know about the stability, spectroscopic and physical properties, and chemistry of these species. We will report on the design of several unique supramolecular macrocycles and the characterization of these species by a range of spectroscopic techniques, including electrospray-ionization Fourier transform ion cyclotron resonance spectrometry. Preliminary data concerning the host-guest chemistry of these macrocycles will also be presented.

  16. 2001 Gordon Research Conference on Organometallic Chemistry. Final progress report [agenda and attendee list

    SciTech Connect

    Burns, Carol

    2001-07-27

    The Gordon Research Conference on Organometallic Chemistry was held at Salve Regina University, Newport, Rhode Island, July 22-27, 2001. The conference had 133 participants. The attendees represented the spectrum of endeavor in this field, coming from academia, industry, and government laboratories, and included US and foreign scientists, senior researchers, young investigators, and students. Emphasis was place on current unpublished research and discussion of the future target areas in this field. There was a conscious effort to stimulate lively discussion about the key issues in the field today. Time for formal presentations was limited in the interest of group discussions; poster sessions were held.

  17. Luminescent Cyclometalated Platinum Complexes with π-Bonded Catecholate Organometallic Ligands.

    PubMed

    Moussa, Jamal; Loch, Aruny; Chamoreau, Lise-Marie; Degli Esposti, Alessandra; Bandini, Elisa; Barbieri, Andrea; Amouri, Hani

    2017-02-20

    A series of cyclometalated platinum(II) complexes of the type [(ppy)Pt(LM)](n+) (n = 0, 1) with π-bonded catecholates acting as organometallic ligands (LM) have been prepared and characterized by analytical techniques. In addition, the structures of two complexes of the series were determined by single-crystal X-ray diffraction. The packing shows the formation of a 1D supramolecular assembly generated by dPt-πCp* interactions among individual units. All complexes are luminescent in the solid state and in solution media. The results of photophysics have been rationalized by means of density functional theory (DFT) and time-dependent DFT investigations.

  18. A ferroelectric olefin-copper(I) organometallic polymer with flexible organic ligand (R)-MbVBP

    NASA Astrophysics Data System (ADS)

    Wang, Guo-Xi; Xing, Zheng; Chen, Li-Zhuang; Han, Guang-Fan

    2015-07-01

    Hydrothermal treatment of (R)-2-methyl-1,4-bis(4-vinylbenzyl)piperazine [(R)-MbVBP] and CuCl afforded a novel olefin-copper(I) coordination compound. Introducing the flexible ligand (R)-MbVBP allowed the olefin-copper(I) organometallic compound to crystallize in a polar point group P21. The compound was ferroelectric, and its electric hysteresis loop showed a remnant polarization (Pr) of 0.13-0.32 μC cm-2 and a coercive field (Ec) of 3.5-11 kV cm-1.

  19. Exploration geochemical technique for the determination of preconcentrated organometallic halides by ICP-AES

    USGS Publications Warehouse

    Motooka, J.M.

    1988-01-01

    An atomic absorption extraction technique which is widely used in geochemical exploration for the determination of Ag, As, Au, Bi, Cd, Cu, Mo, Pb, Sb, and Zn has been modified and adapted to a simultaneous inductively coupled plasma-atomic emission instrument. the experimental and operating parameters are described for the preconcentration of the metals into their organometallic halides and for the determination of the metals. Lower limits of determination are equal to or improved over those for flame atomic absorption (except Au) and ICP results are very similar to the accepted AA values, with precision for the ICP data in excess of that necessary for exploration purposes.

  20. In vitro antimalarial activity of a new organometallic analog, ferrocene-chloroquine.

    PubMed

    Domarle, O; Blampain, G; Agnaniet, H; Nzadiyabi, T; Lebibi, J; Brocard, J; Maciejewski, L; Biot, C; Georges, A J; Millet, P

    1998-03-01

    The in vitro activities of new organometallic chloroquine analogs, based on 4-amino-quinoleine compounds bound to a molecule of ferrocene, were evaluated against chloroquine-susceptible, chloroquine-intermediate, and chloroquine-resistant, culture-adapted Plasmodium falciparum lineages by a proliferation test. One of the ferrocene analogs totally restored the activity of chloroquine against chloroquine-resistant parasites. This compound, associated with tartaric acid for better solubility, was highly effective. The role of the ferrocene in reversing chloroquine resistance is discussed, as is its potential use for human therapy.

  1. In Vitro Antimalarial Activity of a New Organometallic Analog, Ferrocene-Chloroquine

    PubMed Central

    Domarle, O.; Blampain, G.; Agnaniet, H.; Nzadiyabi, T.; Lebibi, J.; Brocard, J.; Maciejewski, L.; Biot, C.; Georges, A. J.; Millet, P.

    1998-01-01

    The in vitro activities of new organometallic chloroquine analogs, based on 4-amino-quinoleine compounds bound to a molecule of ferrocene, were evaluated against chloroquine-susceptible, chloroquine-intermediate, and chloroquine-resistant, culture-adapted Plasmodium falciparum lineages by a proliferation test. One of the ferrocene analogs totally restored the activity of chloroquine against chloroquine-resistant parasites. This compound, associated with tartaric acid for better solubility, was highly effective. The role of the ferrocene in reversing chloroquine resistance is discussed, as is its potential use for human therapy. PMID:9517929

  2. Combined quantum mechanical/molecular mechanics modeling for large organometallic and metallobiochemical systems

    NASA Astrophysics Data System (ADS)

    Leong, Max Kangchien

    A method of combined quantum mechanics/molecular mechanics has been developed to model larger organometallic and metallobiochemical systems where neither quantum mechanics nor molecular mechanics, applied separately, can solve the problem. An electronically transparent interface, which allows charge transfers between the quantum and classical fragments, is devised and realized by employing a special iterative procedure of double (intrafragment and interfragment) self-consistent calculations. The combined QM/MM scheme was successfully applied to model iron picket-fence porphyrin, vitamin B12, aquocobalamin, and vitamin B12 coenzyme molecules.

  3. Organotitanoxanes with unique structure among transition-element organometallic oxide derivatives.

    PubMed

    Buitrago, Olga; Mosquera, Marta E G; Jiménez, Gerardo; Cuenca, Tomás

    2008-05-19

    The synthesis of novel titanoxane compounds, [{(TiCl)(Ti)[mu-(eta(5)-C5Me4SiMe2O-kappaO)]2(mu-O)}2(mu-O)] (4) and [{Ti[mu-(eta(5)-C5Me4SiMe2O-kappaO)](mu-O)}6] (5), by controlled hydrolysis of a dinuclear titanium/oxo complex is described. Complexes 4 and 5 show unprecedented structural features for organometallic oxide derivatives of transition elements and represent unique fully characterized examples of tetra- and hexanuclear organo-transition-metal oxide compounds with an open-chain and a monocyclic structure, respectively.

  4. Mössbauer effect studies on organometallic237Np-compounds

    NASA Astrophysics Data System (ADS)

    Adrian, G.; Appel, H.; Bohlander, R.; Haffner, H.; Kanellakopulos, B.

    1988-02-01

    A series of organometallic compounds of tetravalent Neptunium was studied by Moessbauer methods. Three of them will be presented here. Their molecular structure is close to C3v symmetry. The data were parameterised on the basis of an anisotropic paramagnetic relaxation model and will be interpreted for each individual compound. In general it can be stated that distortions from axially symmetric hyperfine parameters were observed, no magnetic ordering occured at all temperatures above 1.5 K and anisotropic relaxation frequencies had to be introduced to fit the spectra.

  5. Simulation and testing of a vertical organometallic vapor phase epitaxy reactor

    NASA Astrophysics Data System (ADS)

    Sani, R. A.; Barmawi, M.; Mindara, J. Y.

    1998-02-01

    The purpose of the study is to design a single wafer vertical organo-metallic vapor phase epitaxy (OMVPE) reactor which gives a uniform deposition around the symmetry axis. The vertical reactor under the consideration consist of a diffuser and a system of coaxial cylinders to laminarize the flow which may lead to a uniform deposition without rotating the susceptor. The simulation shows that for a susceptor with a radius of 2.5 cm, a uniformity can be achieved in a region of a radius of 2 cm within 1% for certain operating condition. The result is compared with the experimental measurement of TiO2 deposition from TTIP.

  6. Selective growth of GaAs by organometallic vapor phase epitaxy at atmospheric pressure

    NASA Astrophysics Data System (ADS)

    Azoulay, R.; Dugrand, L.

    1991-01-01

    Complete selective epitaxy of GaAs by organometallic vapor phase epitaxy at atmospheric pressure was achieved by using TMG, AsH3, and AsCl3 as starting gases. Selectivity was observed at growth temperatures ranging from 650 to 750 °C. The blocking of polycrystal deposition on the mask, Si3N4, or W, is attributed to the adsorption of HCl on the mask, thus preventing the nucleation of GaAs. On the openings, the growth rate may be adjusted by controlling the TMG/AsCl3 ratio. When TMG/AsCl3<1, no growth occurs, but etching is observed.

  7. Investigation of fragmentation processes following core photoionization of organometallic molecules in the vapor phase

    NASA Astrophysics Data System (ADS)

    Nagaoka, Shin-ichi; Suzuki, Shinzo; Koyano, Inosuke

    1988-04-01

    Ionic fragmentation processes following ( n - 1)d core level photoionization of organometallic molecules have been studied in the vapor phase using synchrotron radiation. Results on tetramethyllead, tetramethyltin and tetramethylgermanium are reported. The threshold electron spectra and the photoionization efficiency curves of these molecules are presented and discussed. It is concluded that the ( n - 1)d 9 core-hole state of M(CH 3) 4 (M  Pb, Sn or Ge) is split into five sublevels owing to both the spin-orbi and the electrostatic perturbations by the methyl groups, and that the M + ions are predominantly produced following ( n - 1)d photoionization.

  8. Organometallic synthesis, reactivity and catalysis in the solid state using well-defined single-site species

    PubMed Central

    Pike, Sebastian D.; Weller, Andrew S.

    2015-01-01

    Acting as a bridge between the heterogeneous and homogeneous realms, the use of discrete, well-defined, solid-state organometallic complexes for synthesis and catalysis is a remarkably undeveloped field. Here, we present a review of this topic, focusing on describing the key transformations that can be observed at a transition-metal centre, as well as the use of well-defined organometallic complexes in the solid state as catalysts. There is a particular focus upon gas–solid reactivity/catalysis and single-crystal-to-single-crystal transformations. PMID:25666064

  9. Improved QM Methods and Their Application in QM/MM Studies of Enzymatic Reactions

    NASA Astrophysics Data System (ADS)

    Jorgensen, William L.

    2007-03-01

    Quantum mechanics (QM) and Monte Carlo statistical mechanics (MC) simulations have been used by us since the early 1980s to study reaction mechanisms and the origin of solvent effects on reaction rates. A goal was always to perform the QM and MC/MM calculations simultaneously in order to obtain free-energy surfaces in solution with no geometrical restrictions. This was achieved by 2002 and complete free-energy profiles and surfaces with full sampling of solute and solvent coordinates can now be obtained through one job submission using BOSS [JCC 2005, 26, 1689]. Speed and accuracy demands also led to development of the improved semiempirical QM method, PDDG-PM3 [JCC 1601 (2002); JCTC 817 (2005)]. The combined PDDG-PM3/MC/FEP methodology has provided excellent results for free energies of activation for many reactions in numerous solvents. Recent examples include Cope, Kemp and E1cb eliminations [JACS 8829 (2005), 6141 (2006); JOC 4896 (2006)], as well as enzymatic reactions catalyzed by the putative Diels-Alderase, macrophomate synthase, and fatty-acid amide hydrolase [JACS 3577 (2005); JACS (2006)]. The presentation will focus on the accuracy that is currently achievable in such QM/MM studies and the accuracy of the underlying QM methodology including extensive comparisons of results from PDDG-PM3 and ab initio DFT methods.

  10. Application of Grote-Hynes theory to the reaction catalyzed by thymidylate synthase.

    PubMed

    Kanaan, Natalia; Roca, Maite; Tuñón, Iñaki; Martí, Sergio; Moliner, Vicent

    2010-10-28

    A theoretical study of dynamic effects on the rate-limiting step of the thymidylate synthase catalyzed reaction has been carried out by means of Grote-Hynes theory, successfully predicting the values of the recrossing effects for a chemical reaction that involves the transfer of a classical light particle. The transmission coefficients, obtained at 278, 293, 303, and 313 K, are almost invariant and in all cases far from unity, revealing a significant coupling of the environment motions and the reaction coordinate. Nevertheless, their energetic contribution to the activation free energy represents less than 0.50 kcal/mol for each of the four tested temperatures. Calculation of the transmission coefficient for the isotopically labeled hydride transfer has rendered almost the same values, in agreement with the experimentally observed temperature-independent KIEs. Fourier transform of the time-dependent friction kernel at these four temperatures has allowed obtaining the transition-state friction spectra, which present very small dependence with temperature. Their analysis has led to the identification of some key vibrational modes governing the coupling between the reaction coordinate and the protein environment, thus identifying the relevant motions in the active site and obtaining a full picture of the role of each amino acid.

  11. Synthesis of Solid 2-Pyridylzinc Reagents and their Application in Negishi Reactions

    PubMed Central

    Colombe, James R.; Bernhardt, Sebastian; Stathakis, Christos

    2013-01-01

    In search of alternatives to unstable or unreliable 2-pyridylboron reagents, we have explored two new varieties of solid, moderately air-stable 2-pyridylzinc reagents. Both reagents can be manipulated in air and are competent nucleophiles in Negishi cross-coupling reactions. PMID:24156393

  12. Application of Mössbauer Spectroscopy to the Carbon Oxides Hydrogenation Reactions

    NASA Astrophysics Data System (ADS)

    Cubeiro, M. L.; González-Jiménez, F.; Goldwasser, M. R.; Pérez-Zurita, M. J.; Pietri, E.; García, L.

    2001-05-01

    Iron-based catalysts have favorable activity and selectivity properties for the CO and CO2 hydrogenation reactions. Several Fe phases (oxides and carbides) can be present in these catalysts. The interaction of Fe with the other components of the catalyst (support, promoters) can affect the ease of reduction and also its transformation during the reactions. In this work, the relationship between catalytic behavior in the CO and CO2 hydrogenation reactions and the Fe phase composition of fresh and reacted catalysts was studied. Two types of catalysts were tested: a laterite and the other one made of iron supported on alumina, both unpromoted and promoted with K and Mn. Only those Fe species which can be reduced-carburized, by means of a pretreatment or by an in situ transformation under the reaction, seem to be able to perform the CO or CO2 hydrogenation. The reoxidation of the Fe carbide to magnetite was not associated to deactivation. The selectivity seems to be more affected by Fe species difficult to reduce than by magnetite produced by reoxidation.

  13. Green chemistry: solvent- and metal-free Prins cyclization. Application to sequential reactions.

    PubMed

    Clarisse, Damien; Pelotier, Béatrice; Piva, Olivier; Fache, Fabienne

    2012-01-04

    Prins cyclization between a homoallylic alcohol and an aldehyde, promoted by trimethylsilyl halide, afforded 4-halo-tetrahydropyrans with good to excellent yields. Thanks to the absence of the solvent and metal, the THP thus obtained have been implicated without purification in several other reactions, in a sequential way, affording in particular new indole derivatives.

  14. Click Reaction-Mediated Functionalization of Near-Infrared Pyrrolopyrrole Cyanine Dyes for Biological Imaging Applications.

    PubMed

    Zhou, Mingzhou; Zhang, Xuan; Bai, Mingfeng; Shen, Duanwen; Xu, Baogang; Kao, Jeffery; Xia, Ge; Achilefu, Samuel

    2013-05-21

    A clickable pyrrolopyrrole cyanine (PPCy) dye was synthesized by incorporating an alkyne moiety, followed by click reaction with azide-functionalized molecules of different polarities. The clickable dyes are readily amenable to labelling diverse molecules and exhibit an exceptionally high photostability and an impressive fluorescence quantum yield.

  15. Synthesis of solid 2-pyridylzinc reagents and their application in Negishi reactions.

    PubMed

    Colombe, James R; Bernhardt, Sebastian; Stathakis, Christos; Buchwald, Stephen L; Knochel, Paul

    2013-11-15

    In search of alternatives to unstable or unreliable 2-pyridylboron reagents, we have explored two new varieties of solid, moderately air-stable 2-pyridylzinc reagents. Both reagents can be manipulated in air and are competent nucleophiles in Negishi cross-coupling reactions.

  16. Applications of dynamic nuclear polarization to the study of reactions and reagents in organic and biomolecular chemistry.

    PubMed

    Hilty, Christian; Bowen, Sean

    2010-08-07

    Nuclear Magnetic Resonance (NMR) is an important spectroscopic tool for the identification and structural characterization of molecules in chemistry and biochemistry. The most significant limitation of NMR compared to other spectroscopies is its relatively low sensitivity, which thus often requires long measurement times or large amounts of sample. A way of increasing sensitivity of single scan NMR spectra by several orders of magnitude is through hyperpolarization of nuclear spins. Dynamic nuclear polarization allows hyperpolarization of most spins in small molecules encountered in chemistry and biochemistry. NMR spectra of small amounts of samples from natural source, or from chemical synthesis can readily be acquired. Perhaps more interestingly, the availability of the entire hyperpolarized NMR signal in one single scan allows the measurement of transient processes in real time, if applied together with a stopped-flow technique. Through observation of chemical shift, different reactant and product species can be distinguished, and kinetics and mechanisms, for example in enzyme catalyzed reactions, can be elucidated. Real-time hyperpolarization-enhanced NMR is uniquely amenable to correlating atomic positions not only through space, but also over time between reactant and product species. Such correlations carry mechanistic information about a reaction, and can prove reaction pathways. Applications of this technique are emerging in different areas of chemistry concerned with rapid reactions, including not only enzymatic processes, but also chemical catalysis and protein folding.

  17. Carbon-supported palladium and ruthenium nanoparticles: application as catalysts in alcohol oxidation, cross-coupling and hydrogenation reactions.

    PubMed

    García-Suárez, Eduardo J; Lara, Patricia; García, Ana B; Philippot, Karine

    2013-11-01

    In the last fifteen-years, the application of metal nanoparticles as catalysts in organic synthesis has received a renewed interest. Therefore, much attention is currently being paid to the synthesis of metal nanoparticles in order to achieve the control of their characteristics in terms of size, shape and surface chemistry. Besides this, the recyclability as well as the recovery from the reaction medium still remain the major drawbacks to widespread the use of nanoparticles in catalysis. To overcome these problems, the immobilization of metal nanoparticles on solid supports appears as a promising alternative. In that context, carbon materials offer several advantages as solid supports such as availability, relatively low cost, high mechanical strength, chemical stability, and a pore structure along with an attractive surface chemistry which allows easy modifications, such as its functionalization, to suit the nanoparticles immobilization needs. Among the transition metals Palladium and Ruthenium are widely employed as efficient catalysts in many reactions. Herein, the most recent advances, from recent papers and patents, in relation to the preparation of carbon-supported Pd or Ru nanoparticles systems as well as their application as catalysts in alcohol oxidation, cross-coupling or hydrogenation reactions, are reviewed.

  18. Structure of adsorbed organometallic rhodium: model single atom catalysts.

    PubMed

    Bennett, R A; McCavish, N D; Basham, M; Dhanak, V R; Newton, M A

    2007-02-02

    We have determined the structure of a complex rhodium carbonyl chloride [Rh(CO)2Cl] molecule adsorbed on the TiO2(110) surface by the normal incidence x-ray standing wave technique. The data show that the technique is applicable to reducible oxide systems and that the dominant adsorbed species is undissociated with Rh binding atop bridging oxygen and to the Cl found close to the fivefold coordinated Ti ions in the surface. A minority geminal dicarbonyl species, where Rh-Cl bond scission has occurred, is found bridging the bridging oxygen ions forming a high-symmetry site.

  19. Epoxide Activated Anionic Polymerization: Application to the Synthesis of (Co)Polyethers with Controlled Structure and Tuned Properties

    NASA Astrophysics Data System (ADS)

    Labbe, Amelie; Rejsek, Virginie; Carlotti, Stephane; Deffieux, Alain

    A ring opening polymerization process allowing the fast and controlled anionic polymerization of epoxide monomers is described and applied to the synthesis of (co)polyethers with novel structure and composition. The approach is based on the simultaneous formation of complexes between an organometallic Lewis acid additive with both the anionic initiator and the monomer. In conjunction with the use of tetraalkylammonium or phosphonium salts as initiators, the addition of such additive allows the synthesis of polyethers and block copolyethers with controlled molar masses and narrow polydispersities, in hydrocarbon media, at low temperature, and in short reaction times. The low nucleophilic character of the propagating species involved in the polymerization avoids transfer to monomer, a side reaction which is often predominant in conventional anionic polymerizations. This also allows the controlled polymerization of functional epoxides such as glycidyl methacrylate and epichlorohydrin. Properties and potential applications of these new polyethers and copolyethers are also reported.

  20. Organometallic rotaxane dendrimers with fourth-generation mechanically interlocked branches

    PubMed Central

    Wang, Wei; Chen, Li-Jun; Wang, Xu-Qing; Sun, Bin; Li, Xiaopeng; Zhang, Yanyan; Shi, Jiameng; Yu, Yihua; Zhang, Li; Liu, Minghua; Yang, Hai-Bo

    2015-01-01

    Mechanically interlocked molecules, such as catenanes, rotaxanes, and knots, have applications in information storage, switching devices, and chemical catalysis. Rotaxanes are dumbbell-shaped molecules that are threaded through a large ring, and the relative motion of the two components along each other can respond to external stimuli. Multiple rotaxane units can amplify responsiveness, and repetitively branched molecules—dendrimers—can serve as vehicles for assembly of many rotaxanes on single, monodisperse compounds. Here, we report the synthesis of higher-generation rotaxane dendrimers by a divergent approach. Linkages were introduced as spacer elements to reduce crowding and to facilitate rotaxane motion, even at the congested periphery of the compounds up to the fourth generation. The structures were characterized by 1D multinuclear (1H, 13C, and 31P) and 2D NMR spectroscopy, MALDI-TOF-MS, gel permeation chromatography (GPC), and microscopy-based methods including atomic force microscopy (AFM) and transmission electron microscopy (TEM). AFM and TEM studies of rotaxane dendrimers vs. model dendrimers show that the rotaxane units enhance the rigidity and reduce the tendency of these assemblies to collapse by self-folding. Surface functionalization of the dendrimers with ferrocenes as termini produced electrochemically active assemblies. The preparation of dendrimers with a well-defined topological structure, enhanced rigidity, and diverse functional groups opens previously unidentified avenues for the application of these materials in molecular electronics and materials science. PMID:25902491

  1. Electrochemical tuning of vertically aligned MoS2 nanofilms and its application in improving hydrogen evolution reaction.

    PubMed

    Wang, Haotian; Lu, Zhiyi; Xu, Shicheng; Kong, Desheng; Cha, Judy J; Zheng, Guangyuan; Hsu, Po-Chun; Yan, Kai; Bradshaw, David; Prinz, Fritz B; Cui, Yi

    2013-12-03

    The ability to intercalate guest species into the van der Waals gap of 2D layered materials affords the opportunity to engineer the electronic structures for a variety of applications. Here we demonstrate the continuous tuning of layer vertically aligned MoS2 nanofilms through electrochemical intercalation of Li(+) ions. By scanning the Li intercalation potential from high to low, we have gained control of multiple important material properties in a continuous manner, including tuning the oxidation state of Mo, the transition of semiconducting 2H to metallic 1T phase, and expanding the van der Waals gap until exfoliation. Using such nanofilms after different degree of Li intercalation, we show the significant improvement of the hydrogen evolution reaction activity. A strong correlation between such tunable material properties and hydrogen evolution reaction activity is established. This work provides an intriguing and effective approach on tuning electronic structures for optimizing the catalytic activity.

  2. Electrochemical tuning of vertically aligned MoS2 nanofilms and its application in improving hydrogen evolution reaction

    PubMed Central

    Wang, Haotian; Lu, Zhiyi; Xu, Shicheng; Kong, Desheng; Cha, Judy J.; Zheng, Guangyuan; Hsu, Po-Chun; Yan, Kai; Bradshaw, David; Prinz, Fritz B.; Cui, Yi

    2013-01-01

    The ability to intercalate guest species into the van der Waals gap of 2D layered materials affords the opportunity to engineer the electronic structures for a variety of applications. Here we demonstrate the continuous tuning of layer vertically aligned MoS2 nanofilms through electrochemical intercalation of Li+ ions. By scanning the Li intercalation potential from high to low, we have gained control of multiple important material properties in a continuous manner, including tuning the oxidation state of Mo, the transition of semiconducting 2H to metallic 1T phase, and expanding the van der Waals gap until exfoliation. Using such nanofilms after different degree of Li intercalation, we show the significant improvement of the hydrogen evolution reaction activity. A strong correlation between such tunable material properties and hydrogen evolution reaction activity is established. This work provides an intriguing and effective approach on tuning electronic structures for optimizing the catalytic activity. PMID:24248362

  3. The preparation and intra- and intermolecular addition reactions of acyclic N-acylimines: application to the synthesis of (+/-)-sertraline.

    PubMed

    DeNinno, M P; Eller, C; Etienne, J B

    2001-10-19

    Intramolecular endo-cyclization reactions of N-acyliminium ions have seen wide application for the synthesis of heterocyclic compounds. The corresponding exocyclic variant, which would provide 1-aminotetralin derivatives, for example, has little precedent. We have discovered that acyclic N-acylcarbamates can be readily reduced to the corresponding N-acylhemiaminal derivatives in high yield using DIBAL as the reducing agent. These intermediates are remarkably stable and, if desired, can be purified and stored. The acyclic N-acylhemiaminals undergo both intra- and intermolecular nucleophilic addition reactions mediated by strong Lewis acids, such as TiCl(4). Diastereoselectivity, induced either by a substituent on the newly formed ring, or by utilizing a chiral ester on the carbamic acid, was disappointingly low. This methodology was successfully applied to the synthesis of the racemic form of the marketed antidepressant sertraline.

  4. Applications of the ETS-NOCV method in descriptions of chemical reactions.

    PubMed

    Mitoraj, Mariusz Paweł; Parafiniuk, Monika; Srebro, Monika; Handzlik, Michał; Buczek, Agnieszka; Michalak, Artur

    2011-09-01

    The present study characterizes changes in the electronic structure of reactants during chemical reactions based on the combined charge and energy decomposition scheme, ETS-NOCV (extended transition state-natural orbitals for chemical valence). Decomposition of the activation barrier, ΔE (#), into stabilizing (orbital interaction, ΔE (orb), and electrostatic, ΔE (elstat)) and destabilizing (Pauli repulsion, ΔE (Pauli), and geometry distortion energy, ΔE (dist)) factors is discussed in detail for the following reactions: (I) hydrogen cyanide to hydrogen isocyanide, HCN → CNH isomerization; (II) Diels-Alder cycloaddition of ethene to 1,3-butadiene; and two catalytic processes, i.e., (III) insertion of ethylene into the metal-alkyl bond using half-titanocene with phenyl-phenoxy ligand catalyst; and (IV) B-H bond activation catalyzed by an Ir-containing catalyst. Various reference states for fragments were applied in ETS-NOCV analysis. We found that NOCV-based deformation densities (Δρ (i)) and the corresponding energies ΔE (orb)(i) obtained from the ETS-NOCV scheme provide a very useful picture, both qualitatively and quantitatively, of electronic density reorganization along the considered reaction pathways. Decomposition of the barrier ΔE(#) into stabilizing and destabilizing contributions allowed us to conclude that the main factor responsible for the existence of positive values of ΔE (#) for all processes (I, II, III and IV) is Pauli interaction, which is the origin of steric repulsion. In addition, in the case of reactions II, III and IV, a significant degree of structural deformation of the reactants, as measured by the geometry distortion energy, plays an important role. Depending on the reaction type, stabilization of the transition state (relatively to the reactants) originating either from the orbital interaction term or from electrostatic attraction can be of vital importance. Finally, use of the ETS-NOCV method to describe catalytic

  5. Application of an Artificial Neural Network to the Prediction of OH Radical Reaction Rate Constants for Evaluating Global Warming Potential.

    PubMed

    Allison, Thomas C

    2016-03-03

    Rate constants for reactions of chemical compounds with hydroxyl radical are a key quantity used in evaluating the global warming potential of a substance. Experimental determination of these rate constants is essential, but it can also be difficult and time-consuming to produce. High-level quantum chemistry predictions of the rate constant can suffer from the same issues. Therefore, it is valuable to devise estimation schemes that can give reasonable results on a variety of chemical compounds. In this article, the construction and training of an artificial neural network (ANN) for the prediction of rate constants at 298 K for reactions of hydroxyl radical with a diverse set of molecules is described. Input to the ANN consists of counts of the chemical bonds and bends present in the target molecule. The ANN is trained using 792 (•)OH reaction rate constants taken from the NIST Chemical Kinetics Database. The mean unsigned percent error (MUPE) for the training set is 12%, and the MUPE of the testing set is 51%. It is shown that the present methodology yields rate constants of reasonable accuracy for a diverse set of inputs. The results are compared to high-quality literature values and to another estimation scheme. This ANN methodology is expected to be of use in a wide range of applications for which (•)OH reaction rate constants are required. The model uses only information that can be gathered from a 2D representation of the molecule, making the present approach particularly appealing, especially for screening applications.

  6. Application of hydrogen peroxide encapsulated in silica xerogels to oxidation reactions.

    PubMed

    Bednarz, Szczepan; Ryś, Barbara; Bogdał, Dariusz

    2012-07-04

    Hydrogen peroxide was encapsulated into a silica xerogel matrix by the sol-gel technique. The composite was tested as an oxidizing agent both under conventional and microwave conditions in a few model reactions: Noyori's method of octanal and 2-octanol oxidation and cycloctene epoxidation in a 1,1,1-trifluoroethanol/Na2WO4 system. The results were compared with yields obtained for reactions with 30% H2O2 and urea-hydrogen peroxide (UHP) as oxidizing agents. It was found that the composite has activity similar to 30% H2O2 and has a several advantages over UHP such as the fact that silica and H2O are the only products of the composite decomposition or no contamination by urea or its derivatives occurs; the xerogel is easier to heated by microwave irradiation than UHP and could be used as both an oxidizing agent and as solid support for microwave assisted solvent-free oxidations.

  7. Application of an independent parallel reactions model on the annealing kinetics of BEPO irradiated graphite

    NASA Astrophysics Data System (ADS)

    Lasithiotakis, Michael; Marsden, Barry J.; James Marrow, T.

    2012-08-01

    Stored energy release rates have been determined for neutron irradiated graphite samples machined from an early air-cooled nuclear reactor (British Experimental Pile Zero or BEPO). The rate of release of stored energy was measured for both isothermal and linear rise heating rate differential scanning calorimetry experiments. The rate of release data were analysed using a thermal kinetics, independent parallel reactions model. The effect of annealing on the graphite crystalline structure was evaluated by investigating changes to X-ray diffraction spectra. A correlation between the calculated crystallite size and stored energy release is presented. A method for calculating the kinetic parameters for the annealing reaction is proposed and tested against the data. The method shows excellent consistency for both the isothermal and linear heating rate experiments (with less than 3% standard deviation).

  8. [Clinical application of moving cupping therapy based on skin reaction observation and syndrome differentiation].

    PubMed

    Deng, Xiao-Lan; Chen, Bo; Chen, Ze-Lin

    2014-12-01

    The diagnostic evidence on clinical diseases and theoretic basis of moving cupping therapy were ex- plored in the paper. By the observation of the local reaction, such as skin appearance and color, the affected location, duration of sickness and nature of disease were judged. Different moving cupping methods were selected for different disorders. It was discovered that the property of syndromes should be recognized by the palpation on skin and muscle in the moving cupping therapy so that the pathogenesis and treating principle could be carefully determined. The moving cupping therapy is the important component of body surface therapy. Skin reaction observation and syndrome differentiation is the essential guidance of the moving cupping therapy.

  9. Thermonuclear breakup reactions of light nuclei. II - Gamma-ray line production and other applications

    NASA Technical Reports Server (NTRS)

    Guessoum, Nidhal

    1989-01-01

    The main consequence of nuclear breakup reactions in high-temperature plasmas is shown to be to reduce the production of the gamma-ray lines, due to the breakup of these species at high temperature. Results of the emissivities of all the relevant gamma-ray lines are discussed. It is shown that the magnitude of the breakup effect on the line emissivities depends strongly on temperature, but more importantly on the plasma density and on the available time for the ion processes. Other effects considered include the production of neutrons (from the breakup of helium) and its consequences (such as the production of gamma rays from n-capture reactions and dynamical effects in accretion disk plasmas).

  10. Controlled silanization-amination reactions on the Ti6Al4V surface for biomedical applications.

    PubMed

    Rodríguez-Cano, Abraham; Cintas, Pedro; Fernández-Calderón, María-Coronada; Pacha-Olivenza, Miguel-Ángel; Crespo, Lara; Saldaña, Laura; Vilaboa, Nuria; González-Martín, María-Luisa; Babiano, Reyes

    2013-06-01

    Formation of thin films on titanium alloys incorporating bioactive small molecules or macromolecules is a route to improve their biocompatibility. Aminoalkylsilanes are commonly employed as interface reagents that combine good adhesion properties with an amino tail group susceptible of further functionalization. This article introduces a reproducible methodology to obtain a cross-linked polymer-type brush structure of covalently-bonded aminoalkylsiloxane chains on Ti6Al4V. The experimental protocol can be fine-tuned to provide a high density of surface-coated amino groups (threshold value: 2.1±0.1×10(-8) mol cm(-2)) as proven by chemical and spectrophotometric analyses. Using a model reaction involving the condensation of 3-aminopropyltrimethoxysilane (APTMS) on Ti6Al4V alloy, we herein show the effects of reaction temperature, reaction time and solvent humidity on the composition and structure of the film. The stability of the resulting coating under physiological-like conditions as well as the possibility of surface re-silanization has also been evaluated. To verify if detrimental effects on the biological performance of the Ti6Al4V alloy were induced by this coverage, human primary osteoblasts behavior, Staphylococci adhesion and biofilm formation have been tested and compared to the Ti6Al4V oxidized surface. Reaction with trans-cinnamaldehyde has used in order to determine useful amino groups at aminosilanized surface, XPS and UV analyses of imino derivatives generated reveal that almost a 50% of these groups are actually available at the siloxane chains.

  11. Pd-catalyzed arylation reactions with phenol diazonium salts: application in the synthesis of diarylheptanoids.

    PubMed

    Schmidt, Bernd; Hölter, Frank; Kelling, Alexandra; Schilde, Uwe

    2011-05-06

    The first total synthesis of the natural product (3S,7R)-5,6-dehydro-de-O-methyl centrolobine and various analogues is reported, using a highly regio- and diastereoselective Mizoroki-Heck reaction of phenol diazonium salts and enantiopure dihydropyrans. The assigned relative configuration was confirmed by single-crystal X-ray structure analysis, but a revision of the absolute configuration is proposed based on polarimetric measurement.

  12. Optimized Conditions for Passerini-Smiles Reactions and Applications to Benzoxazinone Syntheses.

    PubMed

    Martinand-Lurin, Elodie; Dos Santos, Aurélie; Robineau, Emmanuelle; Retailleau, Pascal; Dauban, Philippe; Grimaud, Laurence; El Kaïm, Laurent

    2016-09-21

    Initial conditions disclosed for the Passerini-Smiles reaction are associated with a lack of efficiency that has prevented chemists from using it since its discovery. We wish to report herein our thorough study in the development of new experimental conditions for this coupling between electron-poor phenols, isocyanides, and carbonyl derivatives. These new conditions have been applied to several synthetic strategies towards benzoxazinones.

  13. Unconventional application of the Mitsunobu reaction: Selective flavonolignan dehydration yielding hydnocarpins

    PubMed Central

    Huang, Guozheng; Schramm, Simon; Heilmann, Jörg; Biedermann, David; Křen, Vladimír

    2016-01-01

    Summary Various Mitsunobu conditions were investigated for a series of flavonolignans (silybin A, silybin B, isosilybin A, and silychristin A) to achieve either selective esterification in position C-23 or dehydration in a one-pot reaction yielding the biologically important enantiomers of hydnocarpin D, hydnocarpin and isohydnocarpin, respectively. This represents the only one-pot semi-synthetic method to access these flavonolignans in high yields. PMID:27340458

  14. The direct reaction field hamiltonian: Analysis of the dispersion term and application to the water dimer

    NASA Astrophysics Data System (ADS)

    Thole, B. T.; Van Duijnen, P. Th.

    1982-10-01

    The induction and dispersion terms obtained from quantum-mechanical calculations with a direct reaction field hamiltonian are compared to second order perturbation theory expressions. The dispersion term is shown to give an upper bound which is a generalization of Alexander's upper bound. The model is illustrated by a calculation on the interactions in the water dimer. The long range Coulomb, induction and dispersion interactions are reasonably reproduced.

  15. Syntheses of Papyracillic Acids: Application of the Tandem Chain Extension-Acylation Reaction

    PubMed Central

    Mazzone, Jennifer R.; Zercher, Charles K.

    2012-01-01

    A synthetic approach to the papyracillic acid family of natural products has been developed. The spiroacetal core is rapidly assembled through an unprecedented zinc carbenoid-mediated tandem chain extension-acylation reaction. Subsequent functional group manipulation provided access to papyracillic acid B and 4-epi-papyracillic acid C. The successful preparation of these molecules resulted in the clarification of structural assignments of members of this family of natural products. PMID:23013246

  16. Analysis and application of a velocity command motor as a reaction mass actuator

    NASA Technical Reports Server (NTRS)

    Sulla, Jeffrey L.; Juang, Jer-Nan; Horta, Lucas G.

    1990-01-01

    A commercially available linear stepper motor is applied as a reaction mass (RM) actuator. With the actuator operating in the (RM) relative-velocity command mode, open-loop and closed-loop testing is performed to determine operational limits. With the actuator mounted on a simple beam structure, root strain, RM acceleration, or beam acceleration is used in the feedback loop to augment the structural damping. The RM relative position is also used as feedback to ensure that the RM remains centered.

  17. Organometallic osmium(II) arene anticancer complexes containing picolinate derivatives.

    PubMed

    van Rijt, Sabine H; Peacock, Anna F A; Johnstone, Russell D L; Parsons, Simon; Sadler, Peter J

    2009-02-16

    Chlorido osmium(II) arene [(eta(6)-biphenyl)Os(II)(X-pico)Cl] complexes containing X = Br (1), OH (2), and Me (3) as ortho, or X = Cl (4), CO(2)H (5), and Me (6) as para substituents on the picolinate (pico) ring have been synthesized and characterized. The X-ray crystal structures of 1 and 6 show typical "piano-stool" geometry with intermolecular pi-pi stacking of the biphenyl outer rings of 6. At 288 K the hydrolysis rates follow the order 2 > 6 > 4 > 3 > 5 > 1 with half-lives ranging from minutes to 4.4 h illustrating the influence of both electronic and steric effects of the substituents. The pK(a) values of the aqua adducts 3A, 4A, 5A, and 6A were all in the range of 6.3-6.6. The para-substituted pico complexes 4-6 readily formed adducts with both 9-ethyl guanine (9EtG) and 9-ethyl adenine (9EtA), but these were less favored for the ortho-substituted complexes 1 and 3 showing little reaction with 9EtG and 9EtA, respectively. Density-functional theory calculations confirmed the observed preferences for nucleobase binding for complex 1. In cytotoxicity assays with A2780, cisplatin-resistant A2780cis human ovarian, A549 human lung, and HCT116 colon cancer cells, only complexes 4 (p-Cl) and 6 (p-Me) exhibited significant activity (IC(50) values < 25 microM). Both of these complexes were as active as cisplatin in A2780 (ovarian) and HCT116 (colon) cell lines, and even overcome cisplatin resistance in the A2780cis (ovarian) cell line. The inactivity of 5 is attributed to the negative charge on its para carboxylate substituent. These data illustrate how the chemical reactivity and cancer cell cytotoxicity of osmium arene complexes can be controlled and "fine-tuned" by the use of steric and electronic effects of substituents on a chelating ligand to give osmium(II) arene complexes which are as active as cisplatin but have a different mechanism of action.

  18. Performance and cost of energy transport and storage systems for dish applications using reversible chemical reactions

    NASA Technical Reports Server (NTRS)

    Schredder, J. M.; Fujita, T.

    1984-01-01

    The use of reversible chemical reactions for energy transport and storage for parabolic dish networks is considered. Performance and cost characteristics are estimated for systems using three reactions (sulfur-trioxide decomposition, steam reforming of methane, and carbon-dioxide reforming of methane). Systems are considered with and without storage, and in several energy-delivery configurations that give different profiles of energy delivered versus temperature. Cost estimates are derived assuming the use of metal components and of advanced ceramics. (The latter reduces the costs by three- to five-fold). The process that led to the selection of the three reactions is described, and the effects of varying temperatures, pressures, and heat exchanger sizes are addressed. A state-of-the-art survey was performed as part of this study. As a result of this survey, it appears that formidable technical risks exist for any attempt to implement the systems analyzed in this study, especially in the area of reactor design and performance. The behavior of all components and complete systems under thermal energy transients is very poorly understood. This study indicates that thermochemical storage systems that store reactants as liquids have efficiencies below 60%, which is in agreement with the findings of earlier investigators.

  19. Local tissue reaction after the application of topical hemostatic agents in a rat partial nephrectomy model.

    PubMed

    Chalupová, Marta; Suchý, Pavel; Pražanová, Gabriela; Bartošová, Ladislava; Sopuch, Tomáš; Havelka, Pavel

    2012-06-01

    Various hemostatics are used for renal surgical procedures. We investigated the hemostatic efficacy of cellulose derivatives on the model of partial nephrectomy in rats focusing on the local reaction of renal parenchyma. A total of 50 Wistar rats were divided into five groups of 10 animals each. Partial nephrectomy of the caudal pole without hilar vascular control was performed. Oxidized cellulose (OC), sodium salt of oxycellulose (OCN), carboxymethyl cellulose (CMC), dialdehyde cellulose (DAC), and gelatin-based hemostatic (C) were applied to the bleeding wounds. The time to hemostasis was monitored. Half of the animals were euthanized after 3 days, the second half 30 days from the experiment start date. The left kidney was excised and subjected to histopathological examination. The biochemical data was subjected to statistical analysis. The time to hemostasis in all groups was significantly less than in the C group (in OC p = 0.0057, OCN p = 0.0039, CMC and DAC p = 0.0001). In the C group, massive hemorrhages and necrosis did occur. In the OC and OCN groups, there were regenerative changes, a receding inflammatory reaction and hemorrhage. DAC caused an immune reaction and massive interstitial hemorrhages with biochemical signs of liver damage. Parenchyma in CMC revealed a reduction of necrosis and interstitial hemorrhages with regenerative processes. The most effective hemostatics were CMC and OC, achieving the best results both in the time to hemostasis, and for histopathological evaluation.

  20. Anomalous Doppler broadening caused by exothermic reactions: application to hydrogen Balmer lines

    NASA Astrophysics Data System (ADS)

    Loureiro, J.; Amorim, J.

    2011-08-01

    The three- and one-dimensional velocity distributions of a product species created by an exothermic reaction are calculated using the energy conservation, with the aim of evaluating the impact of such processes on the anomalous broadening of Doppler lines. The calculations are performed to the reaction H{2/+} + H2 → H{3/+} + H, in which according to Christoffersen (1964) an amount of 1.56 eV is transferred to the product species. It is shown that the deviations relatively to Maxwell-Boltzmann distributions are significant as the internal energy defect ΔE increases, even within energies lower than 1.56 eV, and hence the profiles of excited H∗ atoms, associated with the emission of hydrogen Balmer lines, created in the sequence of H( n = 1) produced by the above reaction are not of Gaussian-type. The profiles are markedly flatter and squarer than Gaussian distributions. The validity of the species temperature determined from the full width at half maximum (FWHM) of the lines, as well as the fit of the lines by multimodal Gaussian functions, is then analyzed.

  1. Performance and cost of energy transport and storage systems for dish applications using reversible chemical reactions

    NASA Astrophysics Data System (ADS)

    Schredder, J. M.; Fujita, T.

    1984-10-01

    The use of reversible chemical reactions for energy transport and storage for parabolic dish networks is considered. Performance and cost characteristics are estimated for systems using three reactions (sulfur-trioxide decomposition, steam reforming of methane, and carbon-dioxide reforming of methane). Systems are considered with and without storage, and in several energy-delivery configurations that give different profiles of energy delivered versus temperature. Cost estimates are derived assuming the use of metal components and of advanced ceramics. (The latter reduces the costs by three- to five-fold). The process that led to the selection of the three reactions is described, and the effects of varying temperatures, pressures, and heat exchanger sizes are addressed. A state-of-the-art survey was performed as part of this study. As a result of this survey, it appears that formidable technical risks exist for any attempt to implement the systems analyzed in this study, especially in the area of reactor design and performance. The behavior of all components and complete systems under thermal energy transients is very poorly understood. This study indicates that thermochemical storage systems that store reactants as liquids have efficiencies below 60%, which is in agreement with the findings of earlier investigators.

  2. Analytical study of the hydrogen-air reaction mechanism with application to scramjet combustion

    SciTech Connect

    Jachimowski, C.J.

    1988-02-01

    A chemical kinetic mechanism for the combustion of hydrogen has been assembled and optimized by comparing the observed behavior as determined in shock tube and flame studies with that predicted by the mechanism. The reactions contained in the mechanism reflect the current state of knowledge of the chemistry of the hydrogen/air system, and the assigned rate coefficients are consistent with accepted values. It was determined that the mechanism is capable of satisfactorily reproducing the experimental results for a range of conditions relevant to scramjet combustion. Calculations made with the reaction mechanism for representative scramjet combustor conditions at Mach 8, 16, and 25 showed that chemical kinetic effects can be important and that combustor models which use nonequilibrium chemistry should be used in preference to models that assume equilibrium chemistry. For the conditions examined the results also showed the importance of including the HO/sub 2/ chemistry in the mechanism. For Mach numbers less than 16, the studies suggest that an ignition source will most likely be required to overcome slow ignition chemistry. At Mach 25, the initial temperature and pressure was high enough that ignition was rapid and the presence of an ignition source did not significantly affect reaction rates.

  3. Applications of SXPS for studying surface structure, reaction mechanisms and kinetics

    SciTech Connect

    Mullins, D.R.; Huntley, D.R.; Overbury, S.H.

    1994-12-31

    Soft x-ray photoelectron spectroscopy (SXPS) from the S 2p core level has been used to study adsorbate induced reconstruction, identify reaction intermediates and study reaction kinetics on the Ni(111) surface. The S 2p binding energy is affected by the nature of the surface adsorption site. It has been determined from the number of S 2p states and their relative binding energies that adsorbed S induces a reconstruction of the Ni(111) surface and that the S adsorbs in fourfold sites on terraces and in troughs. S 2p SXPS has also been used to identify adsorbed species during the thermal decomposition of methanethiol on Ni(111). CH{sub 3}SH adsorbs as CH{sub 3}S{minus} at low temperatures. Above 200 K, the CH{sub 3}S{minus} changes adsorption site and the C-S bond begins to cleave. The relative concentrations of CH{sub 3}S{minus} in the two different sites and of atomic S have been monitored as a function of temperature and initial coverage. As a result of the sensitivity and resolution available in SXPS, reaction rates and kinetic parameters have been obtained for the decomposition of benzenethiol on Ni(111) by monitoring the changes in the surface composition continuously as a function of temperature and time.

  4. An analytical study of the hydrogen-air reaction mechanism with application to scramjet combustion

    NASA Technical Reports Server (NTRS)

    Jachimowski, Casimir J.

    1988-01-01

    A chemical kinetic mechanism for the combustion of hydrogen has been assembled and optimized by comparing the observed behavior as determined in shock tube and flame studies with that predicted by the mechanism. The reactions contained in the mechanism reflect the current state of knowledge of the chemistry of the hydrogen/air system, and the assigned rate coefficients are consistent with accepted values. It was determined that the mechanism is capable of satisfactorily reproducing the experimental results for a range of conditions relevant to scramjet combustion. Calculations made with the reaction mechanism for representative scramjet combustor conditions at Mach 8, 16, and 25 showed that chemical kinetic effects can be important and that combustor models which use nonequilibrium chemistry should be used in preference to models that assume equilibrium chemistry. For the conditions examined the results also showed the importance of including the HO2 chemistry in the mechanism. For Mach numbers less than 16, the studies suggest that an ignition source will most likely be required to overcome slow ignition chemistry. At Mach 25, the initial temperature and pressure was high enough that ignition was rapid and the presence of an ignition source did not significantly affect reaction rates.

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

    SciTech Connect

    Nakajima, Atsushi

    2015-12-31

    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{sub 12}X, behaving as a “superatom”.

  6. Quantum Theory of Rearrangement Collisions with Applications to Elementary Chemical Reactions.

    NASA Astrophysics Data System (ADS)

    Bowers, Mark Steven

    A three-dimensional, quantum mechanical, coupled channel distorted wave approximation is developed for calculating cross sections for rearrangement collisions between an atom and a diatomic molecule based on the transition (T matrix) formulation of molecular scattering. In this approximation, both entrance and exit channel wave functions are calculated from the inelastic vibrational and rotational close-coupling approximation, and these wave functions are used in the calculation of the T matrix elements for rearrangement. This method allows for the internal states of both the target and product molecule to be dynamically coupled following the motion of the atom, and the wave functions for the exit and entrance channel have the proper asymptotic behavior. Therefore, this method is capable of yielding more accurate results than those from most of the T matrix schemes employed so far. An efficient computational procedure for calculating cross sections is given utilizing parity conservation and by reducing the six-dimensional integral over complex-valued functions to a real-valued three-dimensional integral. Cross sections calculated from this method are presented for the isotopic reactions H+H(,2), D+H(,2), H+H(,2), and Mu+H(,2) using the most accurate available potential surface for energies in the threshold regions of these reactions, and these are compared to other theoretical results when possible. The calculated cross sections for the H+H(,2) reaction are found to be in excellent agreement with the converged close coupling results. Rate constants obtained from the cross sections show the same temperature dependence and are of the same order of magnitude as experimental results; however, the present results are about a factor of 2-3 smaller than the experimental values at lower temperatures for all systems studied. The results of this study indicate that the present method is capable of correctly predicting all reaction attributes of the elementary chemical

  7. Modeling and Real-Time Process Monitoring of Organometallic Chemical Vapor Deposition of III-V Phosphides and Nitrides at Low and High Pressure

    NASA Technical Reports Server (NTRS)

    Bachmann, K. J.; Cardelino, B. H.; Moore, C. E.; Cardelino, C. A.; Sukidi, N.; McCall, S.

    1999-01-01

    The purpose of this paper is to review modeling and real-time monitoring by robust methods of reflectance spectroscopy of organometallic chemical vapor deposition (OMCVD) processes in extreme regimes of pressure. The merits of p-polarized reflectance spectroscopy under the conditions of chemical beam epitaxy (CBE) and of internal transmission spectroscopy and principal angle spectroscopy at high pressure are assessed. In order to extend OMCVD to materials that exhibit large thermal decomposition pressure at their optimum growth temperature we have designed and built a differentially-pressure-controlled (DCP) OMCVD reactor for use at pressures greater than or equal to 6 atm. We also describe a compact hard-shell (CHS) reactor for extending the pressure range to 100 atm. At such very high pressure the decomposition of source vapors occurs in the vapor phase, and is coupled to flow dynamics and transport. Rate constants for homogeneous gas phase reactions can be predicted based on a combination of first principles and semi-empirical calculations. The pressure dependence of unimolecular rate constants is described by RRKM theory, but requires variational and anharmonicity corrections not included in presently available calculations with the exception of ammonia decomposition. Commercial codes that include chemical reactions and transport exist, but do not adequately cover at present the kinetics of heteroepitaxial crystal growth.

  8. Synthesis of Pd-N-heterocyclic carbene Pd-catalyst and its application in MW-assisted Heck and Suzuki reaction

    EPA Science Inventory

    The first Pd-N-heterocyclic carbene (NHC) complex in the form of organic silica is prepared using sol-gel method and its application in Heck and Suzuki reactions are demonstrated. These C-C coupling reactions proceeded efficiently under the influence of microwave irradiation, wit...

  9. Application of a Double Aza-Michael Reaction in a 'Click, Click, Cy-Click' Strategy: From Bench to Flow.

    PubMed

    Zang, Qin; Javed, Salim; Ullah, Farman; Zhou, Aihua; Knudtson, Christopher A; Bi, Danse; Basha, Fatima Z; Organ, Michael G; Hanson, Paul R

    2011-09-01

    The development of a 'click, click, cy-click' process utilizing a double aza-Michael reaction to generate functionalized 1,2,5-thiadiazepane 1,1-dioxides is reported. Optimization in flow, followed by scale out of the inter-/intramolecular double aza-Michael addition has also been realized using a microwave-assisted, continuous flow organic synthesis platform (MACOS). In addition, a facile one-pot, sequential strategy employing in situ Huisgen cycloaddition post-double aza-Michael has been accomplished, and is applicable to library synthesis.

  10. Phthalocyanine-based organometallic nanocages: properties and gas storage.

    PubMed

    Zhu, Guizhi; Li, Yawei; Lü, Kun; Sun, Qiang

    2014-01-13

    Phthalocyanine (Pc) molecules are well-known flexible structural units for 1D nanotubes and 2D nanosheets. First-principles calculations combined with grand canonical Monte Carlo simulations are used to obtain the geometries, electronic structures, optical properties, and hydrogen-storage capacities of nanocages consisting of six Pc molecules with six Mg or Ca atoms. The primitive Pc cage has Th symmetry with twofold degeneracy in the highest occupied molecular orbital (HOMO), and threefold degeneracy in the lowest unoccupied molecular orbital (LUMO); the corresponding HOMO-LUMO gap is found to be 0.97 eV. The MgPc and CaPc cages have Oh symmetry with a HOMO-LUMO gap of 1.24 and 1.13 eV, respectively. Optical absorption spectra suggest that the Pc-based cages can absorb infrared light, which is different from the visible-light absorption in Pc molecules. We further show that the excess uptake of hydrogen on MgPc and CaPc cages at 298 K and 100 bar (1 bar=0.1 MPa) is about 3.49 and 4.74 wt%, respectively. The present study provides new insight into Pc-based nanostructures with potential applications.

  11. Application of carbon dioxide towards the development of smart materials, green reaction schemes and metallic nanoparticle synthesis

    NASA Astrophysics Data System (ADS)

    Mohammed, Fiaz S.

    Global carbon dioxide (CO2) emissions have steadily risen over the last 50 years, with 34 billion tons of CO2 released in 2009 alone. Its potential as a greenhouse gas has negatively affected of our lives and environment by the resulting ocean acidification and climate change. To mitigate atmospheric CO2, various strategies have been implemented for CO2 separation, capture, storage and use as a chemical feedstock. The use of CO2 in various chemical industries is attractive as its non-flammable, non-toxic, and relatively inert properties have made it an inherently safer alternative to traditional organic solvents, as well as, a greener carbon feedstock. Also, the accessible critical properties, appreciable critical density, high diffusivity and tunable thermophysical properties make liquid and supercritical CO2 an attractive solvent for industrial applications. In recent years, significant progress has been made in the field of tunable solvent media by employing the reversible reaction of CO2 with amines to produce carbamates. This class of compounds possesses ionic properties that are significantly different from their amines resulting in a non-ionic to ionic switching mechanism that provides for switchable solvent properties, reversible surfactants, low molecular weight organogelators and stimuli responsive materials. The focus of this dissertation is therefore the implementation of the reversible CO2—amine reaction for the formation of smart surfaces, greener amine protection mechanisms, and cationic metallic nanoparticle synthesis. Chapter 2 of this dissertation demonstrates the reversible reaction of CO2 with amine-containing self-assembled monolayers to yield "smart" surfaces that undergo a reversible change in structure, charge, and wettability upon reaction with CO2. The formation carbamate esters are also a widely implemented mechanism for amine protection during organic synthesis. However, traditional methods of protection incur increased solvent use and

  12. An investigation of the relationships between rate and driving force in simple uncatalysed and enzyme-catalysed reactions with applications of the findings to chemiosmotic reactions.

    PubMed Central

    Stoner, C D

    1992-01-01

    Both the rate and the driving force of a reaction can be expressed in terms of the concentrations of the reactants and products. Consequently, rate and driving force can be expressed as a function of each other. This has been done for a single-reactant, single-product, uncatalysed reaction and its enzyme-catalysed equivalent using the van't Hoff reaction isotherm and Haldane's generalized Michaelis-Menten rate equation, the primary objective being explanation of the exponential and sigmoidal relationships between reaction rate and delta mu H+ commonly observed in studies on chemiosmotic reactions. Acquisition of a purely thermodynamic rate vs. driving-force relationship requires recognition of the intensive and extensive variables and maintenance of the extensive variables constant. This relationship is identical for the two reactions and is hyperbolic or sigmoidal, depending on whether the equilibrium constant is smaller or larger than unity. In the case of the catalysed reaction, acquisition of the purely thermodynamic relationship requires the assumption that the enzyme be equally effective in catalysing the forward and backward reactions. If this condition is not met, the relationship is modified by the enzyme in a manner which can be determined from the ratio of the Michaelis constants of the reactant and product. Under conditions of enzyme saturation in respect to reactant+product, the rate vs. driving-force relationship is determined exclusively by the thermodynamics of the reaction and a single kinetic parameter, the magnitude of which is determined by the relative effectiveness of the enzyme in catalysing the forward and backward reactions. In view of this finding, it is pointed out that, since the catalytic components of chemiosmotic reactions appear to be saturated with respect to the reactant-product pair that is varied in experimental rate vs. delta mu H+ determinations, and that, since many complex enzymic reactions conform to the simple Michaelis

  13. Single-walled carbon nanotubes as nano-electrode and nano-reactor to control the pathways of a redox reaction.

    PubMed

    McSweeney, Robert L; Chamberlain, Thomas W; Davies, E Stephen; Khlobystov, Andrei N

    2014-11-28

    Single-walled carbon nanotubes have been demonstrated as effective nanoscale containers for a redox active organometallic complex Cp(Me)Mn(CO)3, acting simultaneously as nano-electrode and nano-reactor. Extreme spatial confinement of the redox reaction within the nanotubes changes its pathway compared to bulk solution due to stabilisation of a reactive intermediate.

  14. Transporting and shielding photosensitisers by using water-soluble organometallic cages: a new strategy in drug delivery and photodynamic therapy.

    PubMed

    Therrien, Bruno

    2013-06-24

    Skin photosensitivity remains one of the main limitations in photodynamic therapy. In this Concept article a strategy to overcome this limitation is described, in which the photosensitizer is hidden inside the hydrophobic cavity of a water-soluble organometallic cage. The metallacage not only protects the photosensitizer from light, it also facilitates its delivery to cancer cells.

  15. Physiology, Biochemistry, and Applications of F420- and Fo-Dependent Redox Reactions.

    PubMed

    Greening, Chris; Ahmed, F Hafna; Mohamed, A Elaaf; Lee, Brendon M; Pandey, Gunjan; Warden, Andrew C; Scott, Colin; Oakeshott, John G; Taylor, Matthew C; Jackson, Colin J

    2016-06-01

    5-Deazaflavin cofactors enhance the metabolic flexibility of microorganisms by catalyzing a wide range of challenging enzymatic redox reactions. While structurally similar to riboflavin, 5-deazaflavins have distinctive and biologically useful electrochemical and photochemical properties as a result of the substitution of N-5 of the isoalloxazine ring for a carbon. 8-Hydroxy-5-deazaflavin (Fo) appears to be used for a single function: as a light-harvesting chromophore for DNA photolyases across the three domains of life. In contrast, its oligoglutamyl derivative F420 is a taxonomically restricted but functionally versatile cofactor that facilitates many low-potential two-electron redox reactions. It serves as an essential catabolic cofactor in methanogenic, sulfate-reducing, and likely methanotrophic archaea. It also transforms a wide range of exogenous substrates and endogenous metabolites in aerobic actinobacteria, for example mycobacteria and streptomycetes. In this review, we discuss the physiological roles of F420 in microorganisms and the biochemistry of the various oxidoreductases that mediate these roles. Particular focus is placed on the central roles of F420 in methanogenic archaea in processes such as substrate oxidation, C1 pathways, respiration, and oxygen detoxification. We also describe how two F420-dependent oxidoreductase superfamilies mediate many environmentally and medically important reactions in bacteria, including biosynthesis of tetracycline and pyrrolobenzodiazepine antibiotics by streptomycetes, activation of the prodrugs pretomanid and delamanid by Mycobacterium tuberculosis, and degradation of environmental contaminants such as picrate, aflatoxin, and malachite green. The biosynthesis pathways of Fo and F420 are also detailed. We conclude by considering opportunities to exploit deazaflavin-dependent processes in tuberculosis treatment, methane mitigation, bioremediation, and industrial biocatalysis.

  16. Application of polymerase chain reaction (PCR) for diagnosis of equine herpes virus-1 (EHV-1).

    PubMed

    Gupta, A K; Singh, B K; Yadav, M P

    1996-11-01

    Fifty aborted foetus samples were diagnosed for the presence of equine herpes virus-1 (EHV-1) by polymerase chain reaction (PCR) technique. Specific primer pair for amplification of a particular segment of EHV-1 DNA in gc region having 3 Hae III restriction endonuclease sites was used. A 409 base pair segment obtained as PCR amplification product in 9 samples was digested with Hae III to confirm the presence of EHV-1 as the infectious agent in aborted tissues. It was observed that PCR technique was more sensitive, specific and rapid than the conventional virological diagnostic methods.

  17. Anaphylactic reaction after systemic application of aprotinin triggered by aprotinin-containing fibrin sealant.

    PubMed

    Kober, Benjamin J; Scheule, Albertus M; Voth, Vladimir; Deschner, Norbert; Schmid, Eckhard; Ziemer, Gerhard

    2008-08-01

    We report a 67-yr-old male after multiple surgical procedures for treatment of arterial occlusive disease who suffered an anaphylactic reaction after administration of aprotinin (Trasylol) prior to urgent coronary artery bypass surgery. The patient had been treated with aprotinin-containing fibrin sealant in 2004 and in 2007, 2 wk before coronary artery bypass surgery. The postoperative serologic screening revealed positive results for qualitative aprotinin-specific IgG, highly elevated quantitative aprotinin-specific IgG and moderately elevated aprotinin-specific IgE antibodies.

  18. Application of artificial neural networks and DFT-based parameters for prediction of reaction kinetics of ethylbenzene dehydrogenase

    NASA Astrophysics Data System (ADS)

    Szaleniec, Maciej; Witko, Małgorzata; Tadeusiewicz, Ryszard; Goclon, Jakub

    2006-03-01

    Artificial neural networks (ANNs) are used for classification and prediction of enzymatic activity of ethylbenzene dehydrogenase from EbN1 Azoarcus sp. bacterium. Ethylbenzene dehydrogenase (EBDH) catalyzes stereo-specific oxidation of ethylbenzene and its derivates to alcohols, which find its application as building blocks in pharmaceutical industry. ANN systems are trained based on theoretical variables derived from Density Functional Theory (DFT) modeling, topological descriptors, and kinetic parameters measured with developed spectrophotometric assay. Obtained models exhibit high degree of accuracy (100% of correct classifications, correlation between predicted and experimental values of reaction rates on the 0.97 level). The applicability of ANNs is demonstrated as useful tool for the prediction of biochemical enzyme activity of new substrates basing only on quantum chemical calculations and simple structural characteristics. Multi Linear Regression and Molecular Field Analysis (MFA) are used in order to compare robustness of ANN and both classical and 3D-quantitative structure-activity relationship (QSAR) approaches.

  19. Parallel reaction monitoring using quadrupole-Orbitrap mass spectrometer: Principle and applications.

    PubMed

    Bourmaud, Adele; Gallien, Sebastien; Domon, Bruno

    2016-08-01

    Targeted mass spectrometry-based approaches are nowadays widely used for quantitative proteomics studies and more recently have been implemented on high resolution/accurate mass (HRAM) instruments resulting in a considerable performance improvement. More specifically, the parallel reaction monitoring technique (PRM) performed on quadrupole-Orbitrap mass spectrometers, leveraging the high resolution and trapping capabilities of the instrument, offers a clear advantage over the conventional selected reaction monitoring (SRM) measurements executed on triple quadrupole instruments. Analyses performed in HRAM mode allow for an improved discrimination between signals derived from analytes and those resulting from matrix interferences translating in the reliable quantification of low abundance components. The purpose of the study defines various implementation schemes of PRM, namely: (i) exploratory experiments assessing the detectability of very large sets of peptides (100-1000), (ii) wide-screen analyses using (crude) internal standards to obtain statistically meaningful (relative) quantitative analyses, and (iii) precise/accurate quantification of a limited number of analytes using calibrated internal standards. Each of the three implementation schemes requires specific acquisition methods with defined parameters to appropriately control the acquisition during the actual peptide elution. This tutorial describes the different PRM approaches and discusses their benefits and limitations in terms of quantification performance and confidence in analyte identification.

  20. Theory of multichannel thermal unimolecular reactions. 2. Application to the thermal dissociation of formaldehyde.

    PubMed

    Troe, J

    2005-09-22

    The thermal dissociation of formaldehyde proceeds on three channels, the molecular-elimination channel H2CO --> H2 + CO (1), the radical-forming bond-fission channel H2CO --> H + HCO (2), and the bond-fission-initiated, intramolecular-hydrogen-abstraction channel H2CO --> H...HCO --> H2 + CO (3) which also forms molecular products. The kinetics of this system in the low-pressure range of the unimolecular reaction is shown to be governed by a subtle superposition of collisional channel coupling to be treated by solving a master equation, of rotational channel switching accessible through ab initio calculations of the potential as well as spectroscopic and photophysical determinations of the threshold energies and channel branching above the threshold energy for radical formation which can be characterized through formaldehyde photolysis quantum yields as well as classical trajectory calculations. On the basis of the available information, the rate coefficients for the formation of molecular and radical fragments are analyzed and extrapolated over wide ranges of conditions. The modeled rate coefficients in the low-pressure range of the reaction (neglecting tunneling) over the range 1400-3200 K in the bath-gas Ar in this way are represented by k0,Mol/[Ar] approximately 9.4 x 10(-9) exp(-33,140 K/T) cm3 molecule(-1) s(-1) and k0,Rad/[Ar] approximately 6.2 x 10(-9) exp(-36,980 K/T) cm3 molecule(-1) s(-1). The corresponding values for the bath-gas Kr, on which the analysis relies in particular, are k0,Mol/[Kr] approximately 7.7 x 10(-9) exp(-33,110 K/T) and k0,Rad/[Kr] approximately 4.1 x 10(-9) exp(-36 910 K/T) cm3 molecule(-1) s(-1). While the threshold energy E0,2 for channels 2 and 3 is taken from spectroscopic measurements, the threshold energy E0,1 for channel 1 is fitted on the basis of experimental ratios k0,Rad/k0,Mol in combination with photolysis quantum yields. The derived value of E0,1(1) = 81.2 (+/-0.9) kcal mol(-1) is in good agreement with results from

  1. Interfacial Reaction Studies Using ONIOM

    NASA Technical Reports Server (NTRS)

    Cardelino, Beatriz H.

    2003-01-01

    In this report, we focus on the calculations of the energetics and chemical kinetics of heterogeneous reactions for Organometallic vapor phase epitaxy (OMVPE). The work described in this report builds upon our own previous thermochemical and chemical kinetics studies. The first of these articles refers to the prediction of thermochemical properties, and the latter one deals with the prediction of rate constants for gaseous homolytic dissociation reactions. The calculations of this investigation are at the microscopic level. The systems chosen consisted of a gallium nitride (GaN) substrate, and molecular nitrogen (N2) and ammonia (NH3) as adsorbants. The energetics for the adsorption and the adsorbant dissociation processes were estimated, and reaction rate constants for the dissociation reactions of free and adsorbed molecules were predicted. The energetics for substrate decomposition was also computed. The ONIOM method, implemented in the Gaussian98 program, was used to perform the calculations. This approach has been selected since it allows dividing the system into two layers that can be treated at different levels of accuracy. The atoms of the substrate were modeled using molecular mechanics6 with universal force fields, whereas the adsorbed molecules were approximated using quantum mechanics, based on density functional theory methods with B3LYP functionals and 6-311G(d,p) basis sets. Calculations for the substrate were performed in slabs of several unit cells in each direction. The N2 and NH3 adsorbates were attached to a central location at the Ga-lined surface.

  2. [The application of the polymerase chain reaction technic for the detection of human papillomavirus sequences].

    PubMed

    Soto, Y; Muné, M; Goicolea, A; Morales, E; Santoyo, J M; Valdés, O; Ramírez, R; Pimentel, T

    1998-01-01

    The polymerase chain reaction technique was applied to detect sequences of human Papillomavirus (HPV) by controls of cellular lines of cervical cancer and of tissues obtained through biopsy with a HPV-positive clinical diagnosis. A set of consensus oligonucleotides, which are complementary to a highly conserved region within the open reading frame E1 of the viral genome of HPV affecting the cervical mucosa, was used. With these primers it was possible to amplify DNA sequences corresponding to HPV 6 and 11, considered in the low risk group, and to HPV 16, 18, 31 and 33, included in the high risk group. The study of the sensitivity of the amplification technique showed a level of detection of 3,5 viral particles per each cellular diploid genome.

  3. [Color reaction of chromogenic reagent O-hydroxybenzenediazoaminoazobenzene with thallium (III) and its application].

    PubMed

    Cao, X; Chen, Y; Zhou, H; Fang, D

    2001-06-01

    The chromogenic reaction of the O-hydroxybenzenediazoaminoazobenzene (O-HDAA) with thallium was studied in this paper. In the presence of Triton X-100 and SDBS and in ammonia medium of 0.54-1.1 mol.L-1, O-HDAA reacts with thallium (III) to form a stable red complex with molar radio of 1:5. The apparent molar absorptivity is 1.4 x 10(5) L.mol-1.cm-1 at the maximum absorption wavelength of 520 nm. Beer's law is obeyed in the concentration range of 0-600 micrograms.L-1 Tl(III). The method has been applied to the direct determination of trace amounts of thallium in waste water and in geological samples by using polyurethane foam to absorb and separate Tl(III) with satisfactory results.

  4. A Gas-Kinetic Scheme for Multimaterial Flows and Its Application in Chemical Reaction

    NASA Technical Reports Server (NTRS)

    Lian, Yongsheng; Xu, Kun

    1999-01-01

    This paper concerns the extension of the multicomponent gas-kinetic BGK-type scheme to multidimensional chemical reactive flow calculations. In the kinetic model, each component satisfies its individual gas-kinetic BGK equation and the equilibrium states of both components are coupled in space and time due to the momentum and energy exchange in the course of particle collisions. At the same time, according to the chemical reaction rule one component can be changed into another component with the release of energy, where the reactant and product could have different gamma. Many numerical test cases are included in this paper, which show the robustness and accuracy of kinetic approach in the description of multicomponent reactive flows.

  5. Silver nanoparticle-initiated chemiluminescence reaction of luminol-AgNO3 and its analytical application.

    PubMed

    Liu, Cui; Li, Baoxin

    2011-07-01

    Ag(+) has been regarded as an inert chemiluminescent oxidant. In this work, it was found that in the presence of silver nanoparticles (AgNPs), AgNO(3) could react with luminol to produce strong chemiluminescence (CL). The AgNPs with smaller size could initiate stronger CL emission. To investigate the CL mechanism of the AgNPs-luminol-AgNO(3) system, the UV-visible spectra and the CL spectrum of the CL system were obtained. The CL reaction mechanism involving catalysis was proposed. Compared with the reported nanoparticles-luminol-H(2)O(2) CL system, the AgNPs-luminol-AgNO(3) CL system has the advantages of low background and good stability. Moreover, the new CL system was used in immunoassay for IgG.

  6. Nonlinear phenomena at geological reaction fronts with energy applications. Final report

    SciTech Connect

    Ortoleva, P.

    1989-12-31

    Interaction of aqueous fluids with the rock matrix within which they reside can yield a variety of phenomena due to the coupling of reaction transport and mechanical processes; many of these have potentially important implications for exploration and exploitation of energy and mineral resources. We investigated effects of nucleation to produce banded precipitation; Darcy-mineral dissolution coupling to produce scalloped, fingered and more complex alteration front morphologies, and diagenetic alteration in chemically complex, multi-mineralic systems. Migration of methane driven by buoyancy effects was shown to lead to cellular and temporally oscillatory flows. Sandstones at depth experiencing pressure solution display unstable compaction leading to formation of stylolites and band-like regions of augmented compaction alternating with low porosity bands with augmented overgrowth. It was shown that transfer of natural gas from shale source rock into neighboring sandstones could occur through a series of discrete pulsatile events through a cycle of fracturing and healing.

  7. Kinetic and Reaction Pathway Analysis in the Application of Botulinum Toxin A for Wound Healing

    PubMed Central

    Lebeda, Frank J.; Dembek, Zygmunt F.; Adler, Michael

    2012-01-01

    A relatively new approach in the treatment of specific wounds in animal models and in patients with type A botulinum toxin is the focus of this paper. The indications or conditions include traumatic wounds (experimental and clinical), surgical (incision) wounds, and wounds such as fissures and ulcers that are signs/symptoms of disease or other processes. An objective was to conduct systematic literature searches and take note of the reactions involved in the healing process and identify corresponding pharmacokinetic data. From several case reports, we developed a qualitative model of how botulinum toxin disrupts the vicious cycle of muscle spasm, pain, inflammation, decreased blood flow, and ischemia. We transformed this model into a minimal kinetic scheme for healing chronic wounds. The model helped us to estimate the rate of decline of this toxin's therapeutic effect by calculating the rate of recurrence of clinical symptoms after a wound-healing treatment with this neurotoxin. PMID:22174710

  8. Application of isochronous mass spectrometry for the study of angular momentum population in projectile fragmentation reactions

    NASA Astrophysics Data System (ADS)

    Tu, X. L.; Kelić-Heil, A.; Litvinov, Yu. A.; Podolyák, Zs.; Zhang, Y. H.; Huang, W. J.; Xu, H. S.; Blaum, K.; Bosch, F.; Chen, R. J.; Chen, X. C.; Fu, C. Y.; Gao, B. S.; Ge, Z.; Hu, Z. G.; Liu, D. W.; Litvinov, S. A.; Ma, X. W.; Mao, R. S.; Mei, B.; Shuai, P.; Sun, B. H.; Sun, Y.; Sun, Z. Y.; Walker, P. M.; Wang, M.; Winckler, N.; Xia, J. W.; Xiao, G. Q.; Xing, Y. M.; Xu, X.; Yamaguchi, T.; Yan, X. L.; Yang, J. C.; Yuan, Y. J.; Zeng, Q.; Zhang, W.; Zhao, H. W.; Zhao, T. C.; Zhou, X. H.

    2017-01-01

    Isochronous mass spectrometry was applied to measure isomeric yield ratios of fragmentation reaction products. This approach is complementary to conventional γ -ray spectroscopy in particular for measuring yield ratios for long-lived isomeric states. Isomeric yield ratios for the high-spin I =19 /2 ℏ states in the mirror nuclei 53Fe and 53Co are measured to study angular momentum population following the projectile fragmentation of 78Kr at energies of ˜480 A MeV on a beryllium target. The 19/2 state isomeric ratios of 53Fe produced from different projectiles in the literature have also been extracted as a function of mass number difference between projectile and fragment (mass loss). The results are compared to abrabla07 model calculations. The isomeric ratios of 53Fe produced using different projectiles suggest that the theory underestimates not only the previously reported dependence on the spin but also the dependence on the mass loss.

  9. Principles and applications of polymerase chain reaction in medical diagnostic fields: a review

    PubMed Central

    Valones, Marcela Agne Alves; Guimarães, Rafael Lima; Brandão, Lucas André Cavalcanti; de Souza, Paulo Roberto Eleutério; de Albuquerque Tavares Carvalho, Alessandra; Crovela, Sergio

    2009-01-01

    Recent developments in molecular methods have revolutionized the detection and characterization of microorganisms in a broad range of medical diagnostic fields, including virology, mycology, parasitology, microbiology and dentistry. Among these methods, Polymerase Chain Reaction (PCR) has generated great benefits and allowed scientific advancements. PCR is an excellent technique for the rapid detection of pathogens, including those difficult to culture. Along with conventional PCR techniques, Real-Time PCR has emerged as a technological innovation and is playing an ever-increasing role in clinical diagnostics and research laboratories. Due to its capacity to generate both qualitative and quantitative results, Real-Time PCR is considered a fast and accurate platform. The aim of the present literature review is to explore the clinical usefulness and potential of both conventional PCR and Real-Time PCR assays in diverse medical fields, addressing its main uses and advances. PMID:24031310

  10. Applications of Transport/Reaction Codes to Problems in Cell Modeling

    SciTech Connect

    MEANS, SHAWN A.; RINTOUL, MARK DANIEL; SHADID, JOHN N.

    2001-11-01

    We demonstrate two specific examples that show how our exiting capabilities in solving large systems of partial differential equations associated with transport/reaction systems can be easily applied to outstanding problems in computational biology. First, we examine a three-dimensional model for calcium wave propagation in a Xenopus Laevis frog egg and verify that a proposed model for the distribution of calcium release sites agrees with experimental results as a function of both space and time. Next, we create a model of the neuron's terminus based on experimental observations and show that the sodium-calcium exchanger is not the route of sodium's modulation of neurotransmitter release. These state-of-the-art simulations were performed on massively parallel platforms and required almost no modification of existing Sandia codes.

  11. Study of the 11 B(p,p‧ γ) 11 B reaction for PIGE applications

    NASA Astrophysics Data System (ADS)

    Preketes-Sigalas, K.; Lagoyannis, A.; Axiotis, M.; Harissopulos, S.; Kokkoris, M.; Mertzimekis, T. J.; Paneta, V.; Provatas, G.

    2016-02-01

    The differential cross sections of the 2125 keV γ -ray, emitted by the 11 B(p,p‧ γ) 11 B reaction were measured at six (6) angles and at proton energies from 2.5 to 5.0 MeV. The experimental setup consisted of three (3) 100% relative efficiency HPGe detectors placed on a motorized turntable. The comparison between the present measurements, which have an overall uncertainty of ∼ 8%, and previous ones from literature gives contradictory results. While there are large differences with previous differential cross-section measurements from literature, there is good agreement with previous thick-target yield ones. Additional thick-target measurements were performed in an effort to explain the observed discrepancies.

  12. Ammonium transport and reaction in contaminated groundwater: Application of isotope tracers and isotope fractionation studies

    USGS Publications Warehouse

    Böhlke, J.K.; Smith, R.L.; Miller, D.N.

    2006-01-01

    Ammonium (NH4+) is a major constituent of many contaminated groundwaters, but its movement through aquifers is complex and poorly documented. In this study, processes affecting NH4+ movement in a treated wastewater plume were studied by a combination of techniques including large-scale monitoring of NH4+ distribution; isotopic analyses of coexisting aqueous NH4+, NO3-, N2, and sorbed NH 4+; and in situ natural gradient 15NH 4+ tracer tests with numerical simulations of 15NH4+, 15NO3-, and 15N2 breakthrough data. Combined results indicate that the main mass of NH4+ was moving downgradient at a rate about 0.25 times the groundwater velocity. Retardation factors and groundwater ages indicate that much of the NH4+ in the plume was recharged early in the history of the wastewater disposal. NO3- and excess N2 gas, which were related to each other by denitrification near the plume source, were moving downgradient more rapidly and were largely unrelated to coexisting NH 4+. The ??15N data indicate areas of the plume affected by nitrification (substantial isotope fractionation) and sorption (no isotope fractionation). There was no conclusive evidence for NH 4+-consuming reactions (nitrification or anammox) in the anoxic core of the plume. Nitrification occurred along the upper boundary of the plume but was limited by a low rate of transverse dispersive mixing of wastewater NH4+ and O2 from overlying uncontaminated groundwater. Without induced vertical mixing or displacement of plume water with oxic groundwater from upgradient sources, the main mass of NH4+ could reach a discharge area without substantial reaction long after the more mobile wastewater constituents are gone. Multiple approaches including in situ isotopic tracers and fractionation studies provided critical information about processes affecting NH4+ movement and N speciation.

  13. Development and application of the Model of Aerosol Dynamics, Reaction, Ionization, and Dissolution (MADRID)

    NASA Astrophysics Data System (ADS)

    Zhang, Yang; Pun, Betty; Vijayaraghavan, Krish; Wu, Shiang-Yuh; Seigneur, Christian; Pandis, Spyros N.; Jacobson, Mark Z.; Nenes, Athanasios; Seinfeld, John H.

    2004-01-01

    A new aerosol model, the Model of Aerosol Dynamics, Reaction, Ionization, and Dissolution (MADRID) has been developed to simulate atmospheric particulate matter (PM). MADRID and the Carnegie-Mellon University (CMU) bulk aqueous-phase chemistry have been incorporated into the three-dimensional Models-3/Community Multiscale Air Quality model (CMAQ). The resulting model, CMAQ-MADRID, is applied to simulate the August 1987 episode in the Los Angeles basin. Model performance for ozone and PM is consistent with current performance standards. However, organic aerosol was underpredicted at most sites owing to underestimation of primary organic PM emissions and secondary organic aerosol (SOA) formation. Nitrate concentrations were also sometimes underpredicted, mainly owing to overpredictions in vertical mixing, underpredictions in relative humidity, and uncertainties in the emissions of primary pollutants. Including heterogeneous reactions changed hourly O3 by up to 17% and 24-hour average PM2.5, sulfate2.5, and nitrate2.5 concentrations by up to 3, 7, and 19%, respectively. A SOA module with a mechanistic representation provides results that are more consistent with observations than that with an empirical representation. The moving-center scheme for particle growth predicts more accurate size distributions than a typical semi-Lagrangian scheme, which causes an upstream numerical diffusion. A hybrid approach that simulates dynamic mass transfer for coarse PM but assumes equilibrium for fine PM can predict a realistic particle size distribution under most conditions, and the same applies under conditions with insignificant concentrations of reactive coarse particles to a bulk equilibrium approach that allocates transferred mass to different size sections based on condensational growth law. In contrast, a simple bulk equilibrium approach that allocates transferred mass based on a given distribution tends to cause a downstream numerical diffusion in the predicted particle

  14. Neutrality condition and response law for nonlinear reaction-diffusion equations, with application to population genetics

    NASA Astrophysics Data System (ADS)

    Vlad, Marcel Ovidiu; Moran, Federico; Tsuchiya, Masa; Cavalli-Sforza, L. Luca; Oefner, Peter J.; Ross, John

    2002-06-01

    We study a general class of nonlinear macroscopic evolution equations with ``transport'' and ``reaction'' terms which describe the dynamics of a species of moving individuals (atoms, molecules, quasiparticles, organisms, etc.). We consider that two types of individuals exist, ``not marked'' and ``marked,'' respectively. We assume that the concentrations of both types of individuals are measurable and that they obey a neutrality condition, that is, the kinetic and transport properties of the ``not marked'' and ``marked'' individuals are identical. We suggest a response experiment, which consists in varying the fraction of ``marked'' individuals with the preservation of total fluxes, and show that the response of the system can be represented by a linear superposition law even though the underlying dynamics of the system is in general highly nonlinear. The linear response law is valid even for large perturbations and is not the result of a linearization procedure but rather a necessary consequence of the neutrality condition. First, we apply the response theorem to chemical kinetics, where the ``marked species'' is a molecule labeled with a radioactive isotope and there is no kinetic isotope effect. The susceptibility function of the response law can be related to the reaction mechanism of the process. Secondly we study the geographical distribution of the nonrecurrent, nonreversible neutral mutations of the nonrecombining portion of the Y chromosome from human populations and show that the fraction of mutants at a given point in space and time obeys a linear response law of the type introduced in this paper. The theory may be used for evaluating the geographic position and the moment in time where and when a mutation originated.

  15. Application of the Ugi four-component reaction to the synthesis of ditopic bifunctional chelating agents.

    PubMed

    Tei, Lorenzo; Gugliotta, Giuseppe; Avedano, Stefano; Giovenzana, Giovanni B; Botta, Mauro

    2009-11-07

    The Ugi four-component reaction (Ugi 4CR) was exploited for the first time to obtain in a single synthetic step bifunctional ditopic chelators by using DOTA monoamide (DOTAMA) derivatives as amino and acid components. A number of ditopic systems in which the two DOTAMA units are connected by a central alpha-acylaminoamide group were synthesized by reacting different aldehydes, isocyanides and two DOTAMA chelates containing amino and acid functionalities. Variation of the components allows the insertion of another functional group into the alpha-acylaminoamide skeleton for further conjugation to biomolecules. The optimal reaction conditions were found by using methanol as solvent and ultrasound irradiation at a power of 60 W (20 kHz) for 3 h. The Gd(III) complexes of the dimeric ligands L1 and L2 (bearing a cyclohexyl ring and an octadecyl chain on the central alpha-acylaminoamide moiety, respectively) were fully characterized in aqueous media by relaxometric techniques with varying temperature and magnetic field strength. The relaxivity of Gd(2)L1 and Gd(2)L2 (in the aggregated form), at 20 MHz and 310 K, are 5.6 and 20.0 mM(-1) s(-1), respectively. The enhanced value found for Gd(2)L2 indicates that this lipophilic complex forms micelles at concentrations <0.1 mM. Finally, the binding of Gd(2)L2 to human serum albumin (HSA) was investigated by proton relaxometry, and the affinity constant of the complex and the relaxivity of the macromolecular adduct (r(1p)(b) = 38.1 mM(-1) s(-1); 20 MHz and 310 K) derived.

  16. Stepwise formation of organometallic macrocycles and triangular prisms containing 2,2'-bisbenzimidazole ligands.

    PubMed

    Wu, Tong; Lin, Yue-Jian; Jin, Guo-Xin

    2013-01-07

    A series of organometallic macrocycles have been constructed by an efficient “bottom-up” assembly methodology at ambient temperature. Treatment of [Cp*MCl2]2 (1a: M = Ir, 1b: M = Rh) with pyrazine or 4,4′-bipyridine (bpy) (1:1; Cp* = pentamethylcyclopentadienyl) at room temperature resulted in the formation of binuclear complexes [Cp*MCl2]2(pyrazine) and [Cp*MCl2]2(bpy) (M = Ir or Rh), which were then further reacted with AgOTf (Tf = O2SCF3) and 2,2′-bisbenzimidazole ligand (BiBzIm). Four organometallic macrocyclic complexes formulated as [Cp*4Ir4(BiBzIm)2(pyrazine)2](OTf)4 (2a), [Cp*4Rh4(BiBzIm)2(pyrazine)2](OTf)4 (2b), [Cp*4Ir4(BiBzIm)2(bpy)2](OTf)4 (2c) and [Cp*4Rh4(BiBzIm)2(bpy)2](OTf)4 (2d) each bearing 2,2′-bisbenzimidazole ligand and the half-sandwich Ir, Rh fragments were finally obtained in good yields. In a similar process, if a rigid ligand L (3-pyridyl-bian) was used as the linker, two novel metallacycles (3a and 3b) which enchased a silver atom in the centre were obtained. Organometallic triangular prisms 4a were synthesized via methods similar to those of the rectangles. [Cp*IrCl2]2 reacted with tridentate ligand 2,4,6-tri(4-pyridyl)-1,3,5-triazine (tpt) to give the corresponding trinuclear complexes [Cp*IrCl2]3(tpt), then further reacted with AgOTf and 2,2′-bisbenzimidazole ligand, leading to the formation of the prism-like complexes formulated as [Cp*6M6(BiBzIm)6(tpt)2](OTf)6 (3a: M = Ir, 3b: M = Rh). All complexes were well characterized by 1H NMR and IR spectroscopy, as well as elemental analyses. The molecular structures of 2a, 2b, 2c, 3a, 3b and 4a were characterized by single-crystal X-ray crystallography. We found that the prism-like hexanuclear complexes 4a displayed interesting host–guest chemistry.

  17. Infrared Reflective Filter and Its Applications

    NASA Astrophysics Data System (ADS)

    Honda, Kiyokazu; Ishizaki, Ariyoshi; Yuge, Youji; Saitoh, Tokuyoshi

    1983-12-01

    A thin film, which reflects infra-red ray while transmits visible light, is discussed in a background of energy saving incandescent lamps. The film which consists of multi-layer Ti02-Si02 film reflects infra-red ray effectively and has a high heat resistance. This film is formed from organometallic solutions by dipping method. In order to carry out multi-layer coatings, the organometallic solutions are improved. A film on a substrate turns into a metalic oxide film having desired optical thickness and refractive index. The optical properties of this film and its application to tubular tungsten halogen lamps are discussed in this paper.

  18. Ignition delays, heats of combustion, and reaction rates of aluminum alkyl derivatives used as ignition and combustion enhancers for supersonic combustion

    NASA Technical Reports Server (NTRS)

    Ryan, Thomas W., III; Schwab, S. T.; Harlowe, W. W.

    1992-01-01

    The subject of this paper is the design of supersonic combustors which will be required in order to achieve the needed reaction rates in a reasonable sized combustor. A fuel additive approach, which is the focus of this research, is the use of pyrophorics to shorten the ignition delay time and to increase the energy density of the fuel. Pyrophoric organometallic compounds may also provide an ignition source and flame stabilization mechanism within the combustor, thus permitting use of hydrocarbon fuels in supersonic combustion systems. Triethylaluminum (TEA) and trimethylaluminum (TMA) were suggested for this application due to their high energy density and reactivity. The objective here is to provide comparative data for the ignition quality, the energy content, and the reaction rates of several different adducts of both TEA and TMA. The results of the experiments indicate the aluminum alkyls and their more stable derivatives reduce the ignition delay and total reaction time to JP-10 jet fuel. Furthermore, the temperature dependence of ignition delay and total reaction time of the blends of the adducts are significantly lower than in neat JP-10.

  19. Pressure-driven fast reaction and recovery of peptide receptor for an electronic nose application

    SciTech Connect

    Yoo, Yong Kyoung; Lee, Sang-Myung; Chae, Myung-Sic; Yoon Kang, Ji; Song Kim, Tae; Seon Hwang, Kyo E-mail: jhlee@kw.ac.kr; Hoon Lee, Jeong E-mail: jhlee@kw.ac.kr

    2014-02-24

    Combining a highly sensitive sensor platform with highly selective recognition elements is essential for micro/nanotechnology-based electronic nose applications. Particularly, the regeneration sensor surface and its conditions are key issues for practical e-nose applications. We propose a highly sensitive piezoelectric-driven microcantilever array chip with highly selective peptide receptors. By utilizing the peptide receptor, which was discovered by a phase display screening process, we immobilized a dinitrotoluene (DNT) specific peptide as well as a DNT nonspecific peptide on the surface of the cantilever array. The delivery of DNT gas via pressure-driven flow led to a greater instant response of ∼30 Hz, compared to diffusion only (∼15 Hz for 15 h). Using a simple pressure-driven air flow of ∼50 sccm, we confirmed that a ratio of ∼70% of the specific-bounded sites from DNT gas molecules could be regenerated, showing re-usability of the peptide receptor in on-site monitoring for electronic nose applications.

  20. A hydrogel pen for electrochemical reaction and its applications for 3D printing

    NASA Astrophysics Data System (ADS)

    Kang, Hosuk; Hwang, Seongpil; Kwak, Juhyoun

    2014-12-01

    A hydrogel pen consisting of a microscopic pyramid containing an electrolyte offers a localized electroactive area on the nanometer scale via controlled contact of the apex with a working electrode. The hydrogel pen merges the fine control of atomic force microscopy with non-linear diffusion of an ultramicroelectrode, producing a faradaic current that depends on the small electroactive area. The theoretical and experimental investigations of the mass transport behavior within the hydrogel reveal that the steady-state current from the faradaic reaction is linearly proportional to the deformed length of the hydrogel pen by contact, i.e. signal transduction of deformation to an electrochemical signal, which enables the fine control of the electroactive area in the nanometer-scale regime. Combined with electrodeposition, localized electrochemistry of the hydrogel pen results in the ability to fabricate small sizes (110 nm in diameter), tall heights (up to 30 μm), and arbitrary structures, thereby indicating an additive process in 3 dimensions by localized electrodeposition.A hydrogel pen consisting of a microscopic pyramid containing an electrolyte offers a localized electroactive area on the nanometer scale via controlled contact of the apex with a working electrode. The hydrogel pen merges the fine control of atomic force microscopy with non-linear diffusion of an ultramicroelectrode, producing a faradaic current that depends on the small electroactive area. The theoretical and experimental investigations of the mass transport behavior within the hydrogel reveal that the steady-state current from the faradaic reaction is linearly proportional to the deformed length of the hydrogel pen by contact, i.e. signal transduction of deformation to an electrochemical signal, which enables the fine control of the electroactive area in the nanometer-scale regime. Combined with electrodeposition, localized electrochemistry of the hydrogel pen results in the ability to fabricate

  1. The Concentration Dependence of the (Delta)s Term in the Gibbs Free Energy Function: Application to Reversible Reactions in Biochemistry

    ERIC Educational Resources Information Center

    Gary, Ronald K.

    2004-01-01

    The concentration dependence of (delta)S term in the Gibbs free energy function is described in relation to its application to reversible reactions in biochemistry. An intuitive and non-mathematical argument for the concentration dependence of the (delta)S term in the Gibbs free energy equation is derived and the applicability of the equation to…

  2. Technomimetic molecules: synthesis of ruthenium(II) 1,2,3,4,5-penta(p-bromophenyl)cyclopentadienyl hydrotris(indazolyl)borate, an organometallic molecular turnstile.

    PubMed

    Carella, Alexandre; Jaud, Jöel; Rapenne, Gwénaël; Launay, Jean-Pierre

    2003-10-07

    A short route to prepare a ruthenium complex with a pentaphenyl substituted cyclopentadienyl and a hydrotris(indazolyl)borate ligand is described: this complex can be seen as an organometallic molecular turnstile.

  3. Microelectrode fabrication by laser direct curing of tiny nanoparticle self-generated from organometallic ink.

    PubMed

    Kang, Bongchul; Ko, Seunghwan; Kim, Jongsu; Yang, Minyang

    2011-01-31

    In this paper, we present a new laser direct patterning method that selectively cures nanoparticles self-generated from organometallic ink by proper thermal decomposition. This approach has several advantages in the curing rate, resolution and pattern quality compared with the conventional nanoparticle ink based direct laser curing method. It was found that a laser wavelength which is more weakly absorbed by the nanoparticles could produce a more stable and homogeneous curing condition. Finally, arbitrary shaped silver electrodes with narrow width and uniform profile could be achieved on a polymer substrate at a high curing rate of 25 mm/s. This process can be applied for flexible electronics fabrications on heat sensitive polymer substrates.

  4. Low oxygen and carbon incorporation in AIGaAs using tritertiarybutylaluminum in organometallic vapor phase epitaxy

    NASA Astrophysics Data System (ADS)

    Wang, C. A.; Salimand, S.; Jensen, K. F.; Jones, A. C.

    1996-05-01

    High-quality AIGaAs epilayers have been grown by low pressure organometallic vapor phase epitaxy with a new aluminum precursor tritertiarybutylaluminum (TTBAl). Layers grown at 650°C have a featureless mirror surface morphology and strong room temperature photoluminescence. Carbon was not detectable in chemical analysis by secondary ion mass spectroscopy, nor in low temperature (4K) photoluminescence spectra. Oxygen concentration in Al0.25Ga0.75As is as low as ˜2-3 × 1017 cm-3. Nominally undoped AIGaAs layers exhibit n-type conductiv-ity with electron concentrations at ˜ 1-1.5 × 1016 cm-3. A high degree of compo-sitional uniformity over 5 cm diam substrates (0.268 ±0.001) was obtained. These results indicate the potential for TTBA1 as an aluminum precursor for low temperature growth of Al-containing III-V alloys.

  5. Quasi-one-dimensional spin-orbit-coupled correlated insulator in a multinuclear coordinated organometallic crystal

    NASA Astrophysics Data System (ADS)

    Merino, J.; Jacko, A. C.; Khosla, A. L.; Powell, B. J.

    2016-11-01

    We show how quasi-one-dimensional correlated insulating states arise at two-thirds filling in organometallic multinuclear coordination complexes described by layered decorated honeycomb lattices. The interplay of spin-orbit coupling and electronic correlations leads to pseudospin-one moments arranged in weakly coupled chains with highly anisotropic exchange and a large trigonal splitting. We show that the in-plane exchange coupling is very different from the interlayer coupling; in particular the latter is much larger, despite the underlying hopping integrals being close to isotropic. Surprisingly, the effective dimensionality of the pseudospin model is strongly dependent on the strength of the electronic correlations: With increasing Hubbard U the pseudospin-one model becomes increasingly one dimensional, even though the crystal is almost isotropic. We predict that the trigonal splitting leads to a quantum phase transition from a Haldane phase to a topologically trivial phase as the relative strength of the spin-orbit coupling increases.

  6. Organometallic Chemical Vapor Deposition of ZrF4-Based Fluoride Glasses

    NASA Astrophysics Data System (ADS)

    Fujiura, Kazuo; Ohishi, Yasutake; Takahashi, Shiro

    1989-01-01

    By organometallic chemical vapor deposition (OMCVD), fluoride glasses in a ZrF4-BaF2 binary system are successfully synthesized. β-Diketone chelates of Zr and Ba as starting materials can be volatilized and completely fluorinated with HF gas into ZrF4-BaF2 compounds. 65 mol%ZrF4-35 mol%BaF2 powder synthesized by OMCVD is identified as homogeneous glass by X-ray diffraction (XRD) and differential scanning calorimetry (DSC). By this method, ZrF4 is also obtained in an amorphous state. The OMCVD is available for preparation of fluoride glass, which is promising for optical fiber.

  7. Femtosecond Time-Resolved Infrared Spectra of Organometallic Complexes Bound to a Dinuclear Metal Center

    NASA Astrophysics Data System (ADS)

    Brown-Xu, Samantha E.; Durr, Christopher B.

    2012-06-01

    Compounds of the form M2L2L'2, where M2 is a quadruply bonded metal center (M = Mo or W) and L and L' are conjugated organic ligands, are known to show interesting photophysical properties and exhibit intense metal-to-ligand charge transfer (MLCT) transitions throughout the visible spectrum. Recently, we have modified one of the ligands to incorporate a transition metal carbonyl complex bound to an organic moiety. Following excitation into the MLCT band, the vibrational modes of the organometallic ligand can be observed by fs time-resolved infrared (TRIR) spectroscopy. This allows for a visualization of where the electron density resides in the excited states, which provides useful information for designing new materials that could later be incorporated into solar devices.

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

    PubMed

    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.

  9. Iron-Catalyzed C-C Cross-Couplings Using Organometallics.

    PubMed

    Guérinot, Amandine; Cossy, Janine

    2016-08-01

    Over the last decades, iron-catalyzed cross-couplings have emerged as an important tool for the formation of C-C bonds. A wide variety of alkenyl, aryl, and alkyl (pseudo)halides have been coupled to organometallic reagents, the most currently used being Grignard reagents. Particular attention has been devoted to the development of iron catalysts for the functionalization of alkyl halides that are generally challenging substrates in classical cross-couplings. The high functional group tolerance of iron-catalyzed cross-couplings has encouraged organic chemists to use them in the synthesis of bioactive compounds. Even if some points remain obscure, numerous studies have been carried out to investigate the mechanism of iron-catalyzed cross-coupling and several hypotheses have been proposed.

  10. Preparation and characterization of barium hexaferrite powders produced by decomposition of organometallic complexes

    SciTech Connect

    Chandrasekhar, R.; Charles, S.W.; O'Grady, K. ); Moerup, S.; van Wonterghem, J. )

    1987-01-01

    Barium hexaferrite (BaFe{sub 12}O{sub 19}) particles have been prepared by the decomposition of an organometallic salt. The properties of the ferrite particles have been investigated by x-ray diffractometry, Moessbauer spectroscopy, scanning electron microscopy, and magnetic measurements. The size of the particles produced lie between 0.1 and 0.5 {mu}m. To form the hexaferrite the decomposition product must be heated to > 620{degree}C. Typical values of the saturation magnetization, coercivity, and remanence ratio of the hexaferrite particles are 333 kA{center dot}m{sup {minus}1} (63 emu/g{sup {minus}1}), 320 kA{center dot}m{sup {minus}1} (4 kOe), and 0.49, respectively.

  11. Non-Noble Metal-based Carbon Composites in Hydrogen Evolution Reaction: Fundamentals to Applications.

    PubMed

    Wang, Jing; Xu, Fan; Jin, Haiyan; Chen, Yiqing; Wang, Yong

    2017-02-24

    Hydrogen has been hailed as a clean and sustainable alternative to finite fossil fuels in many energy systems. Water splitting is an important method for hydrogen production in high purity and large quantities. To accelerate the hydrogen evolution reaction (HER) rate, it is highly necessary to develop high efficiency catalysts and to select a proper electrolyte. Herein, the performances of non-noble metal-based carbon composites under various pH values (acid, alkaline and neutral media) for HER in terms of catalyst synthesis, structure and molecular design are systematically discussed. A detailed analysis of the structure-activity-pH correlations in the HER process gives an insight on the origin of the pH-dependence for HER, and provide guidance for future HER mechanism studies on non-noble metal-based carbon composites. Furthermore, this Review gives a fresh impetus to rational design of high-performance noble-metal-free composites catalysts and guide researchers to employ the established electrocatalysts in proper water electrolysis technologies.

  12. Application of polymerase chain reaction based on ITS1 rDNA to speciate Eimeria.

    PubMed

    Jenkins, M C; Miska, K; Klopp, S

    2006-03-01

    A method was developed to recover Eimeria spp. oocysts directly from poultry litter and determine which species of Eimeria were present using polymerase chain reaction (PCR) based on the ITS1 rDNA sequence. The species composition of Eimeria oocysts was also compared before and after propagation in susceptible chickens to determine if the relative proportion of each species changed after expansion. In samples from two broiler operations, ITS1-PCR was able to detect Eimeria spp. oocysts recovered from litter, with Eimeria acervulina, Eimeria maxima, and Eimeria praecox being the predominant species present therein. Although Eimeria tenella was found in one sample, the other species--Eimeria brunetti, Eimeria necatrix, and Eimeria mitis-were not detected. The species composition as determined by ITS1-PCR did not appear to appreciably alter after expansion in susceptible chickens. The described method represents a rapid means for determining the major Eimeria species in a poultry operation and may be helpful in choosing a particular live oocyst vaccine formulation to protect chickens against coccidiosis.

  13. Routine application of the polymerase chain reaction for detection of Mycobacterium tuberculosis in clinical samples.

    PubMed Central

    Noordhoek, G T; Kaan, J A; Mulder, S; Wilke, H; Kolk, A H

    1995-01-01

    AIM--To investigate the use of the polymerase chain reaction (PCR) in the routine laboratory for the detection of Mycobacterium tuberculosis in clinical samples. METHODS--Samples were divided and processed separately for the detection of M tuberculosis by microscopy, culture and PCR. After DNA extraction, PCR was performed with primers specific for the insertion element IS6110 and the product was analysed by agarose gel electrophoresis, Southern blotting or dot blotting and hybridisation with a digoxigenin labelled internal probe. Each sample was tested for inhibitors of Taq polymerase with the aid of an internal control. Multiple negative and positive controls were used to monitor each step of the procedure. RESULTS--The data from two laboratories, using the same operating procedures, were combined. Of 1957 specimens, 79 (4%) were culture and PCR positive, while 1839 (93.9%) were negative in both tests. Thirty specimens (1.5%) were PCR positive only and nine (0.5%) were culture positive but PCR negative. CONCLUSION--Using culture and clinical history as the gold standard, sensitivity and specificity for PCR were 92.1% and 99.8%, respectively. With elaborate precautions, PCR is a suitable and reliable method for the detection of M tuberculosis in clinical samples in a routine microbiology laboratory. Images PMID:7490312

  14. Application of quantitative signal detection in the Dutch spontaneous reporting system for adverse drug reactions.

    PubMed

    van Puijenbroek, Eugène; Diemont, Willem; van Grootheest, Kees

    2003-01-01

    The primary aim of spontaneous reporting systems (SRSs) is the timely detection of unknown adverse drug reactions (ADRs), or signal detection. Generally this is carried out by a systematic manual review of every report sent to an SRS. Statistical analysis of the data sets of an SRS, or quantitative signal detection, can provide additional information concerning a possible relationship between a drug and an ADR. We describe the role of quantitative signal detection and the way it is applied at the Netherlands Pharmacovigilance Centre Lareb. Results of the statistical analysis are implemented in the traditional case-by-case analysis. In addition, for data-mining purposes, a list of associations of ADRs and suspected drugs that are disproportionally present in the database is periodically generated. Finally, quantitative signal generation can be used to study more complex relationships, such as drug-drug interactions and syndromes. The results of quantitative signal detection should be considered as an additional source of information, complementary to the traditional analysis. Techniques for the detection of drug interactions and syndromes offer a new challenge for pharmacovigilance in the near future.

  15. Pyranoside-into-furanoside rearrangement: new reaction in carbohydrate chemistry and its application in oligosaccharide synthesis.

    PubMed

    Krylov, Vadim B; Argunov, Dmitry A; Vinnitskiy, Dmitry Z; Verkhnyatskaya, Stella A; Gerbst, Alexey G; Ustyuzhanina, Nadezhda E; Dmitrenok, Andrey S; Huebner, Johannes; Holst, Otto; Siebert, Hans-Christian; Nifantiev, Nikolay E

    2014-12-08

    Great interest in natural furanoside-containing compounds has challenged the development of preparative methods for their synthesis. Herein a novel reaction in carbohydrate chemistry, namely a pyranoside-into-furanoside (PIF) rearrangement permitting the transformation of selectively O-substituted pyranosides into the corresponding furanosides is reported. The discovered process includes acid-promoted sulfation accompanied by rearrangement of the pyranoside ring into a furanoside ring followed by solvolytic O-desulfation. This process, which has no analogy in organic chemistry, was shown to be a very useful tool for the synthesis of furanoside-containing complex oligosaccharides, which was demonstrated by synthesizing disaccharide derivatives α-D-Galp-(1→3)-β-D-Galf-OPr, 3-O-s-lactyl-β-D-Galf-(1→3)-β-D-Glcp-OPr, and α-L-Fucf-(1→4)-β-D-GlcpA-OPr related to polysaccharides from the bacteria Klebsiella pneumoniae and Enterococcus faecalis and the brown seaweed Chordaria flagelliformis.

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

    NASA Technical Reports Server (NTRS)

    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).

  17. [The applications of thermostable ligase chain reaction in facilitating DNA recombination].

    PubMed

    Xiangda, Zhou; Xiao, Song; Cong, Huai; Haiyan, Sun; Hongyan, Chen; Daru, Lu

    2016-02-01

    The traditional Type Ⅱ restriction enzyme-based method is restricted by the purification steps, and therefore, cannot be applied to specific DNA assembly in chaotic system. To solve this problem, Thermostable Ligase Chain Reaction (TLCR) was introduced in the process of DNA assembly and capture. This technique combines the feature of thermostable DNA ligase and sequence specific oligo ligation template, "Helper", to achieve specific assembly of target fragments and exponential increase of products in multiple thermocyclings. Two plasmid construction experiments were carried out in order to test the feasibility and practical performance of TLCR. One was that, TLCR was used to specifically capture a 1.5 kb fragment into vector from an unpurified chaotic system which contained 7 different sizes of fragments. The results showed that the capturing accuracy was around 80%, which proved the feasibility and accuracy of using TLCR to specific assembly of DNA fragments in a complicated mixed system. In the other experiment, TLCR was used to capture two fragments (total length was 27 kb) from Hind Ⅲ digestion of Lambda genome into vector by order. The results also showed an accuracy of around 80%. As demonstrated in the results, TLCR can simplify the process of DNA recombination experiments and is suitable for the assembly of multiple and large DNA fragments. This technique can provide convenience to biological experiments.

  18. ortho-Lithium/magnesium carboxylate-driven aromatic nucleophilic substitution reactions on unprotected naphthoic acids.

    PubMed

    Aissaoui, Regadia; Nourry, Arnaud; Coquel, Ariane; Dao, Thi Thanh Hà; Derdour, Aicha; Helesbeux, Jean-Jacques; Duval, Olivier; Castanet, Anne-Sophie; Mortier, Jacques

    2012-01-06

    Substitution of an ortho-fluoro or methoxy group in 1- and 2-naphthoic acids furnishing substituted naphthoic acids occurs in good to excellent yields upon reaction with alkyl/vinyl/aryl organolithium and Grignard reagents, in the absence of a metal catalyst without the need to protect the carboxyl (CO(2)H) group. This novel nucleophilic aromatic substitution is presumed to proceed via a precoordination of the organometallic with the substrate, followed by an addition/elimination.

  19. First pre-functionalised polymeric aromatic framework from mononitrotetrakis(iodophenyl)methane and its applications.

    PubMed

    Verde-Sesto, Ester; Pintado-Sierra, Mercedes; Corma, Avelino; Maya, Eva M; de la Campa, Jose G; Iglesias, Marta; Sánchez, Felix

    2014-04-22

    Starting from mononitrotetrakis(iodophenyl)methane as monomer, we report the preparation of the first pre-functionalised porous aromatic frameworks (PAFs) and their application as supports for organometallic catalysts. Neutral coordinate imino-pyridine Schiff base (PAF-NPy) or chiral bis-amino (PAF-NPro) ligands were obtained by post-synthetic treatment of PAF-NH2 and treated with copper(I) or rhodium(I) to yield the corresponding supported transition-metal catalysts. The as-prepared PAF-NN-M catalysts exhibited activity and selectivity similar to that of the corresponding homogeneous catalysts and were easily removed from reaction media and recycled without loss of activity or selectivity.

  20. Recent progress in GaInAsSb thermophotovoltaics grown by organometallic vapor phase epitaxy

    SciTech Connect

    Wang, C.A.; Choi, H.K.; Oakley, D.C.; Charache, G.W.

    1998-06-01

    Studies on the materials development of Ga{sub 1{minus}x}In{sub x}As{sub y}Sb{sub 1{minus}y} alloys for thermophotovoltaic (TPV) devices are reviewed. Ga{sub 1{minus}x}In{sub x}As{sub y}Sb{sub 1{minus}y} epilayers were grown lattice matched to GaSb substrates by organometallic vapor phase epitaxy (OMVPE) using all organometallic precursors including triethylgallium, trimethylindium, tertiarybutylarsine, and trimethylantimony with diethyltellurium and dimethylzinc as the n- and p-type dopants, respectively. The overall material quality of these alloys depends on growth temperature, In content, V/III ratio, substrate misorientation, and to a lesser extent, growth rate. A mirror-like surface morphology and room temperature photoluminescence (PL) are obtained for GaInAsSb layers with peak emission in the wavelength range between 2 and 2.5 {micro}m. The crystal quality improves for growth temperature decreasing from 575 to 525 C, and with decreasing In content, as based on epilayer surface morphology and low temperature PL spectra. A trend of smaller full width at half-maximum for low temperature PL spectra is observed as the growth rate is increased from 1.5 to 2.5 and 5 {micro}m/h. In general, GaInAsSb layers grown on (100) GaSb substrates with a 6{degree} toward (111)B misorientation exhibited overall better material quality than layers grown on the more standard substrate (100)2{degree} toward (110). Consistent growth of high performance lattice-matched GaInAsSb TPV devices is also demonstrated.

  1. Application of In-Line Mid-Infrared (MIR) Spectroscopy Coupled with Calorimetry for the Determination of the Molar Enthalpy of Reaction between Ammonium Chloride and Sodium Nitrite.

    PubMed

    Kartnaller, Vinicius; Mariano, Danielly C O; Cajaiba, João

    2016-03-01

    The reaction between ammonium chloride and sodium nitrite has been known for its application as a source of heat because of its large enthalpy of reaction, for which it has been used by the oil industry. There have been no known calorimetric studies for the experimental determination of its molar enthalpy of reaction, which is necessary in order to predict the limits achieved for up-scale applications. Attenuated total reflection Fourier transform infrared spectroscopy (ATR FT-IR) and reaction calorimetry were used to determine this value by using a simple methodology. Both techniques were used concomitantly as a source of information regarding the time-dependent moles converted (Δn) and the amount of exchanged heat (ΔH). The molar enthalpy of reaction was calculated to be -74 ± 4 kcal mol(-1). The percentage between the confidence interval and the calculated value was 5.4%, which shows that the methodology was precise. After the determination of the molar enthalpy of reaction, it was proved that the ATR FT-IR alone was able to be used as a substitute for the reaction calorimetry technique, in which the IR signal is converted to the heat information, presenting as an easier technique for the monitoring of the heat released by this system for future applications.

  2. Widely applicable MATLAB routines for automated analysis of saccadic reaction times.

    PubMed

    Leppänen, Jukka M; Forssman, Linda; Kaatiala, Jussi; Yrttiaho, Santeri; Wass, Sam

    2015-06-01

    Saccadic reaction time (SRT) is a widely used dependent variable in eye-tracking studies of human cognition and its disorders. SRTs are also frequently measured in studies with special populations, such as infants and young children, who are limited in their ability to follow verbal instructions and remain in a stable position over time. In this article, we describe a library of MATLAB routines (Mathworks, Natick, MA) that are designed to (1) enable completely automated implementation of SRT analysis for multiple data sets and (2) cope with the unique challenges of analyzing SRTs from eye-tracking data collected from poorly cooperating participants. The library includes preprocessing and SRT analysis routines. The preprocessing routines (i.e., moving median filter and interpolation) are designed to remove technical artifacts and missing samples from raw eye-tracking data. The SRTs are detected by a simple algorithm that identifies the last point of gaze in the area of interest, but, critically, the extracted SRTs are further subjected to a number of postanalysis verification checks to exclude values contaminated by artifacts. Example analyses of data from 5- to 11-month-old infants demonstrated that SRTs extracted with the proposed routines were in high agreement with SRTs obtained manually from video records, robust against potential sources of artifact, and exhibited moderate to high test-retest stability. We propose that the present library has wide utility in standardizing and automating SRT-based cognitive testing in various populations. The MATLAB routines are open source and can be downloaded from http://www.uta.fi/med/icl/methods.html .

  3. Closed-time-path functional formalism in curved spacetime: Application to cosmological back-reaction problems

    NASA Astrophysics Data System (ADS)

    Calzetta, E.; Hu, B. L.

    1987-01-01

    We discuss the generalization to curved spacetime of a path-integral formalism of quantum field theory based on the sum over paths first going forward in time in the presence of one external source from an in vacuum to a state defined on a hypersurface of constant time in the future, and then backwards in time in the presence of a different source to the same in vacuum. This closed-time-path formalism which generalizes the conventional method based on in-out vacuum persistence amplitudes yields real and causal effective actions, field equations, and expectation values. We apply this method to two problems in semiclassical cosmology. First we study the back reaction of particle production in a radiation-filled Bianchi type-I universe with a conformal scalar field. Unlike the in-out formalism which yields complex geometries the real and causal effective action here yields equations for real effective geometries, with more readily interpretable results. It also provides a clear identification of particle production as a dissipative process in semiclassical theories. In the second problem we calculate the vacuum expectation value of the stress-energy tensor for a nonconformal massive λφ4 theory in a Robertson-Walker universe. This study serves to illustrate the use of Feynman diagrams and higher-loop calculations in this formalism. It also demonstrates the economy of this method in the calculation of expectation values over the mode-sum Bogolubov transformation methods ordinarily applied to matrix elements calculated in the conventional in-out approach. The capability of the closed-time-path formalism of dealing with Feynman, causal, and correlation functions on the same footing makes it a potentially powerful and versatile technique for treating nonequilibrium statistical properties of dynamical systems as in early-Universe quantum processes.

  4. 3D Printing Carbonate Microstructures: Preliminary Porosity-Permeability Trends with Applications to the Decarbonation Reaction

    NASA Astrophysics Data System (ADS)

    Head, D. A.; Vanorio, T.

    2015-12-01

    The advent of modern 3D printing has provided an unprecedented opportunity to combine the strengths of two of the main approaches used in rock physics analysis - digital and experimental. In the laboratory we can explore still unknown frontiers of rock behaviour, and in digital rock physics each sample and experiment is fully reproducible at a minute, detailed scale. Bringing these two techniques together and applying both to the same rock volumes has become more important than ever as we add layers of complexity to both models and experiments in an attempt understand the coupled thermo-chemo-mechanical changes controlling transport and elastic properties of carbonate diagenesis. In this study, we take a two-pronged approach. First, we investigate the effect of changing the size of a specific natural carbonate pore geometry on the frame independent properties porosity and permeability and compare the laboratory measurements to the results of numerical simulations. These preliminary tests show that it is possible to use an iterative, grain-scale geometry modification and measurement workflow that utilizes 3D printing. Second, we induce the decarbonation reaction in a carbonate deposit injected with silicate-bearing fluids in a temperature-pressure space not previously explored. These results show that we can quantify changes to the acoustic and transport properties of the sample when exposed to such diagenetic conditions. Ultimately we will use a workflow designed to iteratively combine baseline CT-scanned rock volumes, experimentally derived boundary conditions for and modifications to the digital rock volumes, and measurements on 3D printed rock models in order to test hypotheses about grain-scale changes on bulk sample properties.

  5. Time-resolved infrared (TRIR) study on the formation and reactivity of organometallic methane and ethane complexes in room temperature solution

    PubMed Central

    Cowan, Alexander J.; Portius, Peter; Kawanami, Hajime K.; Jina, Omar S.; Grills, David C.; Sun, Xue-Zhong; McMaster, Jonathan; George, Michael W.

    2007-01-01

    We have used fast time-resolved infrared spectroscopy to characterize a series of organometallic methane and ethane complexes in solution at room temperature: W(CO)5(CH4) and M(η5C5R5)(CO)2(L) [where M = Mn or Re, R = H or CH3 (Re only); and L = CH4 or C2H6]. In all cases, the methane complexes are found to be short-lived and significantly more reactive than the analogous n-heptane complexes. Re(Cp)(CO)2(CH4) and Re(Cp*)(CO)2(L) [Cp* = η5C5(CH3)5 and L = CH4, C2H6] were found to be in rapid equilibrium with the alkyl hydride complexes. In the presence of CO, both alkane and alkyl hydride complexes decay at the same rate. We have used picosecond time-resolved infrared spectroscopy to directly monitor the photolysis of Re(Cp*)(CO)3 in scCH4 and demonstrated that the initially generated Re(Cp*)(CO)2(CH4) forms an equilibrium mixture of Re(Cp*)(CO)2(CH4)/Re(Cp*)(CO)2(CH3)H within the first few nanoseconds (τ = 2 ns). The ratio of alkane to alkyl hydride complexes varies in the order Re(Cp)(CO)2(C2H6):Re(Cp)(CO)2(C2H5)H > Re(Cp*)(CO)2(C2H6):Re(Cp*)(CO)2(C2H5)H ≈ Re(Cp)(CO)2(CH4):Re(Cp)(CO)2(CH3)H > Re(Cp*)(CO)2(CH4):Re(Cp*)(CO)2(CH3)H. Activation parameters for the reactions of the organometallic methane and ethane complexes with CO have been measured, and the ΔH‡ values represent lower limits for the CH4 binding enthalpies to the metal center of WCH4 (30 kJ·mol−1), MnCH4 (39 kJ·mol−1), and ReCH4 (51 kJ·mol−1) bonds in W(CO)5(CH4), Mn(Cp)(CO)2(CH4), and Re(Cp)(CO)2(CH4), respectively. PMID:17409190

  6. Time-resolved infrared (TRIR) study on the formation and reactivity of organometallic methane and ethane complexes in room temperature solution.

    PubMed

    Cowan, Alexander J; Portius, Peter; Kawanami, Hajime K; Jina, Omar S; Grills, David C; Sun, Xue-Zhong; McMaster, Jonathan; George, Michael W

    2007-04-24

    We have used fast time-resolved infrared spectroscopy to characterize a series of organometallic methane and ethane complexes in solution at room temperature: W(CO)5(CH4) and M(eta5-C5R5)(CO)2(L) [where M = Mn or Re, R = H or CH3 (Re only); and L = CH4 or C2H6]. In all cases, the methane complexes are found to be short-lived and significantly more reactive than the analogous n-heptane complexes. Re(Cp)(CO)2(CH4) and Re(Cp*)(CO)2(L) [Cp* = eta5-C5(CH3)(5) and L = CH4, C2H6] were found to be in rapid equilibrium with the alkyl hydride complexes. In the presence of CO, both alkane and alkyl hydride complexes decay at the same rate. We have used picosecond time-resolved infrared spectroscopy to directly monitor the photolysis of Re(Cp*)(CO)3 in scCH4 and demonstrated that the initially generated Re(Cp*)(CO)2(CH4) forms an equilibrium mixture of Re(Cp*)(CO)2(CH4)/Re(Cp*)(CO)2(CH3)H within the first few nanoseconds (tau = 2 ns). The ratio of alkane to alkyl hydride complexes varies in the order Re(Cp)(CO)2(C2H6):Re(Cp)(CO)2(C2H5)H > Re(Cp*)(CO)2(C2H6):Re(Cp*)(CO)2(C2H5)H approximately equal to Re(Cp)(CO)2(CH4):Re(Cp)(CO)2(CH3)H > Re(Cp*)(CO)2(CH4):Re(Cp*)(CO)2(CH3)H. Activation parameters for the reactions of the organometallic methane and ethane complexes with CO have been measured, and the DeltaH++ values represent lower limits for the CH4 binding enthalpies to the metal center of W-CH4 (30 kJ.mol(-1)), Mn-CH4 (39 kJ.mol(-1)), and Re-CH4 (51 kJ.mol(-1)) bonds in W(CO)5(CH4), Mn(Cp)(CO)2(CH4), and Re(Cp)(CO)2(CH4), respectively.

  7. Modified transition state theory and negative apparent activation energies of simple metathesis reactions: application to the reaction CH3 + HBr --> CH4 + Br.

    PubMed

    Krasnoperov, Lev N; Peng, Jingping; Marshall, Paul

    2006-03-09

    A modified transition state theory (MTST) has been developed for gas-phase reactions with "negative barriers". The theory was applied to the reactions CH3 + HBr(DBr) --> CH4(CH3D) + Br (1a, 1b), which exhibit negative temperature dependences. Accurate ab initio calculations performed with coupled cluster theory extrapolated to the complete basis set limit revealed a transition state located at -2.3 kJ mol(-1) relative to the ground state of the reactants (in reaction 1a), as well as a shallow bound complex. The negative temperature dependence, the absolute values of the rate constant, and the isotope substitution effect are reproduced with good accuracy (10%), without any adjustment or fitting parameters. Analytical expressions are presented for MTST including angular momentum conservation, centrifugal barriers and tunneling. This analysis uses information about the possibly loose entrance barrier and the transition state but does not invoke a statistical intermediate complex.

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

    NASA Astrophysics Data System (ADS)

    Manzo-Robledo, A.; Costa, Natália J. S.; Philippot, K.; Rossi, Liane M.; Ramírez-Meneses, E.; Guerrero-Ortega, L. P. A.; Ezquerra-Quiroga, S.

    2015-12-01

    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, Pd90Ni10, Pd50Ni50, Pd10Ni90, and Ni) have been synthesized from organometallic precursors, namely tris(dibenzylideneacetone) dipalladium(0), Pd2(dba)3, and bis(1,5-cyclooctadiene)nickel(0), Ni(cod)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.

  9. Toward new organometallic architectures: synthesis of carbene-centered rhodium and palladium bisphosphine complexes. stability and reactivity of [PC(BIm)PRh(L)][PF6] pincers.

    PubMed

    Plikhta, Andriy; Pöthig, Alexander; Herdtweck, Eberhardt; Rieger, Bernhard

    2015-10-05

    In this article, we report the synthesis of a tridentate carbene-centered bisphosphine ligand precursor and its complexes. The developed four-step synthetic strategy of a new PC(BIm)P pincer ligand represents the derivatization of benzimidazole in the first and third positions by (diphenylphosphoryl)methylene synthone, followed by phosphine deprotection and subsequent insertion of a noncoordinating anion. The obtained ligand precursor undergoes complexation, with PdCl2 and [μ-OCH3Rh(COD)]2 smoothly forming the target organometallics [PC(BIm)PPdCl][PF6] and [PC(BIm)PRh(L)][PF6] under mild hydrogenation conditions. A more detailed study of the rhodium complexes [PC(BIm)PRh(L)][PF6] reveals significant thermal stability of the PC(BIm)PRh moiety in the solid state as well as in solution. The chemical behavior of 1,3-bis(diphenylphosphinomethylene)benzimidazol-2-ylrhodium acetonitrile hexafluorophosphate has been screened under decarbonylation, hydrogenation, and hydroboration reaction conditions. Thus, the PC(BIm)PRh(I) complex is a sufficiently stable compound, with the potential to be applied in catalysis.

  10. Mineral solubility and free energy controls on microbial reaction kinetics: Application to contaminant transport in the subsurface

    SciTech Connect

    Taillefert, Martial; Van Cappellen, Philippe

    2016-11-14

    Recent developments in the theoretical treatment of geomicrobial reaction processes have resulted in the formulation of kinetic models that directly link the rates of microbial respiration and growth to the corresponding thermodynamic driving forces. The overall objective of this project was to verify and calibrate these kinetic models for the microbial reduction of uranium(VI) in geochemical conditions that mimic as much as possible field conditions. The approach combined modeling of bacterial processes using new bioenergetic rate laws, laboratory experiments to determine the bioavailability of uranium during uranium bioreduction, evaluation of microbial growth yield under energy-limited conditions using bioreactor experiments, competition experiments between metabolic processes in environmentally relevant conditions, and model applications at the field scale. The new kinetic descriptions of microbial U(VI) and Fe(III) reduction should replace those currently used in reactive transport models that couple catabolic energy generation and growth of microbial populations to the rates of biogeochemical redox processes. The above work was carried out in collaboration between the groups of Taillefert (batch reactor experiments and reaction modeling) at Georgia Tech and Van Cappellen (retentostat experiments and reactive transport modeling) at University of Waterloo (Canada).

  11. Spin densities from subsystem density-functional theory: Assessment and application to a photosynthetic reaction center complex model

    NASA Astrophysics Data System (ADS)

    Solovyeva, Alisa; Pavanello, Michele; Neugebauer, Johannes

    2012-05-01

    Subsystem density-functional theory (DFT) is a powerful and efficient alternative to Kohn-Sham DFT for large systems composed of several weakly interacting subunits. Here, we provide a systematic investigation of the spin-density distributions obtained in subsystem DFT calculations for radicals in explicit environments. This includes a small radical in a solvent shell, a π-stacked guanine-thymine radical cation, and a benchmark application to a model for the special pair radical cation, which is a dimer of bacteriochlorophyll pigments, from the photosynthetic reaction center of purple bacteria. We investigate the differences in the spin densities resulting from subsystem DFT and Kohn-Sham DFT calculations. In these comparisons, we focus on the problem of overdelocalization of spin densities due to the self-interaction error in DFT. It is demonstrated that subsystem DFT can reduce this problem, while it still allows to describe spin-polarization effects crossing the boundaries of the subsystems. In practical calculations of spin densities for radicals in a given environment, it may thus be a pragmatic alternative to Kohn-Sham DFT calculations. In our calculation on the special pair radical cation, we show that the coordinating histidine residues reduce the spin-density asymmetry between the two halves of this system, while inclusion of a larger binding pocket model increases this asymmetry. The unidirectional energy transfer in photosynthetic reaction centers is related to the asymmetry introduced by the protein environment.

  12. Potential of modified iron-rich foundry waste for environmental applications: Fenton reaction and Cr(VI) reduction.

    PubMed

    Oliveira, Patrícia E F; Oliveira, Leandro D; Ardisson, José D; Lago, Rochel M

    2011-10-30

    A magnetic fraction (15%) from a waste of foundry sand (WFS), composed of sand, carbon, bentonite clay and iron (10%) was modified by thermal treatment at 400, 600 and 800°C under inert atmosphere. Mössbauer analyses showed that the thermal treatment increased the amount of Fe(3)O(4) from 25 to 55% by reduction of Fe(2)O(3) and highly dispersed Fe(3+) by the carbon present in the waste. The Fe(3)O(4) caused a significant increase on the activity of two important reactions with application in environmental remediation: the Fenton oxidation of indigo carmine dye with H(2)O(2) and the reduction of Cr(VI) to Cr(III). The magnetic fraction of WFS was also mixed with hematite (Fe(2)O(3)) and thermally treated at 400, 600 and 800°C. This treatment produced large amounts of surface Fe(3)O(4) and increased substantially the rate of Fenton reaction as well as Cr(VI) reduction. This reactivity combined with the presence of carbon (an adsorbent for organic contaminants), bentonite clay (an adsorbent for metallic contaminants) and the granulometry/packing/hydrodynamic features make WFS a promising material for use in reactive permeable barriers.

  13. To Fake or Not to Fake: Antecedents to Interview Faking, Warning Instructions, and Its Impact on Applicant Reactions

    PubMed Central

    Law, Stephanie J.; Bourdage, Joshua; O’Neill, Thomas A.

    2016-01-01

    In the present study, we examined the antecedents and processes that impact job interviewees’ decisions to engage in deceptive impression management (i.e., interview faking). Willingness and capacity to engage in faking were found to be the processes underlying the decision to use deceptive impression management in the interview. We also examined a personality antecedent to this behavior, Honesty-Humility, which was negatively related to the use of deceptive impression management through increased willingness to engage in these behaviors. We also tested a possible intervention to reduce IM. In particular, we found that warnings against faking – specifically, an identification warning - reduced both the perceived capacity to engage in interview faking, and subsequent use of several faking behaviors. Moreover, this warning reduced faking without adversely impacting applicant reactions. PMID:27895609

  14. Application of a reversible chemical reaction system to solar thermal power plants

    NASA Technical Reports Server (NTRS)

    Hanseth, E. J.; Won, Y. S.; Seibowitz, L. P.

    1980-01-01

    Three distributed dish solar thermal power systems using various applications of SO2/SO3 chemical energy storage and transport technology were comparatively assessed. Each system features various roles for the chemical system: (1) energy storage only, (2) energy transport, or (3) energy transport and storage. These three systems were also compared with the dish-Stirling, using electrical transport and battery storage, and the central receiver Rankine system, with thermal storage, to determine the relative merit of plants employing a thermochemical system. As an assessment criterion, the busbar energy costs were compared. Separate but comparable solar energy cost computer codes were used for distributed receiver and central receiver systems. Calculations were performed for capacity factors ranging from 0.4 to 0.8. The results indicate that SO2/SO3 technology has the potential to be more cost effective in transporting the collected energy than in storing the energy for the storage capacity range studied (2-15 hours)

  15. Applications of Endothermic Reaction Technology to the High Speed Civil Transport

    NASA Technical Reports Server (NTRS)

    Glickstein, Marvin R.; Spadaccini, Louis J.

    1998-01-01

    The success of strategies for controlling emissions and enhancing performance in High Speed Research applications may be Increased by more effective utilization of the heat sink afforded by the fuel in the vehicle thermal management system. This study quantifies the potential benefits associated with the use of supercritical preheating and endothermic cracking of let fuel prior to combustion to enhance the thermal management capabilities of the propulsion systems in the High Speed Civil Transport (HSCT). A fuel-cooled thermal management system, consisting of plate-fin heat exchangers and a small auxiliary compressor, is defined for the HSCT, Integrated with the engine, and an assessment of the effect on engine performance, weight, and operating cost is performed. The analysis indicates significant savings due a projected improvement in fuel economy, and the potential for additional benefit if the cycle is modified to take full advantage of all the heat sink available in the fuel.

  16. UV and fluorescent spectra study the reaction between 1, 8-Naphthalimide derivative and hypochlorite their applications

    NASA Astrophysics Data System (ADS)

    Li, Jiawei; Liu, Tao; Huo, Fangjun; Chao, Jianbin; Zhang, Yongbin; Yin, Caixia

    2017-03-01

    Two simple, efficient turn-on fluorescent probes for hypochlorite have been rationally designed and developed by utilizing the oxidation of hypochlorite. Notably, probe 1 and 2 displayed rapid and remarkable turn-on responses to ClO- in PBS buffer solution (pH 7.4). Further, the optical properties of two probes and their ClO--addition products were confirmed by density functional theory calculations. And detection limits of two probes for ClO- based on the definition by IUPAC were calculated for 2.882 nM and 0.354 μM. More importantly, cell imaging experiments demonstrated that probe 1 was more suitable for detecting the ClO- in living A549 cells. And both two probes had the possibility of potentially applied in practical applications such as detecting the hypochlorite concentration of tap water and river water.

  17. Stress reactions in Vitis vinifera L. following soil application of the herbicide flumioxazin.

    PubMed

    Saladin, Gaëlle; Magné, Christian; Clément, Christophe

    2003-10-01

    In order to evaluate the stress effects of flumioxazin (fmx) on grapevine, a non-target plant (Vitis vinifera L.), physiological parameters such as carbohydrate content, water status or nitrogenous metabolites were investigated on fruiting cuttings and plants grown in vineyard. In the leaves of cuttings, the soil-applied herbicide induced stress manifestations including a decrease of the dry weight percentage and the soluble carbohydrate content during the first week after treatment. Thereafter, a decrease of the osmotic potential was observed, as well as a decrease of total protein content and a parallel accumulation of free amino acids, including proline. Altogether, these results suggest that soil-applied fmx induced a stress in grapevines, leading to leaf proteolysis. However, this stress was partially recovered 3 weeks after herbicide application, suggesting that the cuttings were capable to adapt to the fmx exposure. In the vineyard, the flumioxazin effects were still significant 5 months after the treatment, particularly in the CH cv. They included a decrease of the leaf dry weight percentage and soluble carbohydrate content, as well as an increase of the osmotic potential. The decrease of leaf soluble carbohydrates may have dramatic consequences for the berry growth and the reserve constitution. Moreover, treated plants were characterized by a decrease of the free amino acid content and an accumulation of ammonium, while the protein level did not significantly increase, suggesting a degradation of amino acids. The alteration of carbon and nitrogen status after herbicide treatment may affect the grapevine vigour in a long term.

  18. Hybrid approach for free energy calculations with high-level methods: application to the SN2 reaction of CHCl3 and OH- in water.

    PubMed

    Valiev, Marat; Garrett, Bruce C; Tsai, Ming-Kang; Kowalski, Karol; Kathmann, Shawn M; Schenter, Gregory K; Dupuis, Michel

    2007-08-07

    We present an approach to calculate the free energy profile along a condensed-phase reaction path based on high-level electronic structure methods for the reactive region. The bulk of statistical averaging is shifted toward less expensive descriptions by using a hierarchy of representations that includes molecular mechanics, density functional theory, and coupled cluster theories. As an application of this approach we study the reaction of CHCl3 with OH- in aqueous solution.

  19. Hybrid approach for free energy calculations with high-level methods: Application to the SN2 reaction of CHCl3 and OH- in water

    NASA Astrophysics Data System (ADS)

    Valiev, Marat; Garrett, Bruce C.; Tsai, Ming-Kang; Kowalski, Karol; Kathmann, Shawn M.; Schenter, Gregory K.; Dupuis, Michel

    2007-08-01

    We present an approach to calculate the free energy profile along a condensed-phase reaction path based on high-level electronic structure methods for the reactive region. The bulk of statistical averaging is shifted toward less expensive descriptions by using a hierarchy of representations that includes molecular mechanics, density functional theory, and coupled cluster theories. As an application of this approach we study the reaction of CHCl3 with OH- in aqueous solution.

  20. Applications of a single-molecule detection in early disease diagnosis and enzymatic reaction study

    SciTech Connect

    Li, Jiangwei

    2008-01-01

    Various single-molecule techniques were utilized for ultra-sensitive early diagnosis of viral DNA and antigen and basic mechanism study of enzymatic reactions. DNA of human papilloma virus (HPV) served as the screening target in a flow system. Alexa Fluor 532 (AF532) labeled single-stranded DNA probes were hybridized to the target HPV-16 DNA in solution. The individual hybridized molecules were imaged with an intensified charge-coupled device (ICCD) in two ways. In the single-color mode, target molecules were detected via fluorescence from hybridized probes only. This system could detect HPV-16 DNA in the presence of human genomic DNA down to 0.7 copy/cell and had a linear dynamic range of over 6 orders of magnitude. In the dual-color mode, fluorescence resonance energy transfer (FRET) was employed to achieve zero false-positive count. We also showed that DNA extracts from Pap test specimens did not interfere with the system. A surface-based method was used to improve the throughput of the flow system. HPV-16 DNA was hybridized to probes on a glass surface and detected with a total internal reflection fluorescence (TIRF) microscope. In the single-probe mode, the whole genome and target DNA were fluorescently labeled before hybridization, and the detection limit is similar to the flow system. In the dual-probe mode, a second probe was introduced. The linear dynamic range covers 1.44-7000 copies/cell, which is typical of early infection to near-cancer stages. The dual-probe method was tested with a crudely prepared sample. Even with reduced hybridization efficiency caused by the interference of cellular materials, we were still able to differentiate infected cells from healthy cells. Detection and quantification of viral antigen with a novel single-molecule immunosorbent assay (SMISA) was achieved. Antigen from human immunodeficiency virus type 1(HIV-1) was chosen to be the target in this study. The target was sandwiched between a monoclonal capture antibody and a

  1. Hydrogen Atom Transfer Reactions of a Ruthenium Imidazole Complex: Hydrogen Tunneling and the Applicability of the Marcus Cross Relation

    PubMed Central

    Wu, Adam; Mayer, James M.

    2009-01-01

    The reaction of RuII(acac)2(py-imH) (RuIIimH) with TEMPO• (2,2,6,6-tetramethyl-piperidine-1-oxyl radical) in MeCN quantitatively gives RuIII(acac)2(py-im) (RuIIIim) and the hydroxylamine TEMPO-H by transfer of H• (H+ + e−) (acac = 2,4-pentanedionato, py-imH = 2-(2′-pyridyl)imidazole). Kinetic measurements of this reaction by UV-vis stopped-flow techniques indicate a bimolecular rate constant k3H = 1400 ± 100 M−1 s−1 at 298 K. The reaction proceeds via a concerted hydrogen atom transfer (HAT) mechanism, as shown by ruling out the stepwise pathways of initial proton or electron transfer due to their very unfavorable thermochemistry (ΔG°). Deuterium transfer from RuII(acac)2(py-imD) (RuIIimD) to TEMPO• is surprisingly much slower at k3D = 60 ± 7 M−1 s−1, with k3H/k3D = 23 ± 3 at 298 K. Temperature dependent measurements of this deuterium kinetic isotope effect (KIE) show a large difference between the apparent activation energies, Ea3D − Ea3H = 1.9 ± 0.8 kcal mol−1. The large k3H/k3D and ΔEa values appear to be greater than the semi-classical limits and thus suggest a tunneling mechanism. The self-exchange HAT reaction between RuIIimH and RuIIIim, measured by 1H NMR line broadening, occurs with k4H = (3.2 ± 0.3) × 105 M−1 s−1 at 298 K and k4H/k4D = 1.5 ± 0.2. Despite the small KIE, tunneling is suggested by the ratio of Arrhenius pre-exponential factors, log(A4H/A4D) = −0.5 ± 0.3. These data provide a test of the applicability of the Marcus cross relation for H and D transfers, over a range of temperatures, for a reaction that involves substantial tunneling. The cross relation calculates rate constants for RuIIimH(D) + TEMPO• that are greater than those observed: k3H,calc/k3H = 31 ± 4 and k3D,calc/k3D = 140 ± 20 at 298 K. In these rate constants and in the activation parameters, there is a better agreement with the Marcus cross relation for H than for D transfer, despite the greater prevalence of tunneling for H. The cross

  2. Unravelling novel synergies between organometallic and biological partners: a quantum mechanics/molecular mechanics study of an artificial metalloenzyme

    PubMed Central

    Ortega-Carrasco, Elisabeth; Lledós, Agustí; Maréchal, Jean-Didier

    2014-01-01

    In recent years, the design of artificial metalloenzymes obtained by the insertion of homogeneous catalysts into biological macromolecules has become a major field of research. These hybrids, and the corresponding X-ray structures of several of them, are offering opportunities to better understand the synergy between organometallic and biological subsystems. In this work, we investigate the resting state and activation process of a hybrid inspired by an oxidative haemoenzyme but presenting an unexpected reactivity and structural features. An extensive series of quantum mechanics/molecular mechanics calculations show that the resting state and the activation processes of the novel enzyme differ from naturally occurring haemoenzymes in terms of the electronic state of the metal, participation of the first coordination sphere of the metal and the dynamic process. This study presents novel insights into the sensitivity of the association between organometallic and biological partners and illustrates the molecular challenge that represents the design of efficient enzymes based on this strategy. PMID:24829279

  3. Unravelling novel synergies between organometallic and biological partners: a quantum mechanics/molecular mechanics study of an artificial metalloenzyme.

    PubMed

    Ortega-Carrasco, Elisabeth; Lledós, Agustí; Maréchal, Jean-Didier

    2014-07-06

    In recent years, the design of artificial metalloenzymes obtained by the insertion of homogeneous catalysts into biological macromolecules has become a major field of research. These hybrids, and the corresponding X-ray structures of several of them, are offering opportunities to better understand the synergy between organometallic and biological subsystems. In this work, we investigate the resting state and activation process of a hybrid inspired by an oxidative haemoenzyme but presenting an unexpected reactivity and structural features. An extensive series of quantum mechanics/molecular mechanics calculations show that the resting state and the activation processes of the novel enzyme differ from naturally occurring haemoenzymes in terms of the electronic state of the metal, participation of the first coordination sphere of the metal and the dynamic process. This study presents novel insights into the sensitivity of the association between organometallic and biological partners and illustrates the molecular challenge that represents the design of efficient enzymes based on this strategy.

  4. Cyclopentadienyl-ruthenium(II) and iron(II) organometallic compounds with carbohydrate derivative ligands as good colorectal anticancer agents.

    PubMed

    Florindo, Pedro R; Pereira, Diane M; Borralho, Pedro M; Rodrigues, Cecília M P; Piedade, M F M; Fernandes, Ana C

    2015-05-28

    New ruthenium(II) and iron(II) organometallic compounds of general formula [(η(5)-C5H5)M(PP)Lc][PF6], bearing carbohydrate derivative ligands (Lc), were prepared and fully characterized and the crystal structures of five of those compounds were determined by X-ray diffraction studies. Cell viability of colon cancer HCT116 cell line was determined for a total of 23 organometallic compounds and SAR's data analysis within this library showed an interesting dependency of the cytotoxic activity on the carbohydrate moiety, linker, phosphane coligands, and metal center. More importantly, two compounds, 14Ru and 18Ru, matched oxaliplatin IC50 (0.45 μM), the standard metallodrug used in CC chemotherapeutics, and our leading compound 14Ru was shown to be significantly more cytotoxic than oxaliplatin to HCT116 cells, triggering higher levels of caspase-3 and -7 activity and apoptosis in a dose-dependent manner.

  5. Search for the ground-state electronic configurations of correlated organometallic metallocenes from constraint density functional theory

    NASA Astrophysics Data System (ADS)

    Nawa, Kenji; Kitaoka, Yukie; Nakamura, Kohji; Imamura, Hiroshi; Akiyama, Toru; Ito, Tomonori; Weinert, M.

    2016-07-01

    The ground-state electronic configurations of the correlated organometallic metallocenes, M Cp2,M =V , Cr, Mn, Fe, Co, and Ni, are investigated using constraint density functional theory combined with nonempirical Ueff parameters determined from linear-response theory. The relative stability of the various d -orbital electronic configurations of these organometallic molecules is found to be sensitive to the amount of correlation. Using nonempirical values of Ueff, the calculated electronic configurations are in agreement with the experiments: 4A2 g ,3E2 g ,6A1 g ,1A1 g ,2E1 g , and 3A2 g for the VCp2,CrCp2,MnCp2,FeCp2,CoCp2 , and NiCp2, respectively.

  6. Semi-quantitative digital analysis of polymerase chain reaction-electrophoresis gel: Potential applications in low-income veterinary laboratories

    PubMed Central

    Antiabong, John F.; Ngoepe, Mafora G.; Abechi, Adakole S.

    2016-01-01

    Aim: The interpretation of conventional polymerase chain reaction (PCR) assay results is often limited to either positive or negative (non-detectable). The more robust quantitative PCR (qPCR) method is mostly reserved for quantitation studies and not a readily accessible technology in laboratories across developing nations. The aim of this study was to evaluate a semi-quantitative method for conventional PCR amplicons using digital image analysis of electrophoretic gel. The potential applications are also discussed. Materials and Methods: This study describes standard conditions for the digital image analysis of PCR amplicons using the freely available ImageJ software and confirmed using the qPCR assay. Results and Conclusion: Comparison of ImageJ analysis of PCR-electrophoresis gel and qPCR methods showed similar trends in the Fusobacterium necrophorum DNA concentration associated with healthy and periodontal disease infected wallabies (p≤0.03). Based on these empirical data, this study adds descriptive attributes (“more” or “less”) to the interpretation of conventional PCR results. The potential applications in low-income veterinary laboratories are suggested, and guidelines for the adoption of the method are also highlighted. PMID:27733792

  7. Application of Heisenberg's S matrix program to the angular scattering of the state-to-state F + H2 reaction.

    PubMed

    Shan, Xiao; Connor, J N L

    2014-08-21

    This paper makes two applications of Heisenberg's S matrix program (HSMP) to the differential cross section (DCS) of the benchmark reaction F + H2(vi = 0, ji = 0, mi = 0) → FH(vf = 3, jf = 3, mf = 0) + H, at a relative translational energy of 0.119 eV (total energy, 0.3872 eV), where v, j, m are vibrational, rotational, and helicity quantum numbers, respectively, for the initial and final states. (1) The first application employs a "weak" version of HSMP in which no potential energy surface (PES) is employed. It uses four simple S matrix parametrizations, two of which are piecewise continuous, and two are piecewise discontinuous, developed earlier by X. Shan and J. N. L. Connor (J. Phys. Chem. A 2012, 116, 11414-11426) for the state-to-state H + D2 reaction. We find that the small-angle DCS is reproduced for only θR ≲ 10° when compared with the DCS for a numerical S matrix obtained in a large-scale quantum scattering computation using a PES. Here θR is the reactive scattering angle. (2) In our second application, we ask the question "Can simple modifications to the parametrized S matrix be made in order to extend the agreement to larger angles?" To answer this question, we adopt a "hybrid" version of HSMP, as outlined by Shan and Connor (Phys. Chem. Chem. Phys. 2011, 13, 8392-8406), which indirectly uses PES information. We make simple Gaussian-type modifications to both the modulus and argument of the S matrix. We then obtain agreement between the DCSs for the modified and numerical S matrices up to θR ≲ 70°, a significant improvement compared with θR ≲ 10° for the unmodified parametrizations. We find that modifying the argument but not the modulus, or modifying the modulus but not the argument, fails to extend the agreement to larger angles. A semiclassical analysis is used to prove that the enhanced small-angle scattering for the "modified-modulus-modified-argument" parametrized S matrix is an example of a forward glory.

  8. Application of micro X-ray diffraction to investigate the reaction products formed by the alkali silica reaction in concrete structures

    SciTech Connect

    Dähn, R.; Arakcheeva, A.; Schaub, Ph.; Pattison, P.; Chapuis, G.; Grolimund, D.; Wieland, E.; Leemann, A.

    2015-12-21

    Alkali–silica reaction (ASR) is one of the most important deterioration mechanisms in concrete leading to substantial damages of structures worldwide. Synchrotron-based micro-X-ray diffraction (micro-XRD) was employed to characterize the mineral phases formed in micro-cracks of concrete aggregates as a consequence of ASR. This particular high spatial resolution technique enables to directly gain structural information on ASR products formed in a 40-year old motorway bridge damaged due to ASR. Micro-X-ray-fluorescence was applied on thin sections to locate the reaction products formed in veins within concrete aggregates. Micro-XRD pattern were collected at selected points of interest along a vein by rotating the sample. Rietveld refinement determined the structure of the ASR product consisting of a new layered framework similar to mountainite and rhodesite. Furthermore, it is conceivable that understanding the structure of the ASR product may help developing new technical treatments inhibiting ASR.

  9. Analysis of the mechanism of action of potent antibacterial hetero-tri-organometallic compounds: a structurally new class of antibiotics.

    PubMed

    Wenzel, Michaela; Patra, Malay; Senges, Christoph Helmut Rudi; Ott, Ingo; Stepanek, Jennifer Janina; Pinto, Antonio; Prochnow, Pascal; Vuong, Cuong; Langklotz, Sina; Metzler-Nolte, Nils; Bandow, Julia Elisabeth

    2013-07-19

    Two hetero-tri-organometallic compounds with potent activity against Gram-positive bacteria including multi-resistant Staphylococcus aureus (MRSA) were identified. The compounds consist of a peptide nucleic acid backbone with an alkyne side chain, substituted with a cymantrene, a (dipicolyl)Re(CO)3 moiety, and either a ferrocene (FcPNA) or a ruthenocene (RcPNA). Comparative proteomic analysis indicates the bacterial membrane as antibiotic target structure. FcPNA accumulation in the membrane was confirmed by manganese tracing with atomic absorption spectroscopy. Both organometallics disturbed several essential cellular processes taking place at the membrane such as respiration and cell wall biosynthesis, suggesting that the compounds affect membrane architecture. Correlating with enhanced antibacterial activity, oxidative stress was induced only by the ferrocene-substituted compound. The organometallics described here target the cytoplasmic membrane, a clinically proven antibacterial target structure, feature a bactericidal but non-bacteriolytic mode of action and limited cytotoxicity within the limits of solubility. Thus, FcPNA represents a promising lead structure for the development of a new synthetic class of antibiotics.

  10. Use of the Spin-Trapping method to establish the radical steps in the reactions of organic compounds of zinc, cadmium, and mercury with various peroxides

    SciTech Connect

    Dodonov, V.A.; Grishin, D.F.

    1985-06-01

    This paper uses the spin trapping method to investigate the homolytic reactions of group II organometallic compounds (OMC) with organic and heteroorganic peroxides. The radical reactions of the OMC with peroxides was investigated and the reactivity of the spin traps was examined with respect to compounds of zinc, cadmium, and mercury. Phenyl-tert-butylnitron (I), 2-methyl-2-nitrosopropane (II), and tri-bromonitrobenzene (III) were chosen as spin traps. The radicals formed are aable to initiate the polymerization of vinyl monomers.

  11. Transient and End Silicide Phase Formation in Thin Film Ni/polycrystalline-Si Reactions for Fully Silicided Gate Applications

    SciTech Connect

    Kittl,J.; Pawlak, M.; Torregiani, C.; Lauwers, A.; Demeurisse, C.; Vrancken, C.; Absil, P.; Biesemans, S.; Coia, C.; et. al

    2007-01-01

    The Ni/polycrystalline-Si thin film reaction was monitored by in situ x-ray diffraction during ramp annealings, obtaining a detailed view of the formation and evolution of silicide phases in stacks of interest for fully silicided gate applications. Samples consisted of Ni (30-170 nm)/polycrystalline-Si (100 nm)/SiO2 (10-30 nm) stacks deposited on (100) Si. The dominant end phase (after full silicidation) was found to be well controlled by the deposited Ni to polycrystalline-Si thickness ratio (tNi/tSi), with formation of NiSi2 ( {approx} 600 C), NiSi ( {approx} 400 C), Ni3Si2 ( {approx} 500 C), Ni2Si, Ni31Si12 ( {approx} 420 C), and Ni3Si ( {approx} 600 C) in stacks with tNi/tSi of 0.3, 0.6, 0.9, 1.2, 1.4, and 1.7, respectively. NiSi and Ni31Si12 were observed to precede formation of NiSi2 and Ni3Si, respectively, as expected for the phase sequence conventionally reported. Formation of Ni2Si was observed at early stages of the reaction. These studies revealed, in addition, the formation of transient phases that appeared and disappeared in narrow temperature ranges, competing with formation of the phases expected in the conventional phase sequence. These included the transient formation of NiSi and Ni31Si12 in stacks in which these phases are not expected to form (e.g., tNi/tSi of 1.7 and 0.9, respectively), at temperatures similar to those in which these phases normally grow.

  12. The Development and Application of Two-Chamber Reactors and Carbon Monoxide Precursors for Safe Carbonylation Reactions.

    PubMed

    Friis, Stig D; Lindhardt, Anders T; Skrydstrup, Troels

    2016-04-19

    , an array of low-pressure carbonylations were developed applying only near stoichiometric amounts of carbon monoxide. Importantly, carbon isotope variants of the CO precursors, such as (13)COgen, Sila(13)COgen, or even (14)COgen, provide a simple means for performing isotope-labeling syntheses. Finally, the COware applicability has been extended to reactions with other gases, such as hydrogen, CO2, and ethylene including their deuterium and (13)C-isotopically labeled versions where relevant. The COware system has been repeatedly demonstrated to be a valuable reactor for carrying out a wide number of transition metal-catalyzed transformations, and we believe this technology will have a significant place in many organic research laboratories.

  13. Vinyl Acetate Synthesis on Homogeneous and Heterogeneous Pd-Based Catalysts: A Theoretical Analysis on the Reaction Mechanisms#

    NASA Astrophysics Data System (ADS)

    Plata, José J.; García-Mota, Mónica; Braga, Ataualpa A. C.; López, Núria; Maseras, Feliu

    2009-09-01

    Vinyl acetate can be synthetized by both homogeneous and heterogeneous processes involving Pd atoms as reaction centers. We have determined the reaction mechanisms by means of density functional theory applied to molecular models for the homogeneous catalyst and to slabs that model the most active heterogeneous ensemble to unravel the similarities and differences in the reaction networks under these different conditions. We find that although the reaction network is similar, the rate determining step is different. Thus, direct extrapolations from organometallic chemistry to gas-phase heterogeneous catalysis should be handled with care.

  14. Ab initio modeling of the optical properties in organometallic halide perovskites for photovoltaic applications

    NASA Astrophysics Data System (ADS)

    Neukirch, Amanda; Nei, Wanyi; Pedesseau, Laurent; Even, Jacky; Katan, Claudine; Mohite, Aditya; Tretiak, Segrei

    2015-03-01

    The need for an inexpensive, clean, and plentiful source of energy has generated large amounts of research in an assortment of solution processed organic and hybrid organic-inorganic solar cells. A relative newcomer to the field of solution processed photovoltaics is the lead halide perovskite solar cell. In the past 5 years, the efficiencies of devices made from this material have increased from 3.5% to nearly 20%. Despite the rapid development of organic-inorganic perovskite solar cells, a thorough understanding of the fundamental photophysical processes driving the high performance of these devices is not well understood. I am using state-of-the-art ab initio computational techniques in order to characterize the properties at the interface of perovskite devices in order to aide in materials design and device engineering. I will present an in-depth analysis of the electronic and optical properties of bulk and surface states of pure and mixed halide systems. The high-level static quantum mechanical calculations, including spin-orbit-coupling and the many body GW approach, identify the key electronic states involved in photoinduced dynamics. This knowledge provides important information on how the optical properties change with variations to the system. Supported by the DOE, the LANL LDRD program XW11, and CNLS.

  15. Probing organometallic reactions by time-resolved infrared spectroscopy in solution and in the solid state using quantum cascade lasers.

    PubMed

    Calladine, James A; Horvath, Raphael; Davies, Andrew J; Wriglesworth, Alisdair; Sun, Xue-Zhong; George, Michael W

    2015-05-01

    The photochemistry and photophysics of metal carbonyl compounds (W(CO)6, Cp*Rh(CO)2 (Cp* = η(5)-C5Me5), and fac-[Re(CO)3(4,4'-bpy)2Br] [bpy = bipyridine]) have been examined on the nanosecond timescale using a time-resolved infrared spectrometer with an external cavity quantum cascade laser (QCL) as the infrared source. We show the photochemistry of W(CO)6 in alkane solution is easily monitored, and very sensitive measurements are possible with this approach, meaning it can monitor small transients with absorbance changes less than 10(-6) ΔOD. The C-H activation of Cp*Rh(CO)(C6H12) to form Cp*Rh(CO)(C6H11)H occurs within the first few tens of nanoseconds following photolysis, and we demonstrate that kinetics obtained following deconvolution are in excellent agreement with those measured using an ultrafast laser-based spectrometer. We also show that the high flux and tunability of QCLs makes them suited for solid-state and time-resolved measurements.

  16. Electron-Transfer Reactions of Organometallic and Coordination Compounds in the Absence of Solvent: Experimental Results and Theoretical Approaches

    DTIC Science & Technology

    1988-07-07

    OI C FILE COF AD-A 197 086 ). ... ENTA TION PAGE AD A 197 086 b. RESTRICTIVE MARKINGS L~ a. SECURITY CLASSIFICATION AUTH 3. DISTRIBUTION/ AV...and theoretically estimated factors are compared to experiment for a typical metallocene, ferrocene . (’ 20. DISTRIBUItuN/AVAILABILITY OF ABSTRACT 21...is examined, and theoretically estimated factors are ,’or compared to experiment for a typical metallocene, ferrocene . I L) I t *~6% ~ * ’." .-- 4

  17. Extension of a Kinetic Approach to Chemical Reactions to Electronic Energy Levels and Reactions Involving Charged Species With Application to DSMC Simulations

    NASA Technical Reports Server (NTRS)

    Liechty, Derek S.

    2013-01-01

    The ability to compute rarefied, ionized hypersonic flows is becoming more important as missions such as Earth reentry, landing high mass payloads on Mars, and the exploration of the outer planets and their satellites are being considered. Recently introduced molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties are extended in the current work to include electronic energy level transitions and reactions involving charged particles. These extensions are shown to agree favorably with reported transition and reaction rates from the literature for nearequilibrium conditions. Also, the extensions are applied to the second flight of the Project FIRE flight experiment at 1634 seconds with a Knudsen number of 0.001 at an altitude of 76.4 km. In order to accomplish this, NASA's direct simulation Monte Carlo code DAC was rewritten to include the ability to simulate charge-neutral ionized flows, take advantage of the recently introduced chemistry model, and to include the extensions presented in this work. The 1634 second data point was chosen for comparisons to be made in order to include a CFD solution. The Knudsen number at this point in time is such that the DSMC simulations are still tractable and the CFD computations are at the edge of what is considered valid because, although near-transitional, the flow is still considered to be continuum. It is shown that the inclusion of electronic energy levels in the DSMC simulation is necessary for flows of this nature and is required for comparison to the CFD solution. The flow field solutions are also post-processed by the nonequilibrium radiation code HARA to compute the radiative portion of the heating and is then compared to the total heating measured in flight.

  18. Extension of a Kinetic Approach to Chemical Reactions to Electronic Energy Levels and Reactions Involving Charged Species with Application to DSMC Simulations

    NASA Technical Reports Server (NTRS)

    Liechty, Derek S.

    2014-01-01

    The ability to compute rarefied, ionized hypersonic flows is becoming more important as missions such as Earth reentry, landing high mass payloads on Mars, and the exploration of the outer planets and their satellites are being considered. Recently introduced molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties are extended in the current work to include electronic energy level transitions and reactions involving charged particles. These extensions are shown to agree favorably with reported transition and reaction rates from the literature for near-equilibrium conditions. Also, the extensions are applied to the second flight of the Project FIRE flight experiment at 1634 seconds with a Knudsen number of 0.001 at an altitude of 76.4 km. In order to accomplish this, NASA's direct simulation Monte Carlo code DAC was rewritten to include the ability to simulate charge-neutral ionized flows, take advantage of the recently introduced chemistry model, and to include the extensions presented in this work. The 1634 second data point was chosen for comparisons to be made in order to include a CFD solution. The Knudsen number at this point in time is such that the DSMC simulations are still tractable and the CFD computations are at the edge of what is considered valid because, although near-transitional, the flow is still considered to be continuum. It is shown that the inclusion of electronic energy levels in the DSMC simulation is necessary for flows of this nature and is required for comparison to the CFD solution. The flow field solutions are also post-processed by the nonequilibrium radiation code HARA to compute the radiative portion.

  19. An effective rate equation approach to reaction kinetics in small volumes: theory and application to biochemical reactions in nonequilibrium steady-state conditions.

    PubMed

    Grima, R

    2010-07-21

    Chemical master equations provide a mathematical description of stochastic reaction kinetics in well-mixed conditions. They are a valid description over length scales that are larger than the reactive mean free path and thus describe kinetics in compartments of mesoscopic and macroscopic dimensions. The trajectories of the stochastic chemical processes described by the master equation can be ensemble-averaged to obtain the average number density of chemical species, i.e., the true concentration, at any spatial scale of interest. For macroscopic volumes, the true concentration is very well approximated by the solution of the corresponding deterministic and macroscopic rate equations, i.e., the macroscopic concentration. However, this equivalence breaks down for mesoscopic volumes. These deviations are particularly significant for open systems and cannot be calculated via the Fokker-Planck or linear-noise approximations of the master equation. We utilize the system-size expansion including terms of the order of Omega(-1/2) to derive a set of differential equations whose solution approximates the true concentration as given by the master equation. These equations are valid in any open or closed chemical reaction network and at both the mesoscopic and macroscopic scales. In the limit of large volumes, the effective mesoscopic rate equations become precisely equal to the conventional macroscopic rate equations. We compare the three formalisms of effective mesoscopic rate equations, conventional rate equations, and chemical master equations by applying them to several biochemical reaction systems (homodimeric and heterodimeric protein-protein interactions, series of sequential enzyme reactions, and positive feedback loops) in nonequilibrium steady-state conditions. In all cases, we find that the effective mesoscopic rate equations can predict very well the true concentration of a chemical species. This provides a useful method by which one can quickly determine the

  20. Surface organometallic chemistry on metals: Evidence for a new surface organometallic material Rh(Sn(C{sub 4}H{sub 9}){sub x}){sub y} obtained by controlled hydrogenolysis of Sn(C{sub 4}H{sub 9}){sub 4} on Rh/SiO{sub 2}

    SciTech Connect

    Didillon, B.; Clause, O.; Lefevbre, F.; Lamb, H.; Houtman, C.; Shay, T.; Candy, J.P.; Basset, J.M.

    1993-12-31

    It is shown that it is possible to graft organometallic fragments, namely Sn(C{sub 4}H{sub 9}){sub x}(x=1,2,3) at the surface of a rhodium particle supported on silica. These organometallic fragments are obtained by selective hydrogenolysis of Sn(C{sub 4}H{sub 9}){sub 4} on a Rhodium/silica catalyst. They are thermally stable on the particle up to a temperature of 423 K. The surface organometallic fragments have been characterized by micro-analytical data. Electron microscopy (CTEM and STEM), infrared spectroscopy, XPS Analysis, Moessbauer spectroscopy, MAS{sup 13}C NMR, EXAFS and molecular modeling. Depending on experimental conditions, it is possible to propose various surface structures for the organometallic fragments. However, the most likely fragment can be represented by the general formula: Rh{sub 8}Sn[Sn(C{sub 4}H{sub 9}){sub 3}]{sub 2}.