Automated building of organometallic complexes from 3D fragments.

Science.gov (United States)

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

2014-07-28

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

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

International Nuclear Information System (INIS)

Faucher, Nicolas

2000-01-01

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

Organometallic vapor-phase epitaxy theory and practice

CERN Document Server

Stringfellow, Gerald B

1989-01-01

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

Organometallic and Bioorganometallic Chemistry - Ferrocene and Metal Carbonyls

Directory of Open Access Journals (Sweden)

Čakić Semenčić, M.

2011-02-01

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

Organometallic Chemistry. Final Progress Report

Energy Technology Data Exchange (ETDEWEB)

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

2003-07-14

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

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

KAUST Repository

Bakr, Osman M.

2017-03-02

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

Organometallic chemistry of metal surfaces

International Nuclear Information System (INIS)

Muetterties, E.L.

1981-06-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

1996-09-05

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

Organometallic B12-DNA conjugate

DEFF Research Database (Denmark)

Hunger, Miriam; Mutti, Elena; Rieder, Alexander

2014-01-01

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

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

International Nuclear Information System (INIS)

Casey, C.P.

1994-07-01

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

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

KAUST Repository

Bakr, Osman; Shi, Dong

2016-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

Casey, C.P.

1994-07-01

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

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

KAUST Repository

Samantaray, Manoja

2015-08-18

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

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

KAUST Repository

Bakr, Osman; Peng, Wei; Wang, Lingfei

2017-01-01

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

DNA-based asymmetric organometallic catalysis in water

NARCIS (Netherlands)

Oelerich, Jens; Roelfes, Gerard

2013-01-01

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

Ligand Rearrangements of Organometallic Complexes inSolution

Energy Technology Data Exchange (ETDEWEB)

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

2006-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-03-07

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

Enthalpies of vaporization of organometallic compounds

International Nuclear Information System (INIS)

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

1987-01-01

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

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

Science.gov (United States)

Hoffmann, Norbert

2012-02-13

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

Organometallics Roundtable 2011

Energy Technology Data Exchange (ETDEWEB)

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

2012-01-09

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

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

Directory of Open Access Journals (Sweden)

Milene Adriane Luciano

2014-10-01

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

Two-Photon Absorption in Organometallic Bromide Perovskites

KAUST Repository

Walters, Grant

2015-07-21

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

Two-Photon Absorption in Organometallic Bromide Perovskites

KAUST Repository

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

2015-01-01

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

Basic organometallic chemistry: containing comprehensive bibliography

National Research Council Canada - National Science Library

Haiduc, Ionel; Zuckerman, Jerry J

1985-01-01

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

Hydrodeoxygenation of coal using organometallic catalyst precursors

Science.gov (United States)

Kirby, Stephen R.

2002-04-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-03-07

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

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

KAUST Repository

Poater, Albert

2013-03-15

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

Platinum-195 nuclear magnetic resonance of organometallic compounds

OpenAIRE

Ursini, Cleber Vinicius

1997-01-01

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

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

OpenAIRE

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

2002-01-01

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

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

Science.gov (United States)

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

2015-02-10

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

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

KAUST Repository

Bakr, Osman M.

2016-02-18

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

A review of the inorganic and organometallic chemistry of zirconium

International Nuclear Information System (INIS)

Kalvins, A.K.

1985-01-01

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

Fabrication of superconducting wire using organometallic precursors and infiltration

International Nuclear Information System (INIS)

Lee, Y.J.

1991-01-01

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

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

International Nuclear Information System (INIS)

1999-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2008-12-01

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

An Organometallic Future in Green and Energy Chemistry?

Energy Technology Data Exchange (ETDEWEB)

Crabtree, Robert H

2011-01-10

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

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

DEFF Research Database (Denmark)

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

2006-01-01

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

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

Science.gov (United States)

Badran, Hussain Ali

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

Functional Group Analysis.

Science.gov (United States)

Smith, Walter T., Jr.; Patterson, John M.

1984-01-01

Literature on analytical methods related to the functional groups of 17 chemical compounds is reviewed. These compounds include acids, acid azides, alcohols, aldehydes, ketones, amino acids, aromatic hydrocarbons, carbodiimides, carbohydrates, ethers, nitro compounds, nitrosamines, organometallic compounds, peroxides, phenols, silicon compounds,…

Identification of isomers of organometallic compounds

Energy Technology Data Exchange (ETDEWEB)

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

2015-06-15

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

Highvalent and organometallic technetium and rhenium compounds

International Nuclear Information System (INIS)

Oehlke, Elisabeth

2010-01-01

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

Organometallics and related molecules for energy conversion

CERN Document Server

Wong, Wai-Yeung

2015-01-01

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

Mew organometallic complexes of technetium in different oxidation states

International Nuclear Information System (INIS)

Joachim, J.E.

1993-09-01

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

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

NARCIS (Netherlands)

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

2015-01-01

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

Theory of Hydrogen Storage: A New Strategy within Organometallic Chemistry

Science.gov (United States)

Zhao, Yufeng

2006-03-01

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

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

Energy Technology Data Exchange (ETDEWEB)

Dr. Emilio Bunel

2011-07-15

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

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

Science.gov (United States)

Fujie, Tomoya; Hara, Takato; Kaji, Toshiyuki

2016-01-01

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

Volatile organometallic and semiconductor materials

International Nuclear Information System (INIS)

Dickson, R.S.

1991-01-01

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

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

KAUST Repository

Azzi, Joachim

2012-11-01

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

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

DEFF Research Database (Denmark)

Koleini, Mohammad; Paulsson, Magnus; Brandbyge, Mads

2007-01-01

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

Recent Applications of Polymer Supported Organometallic Catalysts in Organic Synthesis

Directory of Open Access Journals (Sweden)

Nina Kann

2010-09-01

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

Molecular orbital studies of the bonding in heavy element organometallics

International Nuclear Information System (INIS)

Bursten, B.E.

1990-01-01

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

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

International Nuclear Information System (INIS)

1999-01-01

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

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

Science.gov (United States)

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

2014-09-01

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

Interplay between experiments and calculations for organometallic clusters and caged clusters

International Nuclear Information System (INIS)

Nakajima, Atsushi

2015-01-01

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

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

NARCIS (Netherlands)

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

2013-01-01

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

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

International Nuclear Information System (INIS)

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

2001-01-01

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

Advanced polymer chemistry of organometallic anions

International Nuclear Information System (INIS)

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

1997-01-01

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

Synthesis, characterization and reactivity of some lanthanide organometallics

International Nuclear Information System (INIS)

Marchal, N.

1991-12-01

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

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

Science.gov (United States)

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

2018-03-21

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

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

Science.gov (United States)

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

2018-06-19

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

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

KAUST Repository

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

2013-01-01

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

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

KAUST Repository

Jantke, Dominik

2013-11-01

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

Sweetening ruthenium and osmium: organometallic arene complexes containing aspartame.

Science.gov (United States)

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

2008-09-01

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

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

Czech Academy of Sciences Publication Activity Database

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

2003-01-01

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

Organometallic compounds of the lanthanides, actinides and early transition metals

Energy Technology Data Exchange (ETDEWEB)

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

1985-01-01

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

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

KAUST Repository

Jeantelot, Gabriel

2014-05-01

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

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

NARCIS (Netherlands)

Bertrand, B.; Casini, A.

2014-01-01

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

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

NARCIS (Netherlands)

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

2015-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2008-02-16

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

Use of ionic liquids as coordination ligands for organometallic catalysts

Science.gov (United States)

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

2009-11-10

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

Mechanisms of inorganic and organometallic reactions

CERN Document Server

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

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

KAUST Repository

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

2014-01-01

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

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

KAUST Repository

Goswami, Subhadip

2014-12-18

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

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

Science.gov (United States)

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

2018-04-26

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

Formyl-ended heterobifunctional poly(ethylene oxide): synthesis of poly(ethylene oxide) with a formyl group at one end and a hydroxyl group at the other end.

Science.gov (United States)

Nagasaki, Y; Kutsuna, T; Iijima, M; Kato, M; Kataoka, K; Kitano, S; Kadoma, Y

1995-01-01

Well-defined poly(ethylene oxide) (PEO) with a formyl group at one end and a hydroxyl group at the other terminus was synthesized by the anionic ring opening polymerization of ethylene oxide (EO) with a new organometallic initiator possessing an acetal moiety, potassium 3,3-diethoxypropyl alkoxide. Hydrolysis of the acetal moiety produced a formyl group-terminated heterobifunctional PEO with a hydroxyl group at the other end.

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

KAUST Repository

Al-Shareef, Reem A.

2017-01-01

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

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

Science.gov (United States)

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

2018-06-28

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

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

International Nuclear Information System (INIS)

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

2006-01-01

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

The organometallic chemistry of neptunium

International Nuclear Information System (INIS)

Bohlander, R.

1986-09-01

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

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

CERN Document Server

Williams, J

1989-01-01

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

Structure of organometallic compounds obtained by plasma of titanium isopropoxide

International Nuclear Information System (INIS)

Arreola R, M. L.

2012-01-01

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

Organic or organometallic template mediated clay synthesis

Science.gov (United States)

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

1994-01-01

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

PREPARATION OF TANTALUM CARBIDE FROM AN ORGANOMETALLIC PRECURSOR

Directory of Open Access Journals (Sweden)

C. P. SOUZA

1999-03-01

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

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

Science.gov (United States)

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

2018-02-01

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

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

International Nuclear Information System (INIS)

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

2016-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-05-15

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

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

CERN Document Server

Ananikov, Valentin P

2014-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2012-12-15

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

Zigzag-shaped nickel nanowires via organometallic template-free route

Energy Technology Data Exchange (ETDEWEB)

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

2013-08-15

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

Phase Transition Enthalpy Measurements of Organic and Organometallic Compounds. Sublimation, Vaporization and Fusion Enthalpies From 1880 to 2015. Part 1. C1 - C10

Science.gov (United States)

Acree, William; Chickos, James S.

2016-09-01

A compendium of phase change enthalpies published in 2010 is updated to include the period 1880-2015. Phase change enthalpies including fusion, vaporization, and sublimation enthalpies are included for organic, organometallic, and a few inorganic compounds. Part 1 of this compendium includes organic compounds from C1 to C10. Part 2 of this compendium, to be published separately, will include organic and organometallic compounds from C11 to C192. Sufficient data are presently available to permit thermodynamic cycles to be constructed as an independent means of evaluating the reliability of the data. Temperature adjustments of phase change enthalpies from the temperature of measurement to the standard reference temperature, T = 298.15 K, and a protocol for doing so are briefly discussed.

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

Energy Technology Data Exchange (ETDEWEB)

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

2014-12-15

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

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

International Nuclear Information System (INIS)

Santos, Rodrigo Luis Silva Ribeiro

2007-01-01

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

Nitrogen doping of ZnSe by OMVPE using a novel organometallic precursor

International Nuclear Information System (INIS)

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

1994-01-01

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

Low-voltage organic field-effect transistors based on novel high-κ organometallic lanthanide complex for gate insulating materials

Directory of Open Access Journals (Sweden)

Qi Liu

2014-08-01

Full Text Available A novel high-κ organometallic lanthanide complex, Eu(tta3L (tta=2-thenoyltrifluoroacetonate, L = 4,5-pinene bipyridine, is used as gate insulating material to fabricate low-voltage pentacene field-effect transistors (FETs. The optimized gate insulator exhibits the excellent properties such as low leakage current density, low surface roughness, and high dielectric constant. When operated under a low voltage of −5 V, the pentacene FET devices show the attractive electrical performance, e.g. carrier mobility (μFET of 0.17 cm2 V−1 s−1, threshold voltage (Vth of −0.9 V, on/off current ratio of 5 × 103, and subthreshold slope (SS of 1.0 V dec−1, which is much better than that of devices obtained on conventional 300 nm SiO2 substrate (0.13 cm2 V−1 s−1, −7.3 V and 3.1 V dec−1 for μFET, Vth and SS value when operated at −30 V. These results indicate that this kind of high-κ organometallic lanthanide complex becomes a promising candidate as gate insulator for low-voltage organic FETs.

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

International Nuclear Information System (INIS)

Babiker, Musa Elaballa Mohamed

2000-01-01

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

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

Science.gov (United States)

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

2014-04-23

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

Synthesis and studies of some organometallic compounds of uranium IV

International Nuclear Information System (INIS)

Marquet-Ellis, Hubert; Folcher, Gerard.

1975-06-01

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

Naturally Efficient Emitters: Luminescent Organometallic Complexes Derived from Natural Products

Science.gov (United States)

Zhang, Wen-Hua; Young, David J.

2013-08-01

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

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

International Nuclear Information System (INIS)

Lu Mang; Wu Xuejiao; Zeng Decai; Liao Yong

2012-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2010-06-15

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

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

Science.gov (United States)

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

2018-01-01

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

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

DEFF Research Database (Denmark)

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

2011-01-01

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

Low-voltage organic field-effect transistors based on novel high-κ organometallic lanthanide complex for gate insulating materials

Energy Technology Data Exchange (ETDEWEB)

Liu, Qi; Li, Yi; Zhang, Yang; Song, You, E-mail: wangxzh@nju.edu.cn, E-mail: yli@nju.edu.cn, E-mail: yousong@nju.edu.cn; Wang, Xizhang, E-mail: wangxzh@nju.edu.cn, E-mail: yli@nju.edu.cn, E-mail: yousong@nju.edu.cn; Hu, Zheng [Key Laboratory of Mesoscopic Chemistry of MOE, Jiangsu Provincial Lab for Nanotechnology, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China. High-Tech Research Institute of Nanjing University (Suzhou), Suzhou 215123 (China); Sun, Huabin; Li, Yun, E-mail: wangxzh@nju.edu.cn, E-mail: yli@nju.edu.cn, E-mail: yousong@nju.edu.cn; Shi, Yi [School of Electronic Science and Engineering and Jiangsu Provincial Key Laboratory of Photonic and Electronic Materials, Nanjing University, Nanjing 210093 (China)

2014-08-15

A novel high-κ organometallic lanthanide complex, Eu(tta){sub 3}L (tta=2-thenoyltrifluoroacetonate, L = 4,5-pinene bipyridine), is used as gate insulating material to fabricate low-voltage pentacene field-effect transistors (FETs). The optimized gate insulator exhibits the excellent properties such as low leakage current density, low surface roughness, and high dielectric constant. When operated under a low voltage of −5 V, the pentacene FET devices show the attractive electrical performance, e.g. carrier mobility (μ{sub FET}) of 0.17 cm{sup 2} V{sup −1} s{sup −1}, threshold voltage (V{sub th}) of −0.9 V, on/off current ratio of 5 × 10{sup 3}, and subthreshold slope (SS) of 1.0 V dec{sup −1}, which is much better than that of devices obtained on conventional 300 nm SiO{sub 2} substrate (0.13 cm{sup 2} V{sup −1} s{sup −1}, −7.3 V and 3.1 V dec{sup −1} for μ{sub FET}, V{sub th} and SS value when operated at −30 V). These results indicate that this kind of high-κ organometallic lanthanide complex becomes a promising candidate as gate insulator for low-voltage organic FETs.

Synthesis of group 10 metal complexes with a new unsymmetrical PN3P-pincer ligand through ligand post-modification: Structure and reactivity

KAUST Repository

Wang, Xiufang

2017-01-01

A post-modification strategy are used to synthesize a new class of diimine-amido PN3P-pincer group-10 transition metal complexes. The coordination chemistry and the thermal stabilities of their organometallic derivatives are characterized and investigated.

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

Science.gov (United States)

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

2000-01-01

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

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

Science.gov (United States)

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

2018-05-31

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

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

International Nuclear Information System (INIS)

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

2008-01-01

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

The ab-initio density matrix renormalization group in practice

Energy Technology Data Exchange (ETDEWEB)

Olivares-Amaya, Roberto; Hu, Weifeng; Sharma, Sandeep; Yang, Jun; Chan, Garnet Kin-Lic [Department of Chemistry, Princeton University, Princeton, New Jersey 08544 (United States); Nakatani, Naoki [Department of Chemistry, Princeton University, Princeton, New Jersey 08544 (United States); Catalysis Research Center, Hokkaido University, Kita 21 Nishi 10, Sapporo, Hokkaido 001-0021 (Japan)

2015-01-21

The ab-initio density matrix renormalization group (DMRG) is a tool that can be applied to a wide variety of interesting problems in quantum chemistry. Here, we examine the density matrix renormalization group from the vantage point of the quantum chemistry user. What kinds of problems is the DMRG well-suited to? What are the largest systems that can be treated at practical cost? What sort of accuracies can be obtained, and how do we reason about the computational difficulty in different molecules? By examining a diverse benchmark set of molecules: π-electron systems, benchmark main-group and transition metal dimers, and the Mn-oxo-salen and Fe-porphine organometallic compounds, we provide some answers to these questions, and show how the density matrix renormalization group is used in practice.

The ab-initio density matrix renormalization group in practice.

Science.gov (United States)

Olivares-Amaya, Roberto; Hu, Weifeng; Nakatani, Naoki; Sharma, Sandeep; Yang, Jun; Chan, Garnet Kin-Lic

2015-01-21

The ab-initio density matrix renormalization group (DMRG) is a tool that can be applied to a wide variety of interesting problems in quantum chemistry. Here, we examine the density matrix renormalization group from the vantage point of the quantum chemistry user. What kinds of problems is the DMRG well-suited to? What are the largest systems that can be treated at practical cost? What sort of accuracies can be obtained, and how do we reason about the computational difficulty in different molecules? By examining a diverse benchmark set of molecules: π-electron systems, benchmark main-group and transition metal dimers, and the Mn-oxo-salen and Fe-porphine organometallic compounds, we provide some answers to these questions, and show how the density matrix renormalization group is used in practice.

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

Energy Technology Data Exchange (ETDEWEB)

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

2008-05-07

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

Study of two examples of non linear interaction of a laser wave with matter: laser-induced damage of dielectrics and non linear optical properties of organometallic molecules in solution

International Nuclear Information System (INIS)

Gaudry, Jean-Baptiste

2000-01-01

This research thesis reports the study of two mechanisms of non linear interaction of a laser wave with matter. More particularly, it reports the experimental investigation of non linear optical properties of organometallic molecules in solution, as well as the damage of perfect silica under laser irradiation by using simulation codes. As far as optical properties are concerned, the author highlights the influence of the electronic configuration of the metal present in the organometallic compound, and the influence of the ligand on the second-order non-linear response. As far as the simulation is concerned, some experimental results have been reproduced. This work can be useful for the investigation of the extrinsic damage of imperfect materials, and for the design of experiments of transient measurements of excited silica [fr

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

KAUST Repository

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

2016-01-01

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

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

KAUST Repository

Pump, Eva

2016-08-15

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

Mechanistic Studies at the Interface Between Organometallic Chemistry and Homogeneous Catalysis

Energy Technology Data Exchange (ETDEWEB)

Casey, Charles P

2012-11-14

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

Dissolved oxygen sensing using organometallic dyes deposited within a microfluidic environment

Science.gov (United States)

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

2008-02-01

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

Phase Transition Enthalpy Measurements of Organic and Organometallic Compounds and Ionic Liquids. Sublimation, Vaporization, and Fusion Enthalpies from 1880 to 2015. Part 2. C11-C192

Science.gov (United States)

Acree, William; Chickos, James S.

2017-03-01

The second part of this compendium concludes with a collection of phase change enthalpies of organic molecules inclusive of C11-C192 reported over the period 1880-2015. Also included are phase change enthalpies including fusion, vaporization, and sublimation enthalpies for organometallic, ionic liquids, and a few inorganic compounds. Paper I of this compendium, published separately, includes organic compounds from C1 to C10 and describes a group additivity method for evaluating solid, liquid, and gas phase heat capacities as well as temperature adjustments of phase changes. Paper II of this compendium also includes an updated version of a group additivity method for evaluating total phase change entropies which together with the fusion temperature can be useful in estimating total phase change enthalpies. Other uses include application in identifying potential substances that either form liquid or plastic crystals or exhibit additional phase changes such as undetected solid-solid transitions or behave anisotropically in the liquid state.

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

International Nuclear Information System (INIS)

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

2012-01-01

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

High-Permeability Magnetic Polymer Additives for Lightweight Electromagnetic Shielding

Science.gov (United States)

2015-08-01

incorporation) or chemical incorporation as part of the polymer chain backbone or linked as pendant groups.13 Many transition-metal organometallic...10.1002/9781119951438. 15. Poli R. Open-shell organometallics as a bridge between Werner-type and low-valent organometallic complexes: the effect

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

Directory of Open Access Journals (Sweden)

M. Masteri-Farahani

2015-10-01

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

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

International Nuclear Information System (INIS)

Barros, N.

2007-06-01

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

Organometallic Routes into the Nanorealms of Binary Fe-Si Phases

Directory of Open Access Journals (Sweden)

Teddy M. Keller

2010-02-01

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

Air-tolerant C–C bond formation via organometallic ruthenium catalysis: diverse catalytic pathways involving (C5Me5)Ru or (C5H5)Ru are robust to molecular oxygen

Czech Academy of Sciences Publication Activity Database

Severa, Lukáš; Vávra, Jan; Kohoutová, Anna; Čížková, Martina; Šálová, Tereza; Hývl, Jakub; Šaman, David; Pohl, Radek; Adriaenssens, Louis; Teplý, Filip

2009-01-01

Roč. 50, č. 31 (2009), s. 4526-4528 ISSN 0040-4039 Institutional research plan: CEZ:AV0Z40550506 Keywords : ruthenium * organometallic catalysis * [2+2+2] cycloaddition * terminal alkynes Subject RIV: CC - Organic Chemistry Impact factor: 2.660, year: 2009

CVD of SiC and AlN using cyclic organometallic precursors

Science.gov (United States)

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

1992-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2008-04-30

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

Protective Actions of 17β-Estradiol and Progesterone on Oxidative Neuronal Injury Induced by Organometallic Compounds

Directory of Open Access Journals (Sweden)

Yasuhiro Ishihara

2015-01-01

Full Text Available Steroid hormones synthesized in and secreted from peripheral endocrine glands pass through the blood-brain barrier and play a role in the central nervous system. In addition, the brain possesses an inherent endocrine system and synthesizes steroid hormones known as neurosteroids. Increasing evidence shows that neuroactive steroids protect the central nervous system from various harmful stimuli. Reports show that the neuroprotective actions of steroid hormones attenuate oxidative stress. In this review, we summarize the antioxidative effects of neuroactive steroids, especially 17β-estradiol and progesterone, on neuronal injury in the central nervous system under various pathological conditions, and then describe our recent findings concerning the neuroprotective actions of 17β-estradiol and progesterone on oxidative neuronal injury induced by organometallic compounds, tributyltin, and methylmercury.

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

KAUST Repository

Espinas, Jeff

2012-11-12

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

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

KAUST Repository

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

2012-01-01

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

Effects of organometallic chelates and inulin in diets for laying hens on Mn and Fe absorption coefficients and their content in egg and tissue

Directory of Open Access Journals (Sweden)

Cornescu Gabriela Maria

2015-01-01

Full Text Available The aim of this study was to evaluate effects of organic sources of manganese (Mn and iron (Fe and inulin in diets for laying hens on absorption of these minerals and their deposition in egg and tissue. The study was conducted on 90 Lohmann Brown laying hens in the period from 46-52 weeks of age, assigned to 3 groups with 30 hens/group and 3 hens/cage. The hens from the control group (C received a diet based on corn, rice bran and soybean meal with 16% of crude protein, as well as 60 mg Fe/kg and 71.9 mg Mn/kg of diet in form of inorganic salts. The formulation of the experimental diets (E1 and E2 differed from C group diet by the replacement of inorganic Fe and Mn salts by organometallic chelates of these elements, at a level of 25% lower than in the premix for group C. As source of inulin, group E1 diet also included 0.5% of dry Jerusalem artichoke, while group E2 diet included 0.5% of a product based on chicory root extract. At the end of the experiment, 6 hens from each group were slaughtered and blood serum and liver samples were collected and assayed for concentration of Fe and Mn. In the final week of the experiment, 18 eggs/group were collected for determination of Fe and Mn concentration in egg yolk. Concentration of measured blood serum parameters (haemoglobin, haematocrit, Fe and Mn in experimental (E groups were lower than in group C, but no significant differences (P>0.05 were registered. Absorption coefficients of Mn had higher values in E groups than in group C, with significant increase (P0.05 between groups were observed for Mn and Fe concentration in egg yolk.

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

Science.gov (United States)

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

2014-03-01

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

Well-Defined Molybdenum Oxo Alkyl Complex Supported on Silica by Surface Organometallic Chemistry: A Highly Active Olefin Metathesis Precatalyst

KAUST Repository

Merle, Nicolas; Le Qué mé ner, Fré dé ric; Bouhoute, Yassine; Szeto, Kai C.; De Mallmann, Aimery; Barman, Samir; Samantaray, Manoja; Delevoye, Laurent; Gauvin, Ré gis M.; Taoufik, Mostafa; Basset, Jean-Marie

2016-01-01

The well-defined silica-supported molybdenum oxo alkyl species (SiO−)MoO(CH Bu) was selectively prepared by grafting of MoO(CH Bu)Cl onto partially dehydroxylated silica (silica) using the surface organometallic chemistry approach. This surface species was fully characterized by elemental analysis and DRIFT, solid-state NMR, and EXAFS spectroscopy. This new material is related to the active species of industrial supported MoO/SiO olefin metathesis catalysts. It displays very high activity in propene self-metathesis at mild (turnover number = 90 000 after 25 h). Remarkably, its catalytic performance outpaces those of the parent imido derivative and its tungsten oxo analogue.

Well-Defined Molybdenum Oxo Alkyl Complex Supported on Silica by Surface Organometallic Chemistry: A Highly Active Olefin Metathesis Precatalyst

KAUST Repository

Merle, Nicolas

2016-12-05

The well-defined silica-supported molybdenum oxo alkyl species (SiO−)MoO(CH Bu) was selectively prepared by grafting of MoO(CH Bu)Cl onto partially dehydroxylated silica (silica) using the surface organometallic chemistry approach. This surface species was fully characterized by elemental analysis and DRIFT, solid-state NMR, and EXAFS spectroscopy. This new material is related to the active species of industrial supported MoO/SiO olefin metathesis catalysts. It displays very high activity in propene self-metathesis at mild (turnover number = 90 000 after 25 h). Remarkably, its catalytic performance outpaces those of the parent imido derivative and its tungsten oxo analogue.

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

Science.gov (United States)

Serna, Pedro; Gates, Bruce C

2014-08-19

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

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

Science.gov (United States)

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

2009-04-07

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2004-05-01

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

The use of a well-defined surface organometallic complex as a probe molecule: [(≡SiO)TaVCl2Me2] shows different isolated silanol sites on the silica surface

KAUST Repository

Chen, Yin

2014-01-01

TaVCl2Me3 reacts with silica(700) and produces two different [(≡SiO)TaVCl2Me2] surface organometallic species, suggesting a heterogeneity of the highly dehydroxylated silica surface, which was studied with a combined experimental and theoretical approach. This journal is © the Partner Organisations 2014.

Synthesis of a sugar-organometallic compound 1,1′-difurfurylferrocene and its microwave preparation of carbon/iron oxide nanocomposite

International Nuclear Information System (INIS)

Zhao Shanyu; Cooper, Daniel C.; Xu, Haixun; Zhu Pinghua; Suggs, J. William

2013-01-01

Graphical abstract: In order to synthesize a carbon–metal or metal oxide combination sphere, carbonaceous resource furfural was introduced, which was nucleophilic treated with 1,1′-dilithioferrocene to form a sugar-organometallic compound: ferrocenyl monosaccharide derivative 1,1′-difurfurylferrocene, which can be hydrothermally treated in a microwave reactor to give 300–500 nm microspheres with the α-Fe 2 O 3 or Fe 3 O 4 formed on the surface, which may be favorable for new magnetic materials preparation or instead of iron with other metal ions, versatile carbon/metal composites will be possibly synthesized for catalysis, drug delivery and magnetic uses. Highlights: ► We synthesized 1,1′-difurfurylferrocene by nucleophilic treating furfural with 1,1′-dilithioferrocene. ► 1,1′-Difurfurylferrocene can be hydrothermally treated by microwave to give microspheres with iron oxides on the surface. ► 1,1′-Difurfurylferrocene has 2 reactive furanose units, which form carbonspheres and ferrocenyl can give iron oxides. ► REDOX atmosphere influences the coating structures. - Abstract: In order to synthesize a carbon–metal or metal oxide combination sphere, carbonaceous resource furfural 1 was introduced, which was nucleophilic treated with 1,1′-dilithioferrocene 2 to form a sugar-organometallic compound: ferrocenyl monosaccharide derivative 1,1′-difurfurylferrocene 3. 1,1′-Difurfurylferrocene 3 can be hydrothermally treated in a microwave reactor to give 300–500 nm microspheres with the α-Fe 2 O 3 or Fe 3 O 4 nanocrystals formed on the surface, which may be favorable for new magnetic materials preparation or instead of iron with other metal ions, versatile carbon/metal composites will be possibly synthesized for catalysis, drug delivery and magnetic uses.

Synthesis of a sugar-organometallic compound 1,1 Prime -difurfurylferrocene and its microwave preparation of carbon/iron oxide nanocomposite

Energy Technology Data Exchange (ETDEWEB)

Zhao Shanyu, E-mail: syzhao65@gmail.com [School of Environmental and Safty Engineering, Changzhou University, Changzhou, Jiangsu 213164 (China); Department of Chemistry, Brown University, Providence, RI 02912-9108 (United States); Cooper, Daniel C. [Department of Chemistry, Brown University, Providence, RI 02912-9108 (United States); Xu, Haixun [Institute of Building Materials, Dalian University of Technology, Dalian, Liaoning 116024 (China); Zhu Pinghua [School of Environmental and Safty Engineering, Changzhou University, Changzhou, Jiangsu 213164 (China); Suggs, J. William, E-mail: j_suggs@brown.edu [Department of Chemistry, Brown University, Providence, RI 02912-9108 (United States)

2013-01-01

Graphical abstract: In order to synthesize a carbon-metal or metal oxide combination sphere, carbonaceous resource furfural was introduced, which was nucleophilic treated with 1,1 Prime -dilithioferrocene to form a sugar-organometallic compound: ferrocenyl monosaccharide derivative 1,1 Prime -difurfurylferrocene, which can be hydrothermally treated in a microwave reactor to give 300-500 nm microspheres with the {alpha}-Fe{sub 2}O{sub 3} or Fe{sub 3}O{sub 4} formed on the surface, which may be favorable for new magnetic materials preparation or instead of iron with other metal ions, versatile carbon/metal composites will be possibly synthesized for catalysis, drug delivery and magnetic uses. Highlights: Black-Right-Pointing-Pointer We synthesized 1,1 Prime -difurfurylferrocene by nucleophilic treating furfural with 1,1 Prime -dilithioferrocene. Black-Right-Pointing-Pointer 1,1 Prime -Difurfurylferrocene can be hydrothermally treated by microwave to give microspheres with iron oxides on the surface. Black-Right-Pointing-Pointer 1,1 Prime -Difurfurylferrocene has 2 reactive furanose units, which form carbonspheres and ferrocenyl can give iron oxides. Black-Right-Pointing-Pointer REDOX atmosphere influences the coating structures. - Abstract: In order to synthesize a carbon-metal or metal oxide combination sphere, carbonaceous resource furfural 1 was introduced, which was nucleophilic treated with 1,1 Prime -dilithioferrocene 2 to form a sugar-organometallic compound: ferrocenyl monosaccharide derivative 1,1 Prime -difurfurylferrocene 3. 1,1 Prime -Difurfurylferrocene 3 can be hydrothermally treated in a microwave reactor to give 300-500 nm microspheres with the {alpha}-Fe{sub 2}O{sub 3} or Fe{sub 3}O{sub 4} nanocrystals formed on the surface, which may be favorable for new magnetic materials preparation or instead of iron with other metal ions, versatile carbon/metal composites will be possibly synthesized for catalysis, drug delivery and magnetic uses.

Investigation of Spectral Characteristics of Pulsed Xenon Lamps for Combined Photochemical Degradation of Organometallic Compounds in Liquid Radioactive Waste

Directory of Open Access Journals (Sweden)

M. A. Mishakov

2017-01-01

Full Text Available The paper considers the composition of liquid radioactive wastes from the nuclear plants. Using traditional ways to extract organometallic compounds formed, when using the deactivation solutions to clean the surfaces of nuclear plant rooms, are complicated. The paper studies the edge-cutting methods of solving this problem. Its proposal is to use a combined ultraviolet treatment for organometallic compounds degradation based on ethylenediaminetetraacetic acid (EDTA via pulsed xenon lamps. A potential use of the tubular and spherical geometry lamps is examined and advantages, disadvantages and features of these lamps are described. Instead of the pure EDTA the experiments used its disodium salt (Na2-EDTA. The hydrogen peroxide was used as an extra oxidizer. Absorption spectrums of solutions with various Na2-EDTA - hydrogen peroxide ratio were measured. It is found that the absorbance curve maximum is in the shortwave spectrum region (λ < 210 nm. The use of amalgam lamps of monochromatic radiation at wavelength λ = 254 nm will result only in formation of hydroxyl radicals but direct destruction processes of EDTA molecules due to radiation will be rare, and this decreases efficiency of their use.The spectral radiation characteristics of various continuum spectrum pulsed xenon lamps was measured. The experimental data expressed in relative units were compared with the emission spectrum of an absolutely black body. The paper shows that in spherical lamps high brightness temperature can be reached. Thus, in spherical lamps it is possible to obtain a spectrum, which is in maximum correlation with the absorption spectrum of the solutions under study, thereby making them a prospective radiation source for photo-degradation of EDTA compounds. For drawing a final conclusion it is necessary to conduct researches in order to compare Na2-EDTA degradation via tubular and spherical xenon lamps.

Lattice site location of optical centers in GaN:Eu light emitting diode material grown by organometallic vapor phase epitaxy

KAUST Repository

Lorenz, K.; Alves, E.; Roqan, Iman S.; O’ Donnell, K. P.; Nishikawa, A.; Fujiwara, Y.; Boćkowski, M.

2010-01-01

Eu-doped GaN was grown by organometallic vapor phase epitaxy at temperatures from 900 to 1100 °C. Eu incorporation is influenced by temperature with the highest concentration found for growth at 1000 °C. In all samples, Eu is incorporated entirely on substitutional Ga sites with a slight displacement which is highest (∼0.2 Å) in the sample grown at 900 °C and mainly directed along the c-axis. The major optical Eu3+ centers are identical for in situdoped and ion-implanted samples after high temperature and pressure annealing. The dominant Eu3+luminescence lines are attributed to isolated, substitutional Eu.

Lattice site location of optical centers in GaN:Eu light emitting diode material grown by organometallic vapor phase epitaxy

KAUST Repository

Lorenz, K.

2010-09-16

Eu-doped GaN was grown by organometallic vapor phase epitaxy at temperatures from 900 to 1100 °C. Eu incorporation is influenced by temperature with the highest concentration found for growth at 1000 °C. In all samples, Eu is incorporated entirely on substitutional Ga sites with a slight displacement which is highest (∼0.2 Å) in the sample grown at 900 °C and mainly directed along the c-axis. The major optical Eu3+ centers are identical for in situdoped and ion-implanted samples after high temperature and pressure annealing. The dominant Eu3+luminescence lines are attributed to isolated, substitutional Eu.

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

International Nuclear Information System (INIS)

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

1990-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2011-09-15

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

Chemistry of the Colloidal Group II-VI Nanocrystal Synthesis

Energy Technology Data Exchange (ETDEWEB)

Liu, Haitao [Univ. of California, Berkeley, CA (United States)

2007-05-17

In the last two decades, the field of nanoscience andnanotechnology has witnessed tremendous advancement in the synthesis andapplication of group II-VI colloidal nanocrystals. The synthesis based onhigh temperature decomposition of organometallic precursors has becomeone of the most successful methods of making group II-VI colloidalnanocrystals. This methodis first demonstrated by Bawendi and coworkersin 1993 to prepare cadmium chalcogenide colloidal quantum dots and laterextended by others to prepare other group II-VI quantum dots as well asanisotropic shaped colloidal nanocrystals, such as nanorod and tetrapod.This dissertation focuses on the chemistry of this type of nanocrystalsynthesis. The synthesis of group II-VI nanocrystals was studied bycharacterizing the molecular structures of the precursors and productsand following their time evolution in the synthesis. Based on theseresults, a mechanism was proposed to account for the 2 reaction betweenthe precursors that presumably produces monomer for the growth ofnanocrystals. Theoretical study based on density functional theorycalculations revealed the detailed free energy landscape of the precursordecomposition and monomerformation pathway. Based on the proposedreaction mechanism, a new synthetic method was designed that uses wateras a novel reagent to control the diameter and the aspect ratio of CdSeand CdS nanorods.

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

Energy Technology Data Exchange (ETDEWEB)

Arreola R, M. L.

2012-07-01

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

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

Directory of Open Access Journals (Sweden)

Eric Monflier

2012-11-01

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

Synthesis and purification of some main group organometallic ...

Indian Academy of Sciences (India)

Unknown

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

Neutron radiation characteristics of the IVth generation reactor spent fuel

Science.gov (United States)

Bedenko, Sergey; Shamanin, Igor; Grachev, Victor; Knyshev, Vladimir; Ukrainets, Olesya; Zorkin, Andrey

2018-03-01

Exploitation of nuclear power plants as well as construction of new generation reactors lead to great accumulation of spent fuel in interim storage facilities at nuclear power plants, and in spent fuel «wet» and «dry» long-term storages. Consequently, handling the fuel needs more attention. The paper is focused on the creation of an efficient computational model used for developing the procedures and regulations of spent nuclear fuel handling in nuclear fuel cycle of the new generation reactor. A Thorium High-temperature Gas-Cooled Reactor Unit (HGTRU, Russia) was used as an object for numerical research. Fuel isotopic composition of HGTRU was calculated using the verified code of the MCU-5 program. The analysis of alpha emitters and neutron radiation sources was made. The neutron yield resulting from (α,n)-reactions and at spontaneous fission was calculated. In this work it has been shown that contribution of (α,n)-neutrons is insignificant in case of such (Th,Pu)-fuel composition and HGTRU operation mode, and integral neutron yield can be approximated by the Watt spectral function. Spectral and standardized neutron distributions were achieved by approximation of the list of high-precision nuclear data. The distribution functions were prepared in group and continuous form for further use in calculations according to MNCP, MCU, and SCALE.

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

International Nuclear Information System (INIS)

Aly, K.I.

2005-01-01

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

Size distribution of silver nanoclusters induced by ion, electron, laser beams and thermal treatments of an organometallic precursor

International Nuclear Information System (INIS)

D'Urso, L.; Nicolosi, V.; Compagnini, G.; Puglisi, O.

2004-01-01

Recently, a huge variety of physical and chemical synthetic processes have been reported to prepare nanostructured materials made of very small (diameter<50 nm) metallic clusters. Depending on the nature of clusters, this new kind of materials posses interesting properties (electronic, optical, magnetic, catalytic) that can be tailored as a function of the particles size and shape. Silver nanoparticles have been obtained by direct thermal treatment or by beam-enhanced decomposition (ion, electron and laser) of a silver organometallic compound (precursor) spinned onto suitable substrates. In this paper, we present the results of a study on the size distribution of such nanoparticles as a function of the different synthesis methods. It was found that the methods employed strongly affect the silver nanoparticles formation. Smaller silver nanoclusters were obtained after reduction by ion beam irradiation and thermal treatment, as observed by using different techniques (AFM, XRD and UV-Vis)

The use of a well-defined surface organometallic complex as a probe molecule: [(≡SiO)Ta^VCl₂Me₂] shows different isolated silanol sites on the silica surface

KAUST Repository

Chen, Yin; Zheng, Bin; Abou-Hamad, Edy; Hamieh, Ali Imad Ali; Hamzaoui, Bilel; Huang, Kuo-Wei; Basset, Jean-Marie

2014-01-01

TaVCl2Me3 reacts with silica(700) and produces two different [(≡SiO)TaVCl2Me2] surface organometallic species, suggesting a heterogeneity of the highly dehydroxylated silica surface, which was studied with a combined experimental and theoretical approach. This journal is © the Partner Organisations 2014.

Chemistry of the Colloidal Group II-VI Nanocrystal Synthesis

International Nuclear Information System (INIS)

Liu, Haitao

2007-01-01

In the last two decades, the field of nanoscience and nanotechnology has witnessed tremendous advancement in the synthesis and application of group II-VI colloidal nanocrystals. The synthesis based on high temperature decomposition of organometallic precursors has become one of the most successful methods of making group II-VI colloidal nanocrystals. This method is first demonstrated by Bawendi and coworkers in 1993 to prepare cadmium chalcogenide colloidal quantum dots and later extended by others to prepare other group II-VI quantum dots as well as anisotropic shaped colloidal nanocrystals, such as nanorod and tetrapod. This dissertation focuses on the chemistry of this type of nanocrystal synthesis. The synthesis of group II-VI nanocrystals was studied by characterizing the molecular structures of the precursors and products and following their time evolution in the synthesis. Based on these results, a mechanism was proposed to account for the 2 reaction between the precursors that presumably produces monomer for the growth of nanocrystals. Theoretical study based on density functional theory calculations revealed the detailed free energy landscape of the precursor decomposition and monomer formation pathway. Based on the proposed reaction mechanism, a new synthetic method was designed that uses water as a novel reagent to control the diameter and the aspect ratio of CdSe and CdS nanorods

Conception, characterization and evaluation of new radiotracers for diagnosis and treatment of breast and prostate cancers

International Nuclear Information System (INIS)

Dallagi, T.

2010-01-01

The medicinal and organometallic chemistry group of the Charles Friedel Laboratory has been developing therapeutic approaches based on organometallic compounds for many years. It has been found that these compounds may be used as cytotoxic agents or as radiopharmaceuticals for the treatment or diagnosis of diseases. The goal of the present work is the synthesis of organometallic analogs of biological substances (such as drugs) bearing a ferrocenyl, cymantrenyl, cerhetrenyl, or cyclo-pentadienyl-tricarbonyl-technetium group. We have especially focused our research on the preparation of Tc-99m derivatives and their purification. We have found suitable methods which are easy to handle and give high yields and high specific activities. These technetium compounds have been used for the study of in vivo biodistribution in animals. (author)

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

International Nuclear Information System (INIS)

Clavaud, C.

2006-02-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2008-01-01

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

Iron selenide films by aerosol assisted chemical vapor deposition from single source organometallic precursor in the presence of surfactants

Energy Technology Data Exchange (ETDEWEB)

Hussain, Raja Azadar [Department of Chemistry, Quaid-i-Azam University, 45320 Islamabad (Pakistan); Badshah, Amin, E-mail: aminbadshah@yahoo.com [Department of Chemistry, Quaid-i-Azam University, 45320 Islamabad (Pakistan); Younis, Adnan [School of Materials Science and Engineering, University of New South Wales, Sydney 2052, NSW (Australia); Khan, Malik Dilshad [Department of Chemistry, Quaid-i-Azam University, 45320 Islamabad (Pakistan); Akhtar, Javeed [Department of Physics, COMSATS Institute of Information Technology, Park Road, Chak Shahzad, Islamabad (Pakistan)

2014-09-30

This article presents the synthesis and characterization (multinuclear nuclear magnetic resonance, Fourier transform infrared spectroscopy, carbon–hydrogen–nitrogen–sulfur analyzer, atomic absorption spectrometry and thermogravimetric analysis) of a single source organometallic precursor namely 1-acetyl-3-(4-ferrocenylphenyl)selenourea for the fabrication of iron selenide (FeSe) films on glass substrates using aerosol assisted chemical vapor deposition (AACVD). The changes in the morphologies of the films have been monitored by the use of two different surfactants i.e. triton X-100 and tetraoctylphosphonium bromide during AACVD. The role of surfactant has been evaluated by examining the interaction of the surfactants with the precursor by using UV–vis spectroscopy and cyclic voltammetry. The fabricated FeSe films have been characterized with powder X-ray diffraction, scanning electron microscopy and energy dispersive spectroscopy. - Highlights: • Ferrocene incorporated selenourea (FIS) has been synthesized and characterized. • FeSe thin films have been fabricated from FIS. • Mechanism of film growth was studied with cyclic voltammetry and UV–vis spectroscopy.

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

Science.gov (United States)

Wong, Wai-Yeung; Ho, Cheuk-Lam

2010-09-21

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

Cambio de propiedades fisicoquímicas y químicas de los tepetates producidos en corto y mediano plazo por el cultivo.

OpenAIRE

Pajares, Silvia; Covaleda, Sara; Gallardo, Juan F.; Padilla C., Juliana; Etchevers, Jorge D.

2006-01-01

IVth INTERNATIONAL SYMPOSIUM ON DETERIORATED VOLCANIC SOILS (ISVO’06) (Use and Management of Tepetates, Talpetates, Cangahuas, Trumaos, etc.) July, 1 to 8, 2006 in Morelia, State of Michoacán and Tlaxcala, State of Tlaxcala, MEXICO

Characterization of B-H agostic compounds involved in the dehydrogenation of amine-boranes by group 4 metallocenes.

Science.gov (United States)

Zhu, Jingwen; Zins, Emilie-Laure; Alikhani, Mohammad Esmaïl

2016-12-01

For over a decade, amine-borane has been considered as a potential chemical hydrogen vector in the context of a search for cleaner energy sources. When catalyzed by organometallic complexes, the reaction mechanisms currently considered involve the formation of β-BH agostic intermediates. A thorough understanding of these intermediates may constitute a crucial step toward the identification of ideal catalysts. Topological approaches such as QTAIM and ELF revealed to be particularly suitable for the description of β-agostic interactions. When studying model catalysts, accurate theoretical calculations may be carried out. However, for a comparison with experimental data, calculations should also be carried out on large organo-metallic species, often including transition metals belonging to the second or the third row. In such a case, DFT methods are particularly attractive. Unfortunately, triple-ζ all electrons basis sets are not easily available for heavy transition metal elements. Thus, a subtle balance should be reached between the affordable level of calculations and the required accuracy of the electronic description of the systems. Herein we propose the use of B3LYP functional in combination with the LanL2DZ pseudopotential for the metal atom and 6-311++G(2d,2p) basis set for the other atoms, followed by a single point using the DKH2 relativistic Hamiltonian in combination with the B3LYP/DZP-DKH level, as a "minimum level of theory" leading to a consistent topological description of the interaction within the ELF and QTAIM framework, in the context of isolated (gas-phase) group 4 metallocene catalysts.

Growth and physicochemical properties of organometallic (DL)-trithioureatartrato-O1,O2,O3-cadmium(II) single crystals

Science.gov (United States)

Sathyamoorthy, K.; Vinothkumar, P.; Irshad Ahamed, J.; Murali Manohar, P.; Priya, M.; Liu, Jinghe

2018-04-01

Single crystals of organometallic (DL)-trithioureatartrato-O1,O2,O3-cadmium(II) (TUDLC) have been grown from methanol solution by using the slow evaporation of solvent growth technique. The lattice structure and crystalline perfection have been determined by carrying out single crystal X-ray diffraction and high resolution X-ray diffraction measurements. The grown crystal was characterized thermally and mechanically by carrying out thermo-gravimetric and micro hardness measurements. The linear and nonlinear optical characterizations were made by carrying out optical transmittance, surface laser damage threshold, particle size-dependent second harmonic generation (SHG) efficiency and photo conductivity measurements. The grown crystal was electrically characterized by carrying out frequency-dependent dielectric measurements. Chemical etching study was also carried out and the dislocation density was estimated. Results obtained in the present study indicate that the grown TUDLC crystal is optically transparent with lower cut-off wavelength 304 nm, mechanically soft, thermally stable up to 101 °C and NLO active with SHG efficiency 2.13 (in KDP unit). The grown crystal is found to have considerably large size, good crystalline perfection, large specific heat capacity, higher surface laser damage threshold and negative photoconductivity.

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

Energy Technology Data Exchange (ETDEWEB)

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

2015-07-15

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

Growth and optical characteristics of Tm-doped AlGaN layer grown by organometallic vapor phase epitaxy

Science.gov (United States)

Takatsu, J.; Fuji, R.; Tatebayashi, J.; Timmerman, D.; Lesage, A.; Gregorkiewicz, T.; Fujiwara, Y.

2018-04-01

We report on the growth and optical properties of Tm-doped AlGaN layers by organometallic vapor phase epitaxy (OMVPE). The morphological and optical properties of Tm-doped GaN (GaN:Tm) and Tm-doped AlGaN (AlGaN:Tm) were investigated by Nomarski differential interference contrast microscopy and photoluminescence (PL) characterization. Nomarski images reveal an increase of surface roughness upon doping Tm into both GaN and AlGaN layers. The PL characterization of GaN:Tm shows emission in the near-infrared range originating from intra-4f shell transitions of Tm3+ ions. In contrast, AlGaN:Tm also exhibits blue light emission from Tm3+ ions. In that case, the wider band gap of the AlGaN host allows energy transfer to higher states of the Tm3+ ions. With time-resolved PL measurements, we could distinguish three types of luminescent sites of Tm3+ in the AlGaN:Tm layer, having different decay times. Our results confirm that Tm ions can be doped into GaN and AlGaN by OMVPE, and show potential for the fabrication of novel high-color-purity blue light emitting diodes.

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

KAUST Repository

Bendjeriou-Sedjerari, Anissa

2013-11-27

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

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

KAUST Repository

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

2013-01-01

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

The synthesis of CdSe quantum dots with carboxyl group and study on their optical characteristics

International Nuclear Information System (INIS)

Ye, Chen; Park, Sangjoon; Kim, Jongsung

2009-01-01

Quantum dots are nanocrystal semiconductors which attract lots of research interests due to their peculiar optical properties. CdSe/ZnS quantum dots have been synthesized via pyrolysis of organometallic reagents. The color of the quantum dot changes from yellow-green to red as their size increases with reaction time. Photoluminescence quantum efficiency of CdSe quantum dots have been enhanced by passivating the surface of CdSe quantum dots with ZnS layers. Quantum dots are nanocrystal semiconductors which attract lots of research interests due to their peculiar optical properties. CdSe/ZnS quantum dots have been synthesized via pyrolysis of organometallic reagents. The color of the quantum dot changes from yellow-green to red as their size increases with reaction time. Photoluminescence quantum efficiency of CdSe quantum dots have been enhanced by passivating the surface of CdSe quantum dots with ZnS layers. (copyright 2009 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

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

Science.gov (United States)

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

2018-05-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2017-02-28

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

Surface and Interface Engineering of Organometallic and Two Dimensional Semiconductor

Science.gov (United States)

Park, Jun Hong

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

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

Directory of Open Access Journals (Sweden)

Jian Wu

2016-01-01

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

Catalysed hydrogen isotope exchange

International Nuclear Information System (INIS)

1973-01-01

A method is described for enhancing the rate of exchange of hydrogen atoms in organic compounds or moieties with deuterium or tritium atoms. It comprises reacting the organic compound or moiety and a compound which is the source of deuterium or tritium in the presence of a catalyst consisting of a non-metallic, metallic or organometallic halide of Lewis acid character and which is reactive towards water, hydrogen halides or similar protonic acids. The catalyst is a halide or organometallic halide of: (i) zinc or another element of Group IIb; (ii) boron, aluminium or another element of Group III; (iii) tin, lead, antimony or another element of Groups IV to VI; or (iv) a transition metal, lanthanide or stable actinide; or a halohalide. (author)

The Reduction of a Nitrile (CN) Group by Sodium Borohydride. The Preparation of Phosphine--Amine and Phosphine--Iimidate Complesex of Tungsten Carbonyl.

Science.gov (United States)

Faust, Kristen E.; Storhoff, Bruce N.

1989-01-01

Describes an experiment for advanced-level undergraduate students for extending student experiences involving recording and interpreting infrared (IR) and nuclear magnetic resonance (NMR) spectra from reactions of organometallic compounds. Experimental procedures, analyses and structural assignments, and suggestions for extension and modification…

Rhenium and technetium: application of organometallic rhenium and technetium complexes in radiopharmacy. Evaluation of optimal anchor groups

International Nuclear Information System (INIS)

Alberto, R.; Schibli, R.; Egli, A.; Schaffland, A.; Rattat, D.; Mueller, J.; Iftimia, M.; Berke, H.; Kaden, T.A.; Abram, U.

1997-01-01

The coordinative properties of the '[fac-M(CO) 3 ] + ' moiety (M= 188 Re, Re, 99 Tc and 99m Tc) have been investigated in water and organic solvents in order to evaluate the anchor group attached to antibodies, small peptides and biologically active molecules. The preparation of [M(OH 2 ) 3 (CO) 3 ] + has been improved in a way that this complex can be prepared from a Kit formulation. The '[fac-M(CO) 3 ] + ' has been transformed to the '[fac-M(NO)(CO) 2 ] 2+ ' moiety to achieve higher direct labelling yields and faster incorporation kinetics. (author) 5 figs

Biodegradable materials as binders for IVth generation moulding sands

OpenAIRE

K. Major-Gabry

2015-01-01

This paper focuses on the possibility of using the biodegradable materials as binders (or parts of binders?compositions) for foundry moulding and core sands. Results showed that there is a great possibility of using available biodegradable materials as foundry moulding sand binders. Using biodegradable materials as partial content of new binders, or additives to moulding sands may not only decrease the toxicity and increase reclamation ability of tested moulding sands, but also accelerate the...

Recombination of charge carriers on radiation-induced defects in silicon doped by transition metals impurities

CERN Document Server

Kazakevich, L A

2003-01-01

It has been studied the peculiarities of recombination of nonequilibrium charge carriers on radiation-induced defects in received according to Czochralski method p-silicon (p approx 3 - 20 Ohm centre dot cm), doped by one of the impurities of transition metals of the IV-th group of periodic table (titanium, zirconium, hafnium). Experimental results are obtained out of the analysis of temperature and injection dependence of the life time of charge carriers. The results are explained taking into consideration the influences of elastic stress fields created by the aggregates of transition metals atoms on space distribution over the crystal of oxygen and carbon background impurities as well as on the migration of movable radiation-induced defects during irradiation. (authors).

Catalytic Hydration of Alkenes and Alkynes

Energy Technology Data Exchange (ETDEWEB)

Atwood, Jim, D.

2003-03-18

The fifteen years of DOE support have encompassed two different projects, electron-transfer reactions of metal carbonyl anions and water-soluble organometallic complexes. Each of these is related to homogeneous catalysis and will be described in separate sections. Electron Transfer--Twenty-one manuscripts resulted from our studies of electron-transfer reactions of metal carbonyl anions and acknowledge DOE support. Construction of an infrared stopped-flow system allowed us to measure rates of reactions for the extremely air-sensitive metal carbonyl anions. As for carbanions, both one-electron and two-electron processes occur for metal carbonyl anions. The most unexpected feature was examples of a very rapid two-electron process, followed by a much slower one-electron back transfer. The two-electron processes were accompanied by transfer of a ligand between two metals, M-X + M{prime}{sup -} {yields} M{sup -} + M{prime}-X with X groups of CO{sup 2}, H{sup +}, CH{sub 3}{sup +} and Br{sup +}. These transfers, which can be considered nucleophilic displacements, occurred when M{prime}{sup -} was more nucleophilic than M{sup -}. The 21 published manuscripts explore one- and two-electron processes for many such organometallic complexes. Water-Soluble Organometallic Complexes--The potential of water-soluble organometallic complexes in ''green chemistry'' intrigued us. Sixteen manuscripts acknowledging DOE support have appeared thus far in this field. Our research centered on sulfonated phosphine ligands, PPh{sub 2}(m-C{sub 6}H{sub 4}SO{sub 3}Na) and P(m-C{sub 6}H{sub 4}SO{sub 3}Na){sub 3}, to solubilize organometallic complexes in water. These analogues of PPH{sub 3} allowed us to synthesize complexes of Ir, Rh, Ru, Ni, Pd, Pt and Ag that are water-soluble and contain such common organometallic ligands as CO, H and CH{sub 3} in addition to halides and the phosphine ligands. These metal complexes show the ability to activate H{sub 2}, CO, C{sub 2}H{sub 4

Catalytic Organometallic Reactions of Ammonia

Science.gov (United States)

Klinkenberg, Jessica L.

2012-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2010-06-15

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

The value of scintigraphic examinations in the diagnosis of pathologic processes in the posterior scala in childhood and youth

International Nuclear Information System (INIS)

Piepgras, U.; Huber, G.; Emde, H.

1980-01-01

The diagnostical possibilities of computerized tomography (CT) and brain scintigraphy are compared. Serial scintigraphy by gamma cameras, scintigraphic examinations of the liquor space and the ventricles are discussed, too. In addition to CT, scintigraphy is also recommended in the following cases: hydrocephalus of unknown origin, dilatation of the IVth ventricle, diagnosis of recidive tumours, and unclear density differences. (L.E.)

Single-Site VO x Moieties Generated on Silica by Surface Organometallic Chemistry: A Way To Enhance the Catalytic Activity in the Oxidative Dehydrogenation of Propane

KAUST Repository

Barman, Samir

2016-07-26

We report here an accurate surface organometallic chemistry (SOMC) approach to propane oxidative dehydrogenation (ODH) using a μ2-oxo-bridged, bimetallic [V2O4(acac)2] (1) (acac = acetylacetonate anion) complex as a precursor. The identity and the nuclearity of the product of grafting and of the subsequent oxidative treatment have been systematically studied by means of FT-IR, Raman, solid-state (SS) NMR, UV-vis DRS, EPR and EXAFS spectroscopies. We show that the grafting of 1 on the silica surface under a rigorous SOMC protocol and the subsequent oxidative thermal treatment lead exclusively to well-defined and isolated monovanadate species. The resulting material has been tested for the oxidative dehydrogenation of propane in a moderate temperature range (400-525 °C) and compared with that of silica-supported vanadium catalysts prepared by the standard impregnation technique. The experimental results show that the catalytic activity in propane ODH is strongly upgraded by the degree of isolation of the VOx species that can be achieved by employing the SOMC protocol. © 2016 American Chemical Society.

Single-Site VO x Moieties Generated on Silica by Surface Organometallic Chemistry: A Way To Enhance the Catalytic Activity in the Oxidative Dehydrogenation of Propane

KAUST Repository

Barman, Samir; Maity, Niladri; Bhatte, Kushal; Ould-Chikh, Samy; Dachwald, Oliver; Haeß ner, Carmen; Saih, Youssef; Abou-Hamad, Edy; Llorens, Isabelle; Hazemann, Jean-Louis; Kö hler, Klaus; D’ Elia, Valerio; Basset, Jean-Marie

2016-01-01

We report here an accurate surface organometallic chemistry (SOMC) approach to propane oxidative dehydrogenation (ODH) using a μ2-oxo-bridged, bimetallic [V2O4(acac)2] (1) (acac = acetylacetonate anion) complex as a precursor. The identity and the nuclearity of the product of grafting and of the subsequent oxidative treatment have been systematically studied by means of FT-IR, Raman, solid-state (SS) NMR, UV-vis DRS, EPR and EXAFS spectroscopies. We show that the grafting of 1 on the silica surface under a rigorous SOMC protocol and the subsequent oxidative thermal treatment lead exclusively to well-defined and isolated monovanadate species. The resulting material has been tested for the oxidative dehydrogenation of propane in a moderate temperature range (400-525 °C) and compared with that of silica-supported vanadium catalysts prepared by the standard impregnation technique. The experimental results show that the catalytic activity in propane ODH is strongly upgraded by the degree of isolation of the VOx species that can be achieved by employing the SOMC protocol. © 2016 American Chemical Society.

Convergent synthesis of 6-substituted phenanthridines via anionic ring closure

DEFF Research Database (Denmark)

Lysén, M.; Kristensen, Jesper Langgaard; Vedsø, P.

2002-01-01

Chemical equation presented The addition of organometallic derivatives to the cyano group of 2-(2-fluorophenyl)benzonitrile followed by intramolecular nucleophilic substitution produces 6-substituted phenanthridines. Alkyllithiums, aryllithiums, and sterically nondemanding lithium amides reacted ...

Free Electron Laser in Poland

CERN Document Server

Romaniuk, Ryszard

2009-01-01

The idea of building a new IVth generation of light sources of high luminosity, which use accelerators, arose in the 80ties of XXth century. Now, in a numerable synchrotron and laser laboratories in Europe, there is carried out, since a couple of years, intense applied research on free electron lasers (FEL) [17,18]. Similarly, in this country, free electron laser in Poland – POLFEL [9] is, in a design, a coherent light source of the IVth generation, characterized by very short pulses in the range of 10-100fs, of big power 0,2GW and UV wavelength of 27nm, of average power 1W, with effective high power third harmonic of 9nm. The laser consists of a linear superconducting accelerator 100m in length, undulator and experimental lines. It generates a monochromatic and coherent radiation and can be tuned from THz range via IR, visible to UV, and potentially to X-rays. The linac works in quasi-CW or real-CW mode. It is planned by IPJ [9,10] and XFEL-Poland Consortium [16] as a part of the ESFRI [1] priority EuroFEL...

Electrooxidative Ruthenium-Catalyzed C-H/O-H Annulation by Weak O-Coordination.

Science.gov (United States)

Qiu, Youai; Tian, Cong; Massignan, Leonardo; Rogge, Torben; Ackermann, Lutz

2018-05-14

Electrocatalysis has been identified as a powerful strategy for organometallic catalysis, and yet electrocatalytic C-H activation is restricted to strongly N-coordinating directing groups. The first example of electrocatalytic C-H activation by weak O-coordination is presented, in which a versatile ruthenium(II) carboxylate catalyst enables electrooxidative C-H/O-H functionalization for alkyne annulations in the absence of metal oxidants; thereby exploiting sustainable electricity as the sole oxidant. Mechanistic insights provide strong support for a facile organometallic C-H ruthenation and an effective electrochemical reoxidation of the key ruthenium(0) intermediate. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Energy Technology Data Exchange (ETDEWEB)

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

2015-12-15

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

Iron(III-salophene: an organometallic compound with selective cytotoxic and anti-proliferative properties in platinum-resistant ovarian cancer cells.

Directory of Open Access Journals (Sweden)

Thilo S Lange

2008-05-01

Full Text Available In this pioneer study to the biological activity of organometallic compound Iron(III-salophene (Fe-SP the specific effects of Fe-SP on viability, morphology, proliferation, and cell-cycle progression on platinum-resistant ovarian cancer cell lines were investigated.Fe-SP displayed selective cytotoxicity against SKOV-3 and OVCAR-3 (ovarian epithelial adenocarcinoma cell lines at concentrations between 100 nM and 1 microM, while the viability of HeLa cells (epithelial cervix adenocarcinoma or primary lung or skin fibroblasts was not affected. SKOV-3 cells in contrast to fibroblasts after treatment with Fe-SP revealed apparent hallmarks of apoptosis including densely stained nuclear granular bodies within fragmented nuclei, highly condensed chromatin and chromatin fragmentation. Fe-SP treatment led to the activation of markers of the extrinsic (Caspase-8 and intrinsic (Caspase-9 pathway of apoptosis as well as of executioner Caspase-3 while PARP-1 was deactivated. Fe-SP exerted effects as an anti-proliferative agent with an IC(50 value of 300 nM and caused delayed progression of cells through S-phase phase of the cell cycle resulting in a complete S-phase arrest. When intra-peritoneally applied to rats Fe-SP did not show any systemic toxicity at concentrations that in preliminary trials were determined to be chemotherapeutic relevant doses in a rat ovarian cancer cell model.The present report suggests that Fe-SP is a potent growth-suppressing agent in vitro for cell lines derived from ovarian cancer and a potential therapeutic drug to treat such tumors in vivo.

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

Energy Technology Data Exchange (ETDEWEB)

Barros, N

2007-06-15

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

Organometallic Polymeric Conductors

Science.gov (United States)

Youngs, Wiley J.

1997-01-01

over 150 days in air at ambient temperature. The conductivity of the films dropped only half an order of magnitude in that time. Films aged under vacuum at ambient temperature diminished slightly in conductivity in the first day, but did not change thereafter. An experimental design approach will be applied to maximize the efficiency of the laboratory effort. The material properties (initial and long term) will also be monitored and assessed. The experimental results will add to the existing database for electrically conductive polymer materials. Attachments: 1) Synthesis Crystal Structure, and Polymerization of 1,2:5,6:9,10-Tribenzo-3,7,11,13-tetradehydro(14) annulene. 2) Reinvestigation of the Photocyclization of 1,4-Phenylene Bis(phenylmaleic anhydride): Preparation and Structure of (5)Helicene 5,6:9,10-Dianhydride. 3) Preparation and Structure Charecterization of a Platinum Catecholate Complex Containing Two 3-Ethynyltheophone Groups. and 4) Rigid-Rod Polymers Based on Noncoplanar 4,4'-Biphenyldiamines: A Review of Polymer Properties vs Configuration of Diamines.

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

KAUST Repository

Al-Shareef, Reem A.

2017-11-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-01-01

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

White light emission and second harmonic generation from secondary group participation (SGP) in a coordination network.

Science.gov (United States)

He, Jun; Zeller, Matthias; Hunter, Allen D; Xu, Zhengtao

2012-01-25

We describe a white emitting coordination network solid that can be conveniently applied as a thin film onto a commercial UV-LED lamp for practical white lighting applications. The solid state material was discovered in an exercise of exploring molecular building blocks equipped with secondary groups for fine-tuning the structures and properties of coordination nets. Specifically, CH(3)SCH(2)CH(2)S- and (S)-CH(3)(OH)CHCH(2)S- (2-hydroxylpropyl) were each attached as secondary groups to the 2,5- positions of 1,4-benzenedicarboxylic acid (bdc), and the resultant molecules (L1 and L2, respectively) were crystallized with Pb(II) into the topologically similar 3D nets of PbL1 and PbL2, both consisting of interlinked Pb-carboxyl chains. While the CH(3)S- groups in PbL1 are not bonded to the Pb(II) centers, the hydroxy groups in PbL2 participate in coordinating to Pb(II) and thus modify the bonding features around the Pb(II), but only to a slight and subtle degree (e.g., Pb-O distances 2.941-3.116 Å). Interestingly, the subtle change in structure significantly impacts the properties, i.e., while the photoluminescence of PbL1 is yellowish green, PbL2 features bright white emission. Also, the homochiral side group in PbL2 imparts significant second harmonic generation, in spite of its seemingly weak association with the main framework (the NLO-phore). In a broad perspective, this work showcases the idea of secondary group participation (SGP) in the construction of coordination networks, an idea that parallels that of hemilabile ligands in organometallics and points to an effective strategy in developing advanced functions in solid state framework materials. © 2011 American Chemical Society

Cycle thorium et réacteurs à sel fondu. Exploration du champ des paramètres et des contraintes définissant le "Thorium Molten Salt Reactor"

OpenAIRE

Mathieu , Ludovic

2005-01-01

Producing nuclear energy in order to reduce the anthropic CO2 emission requires major technological advances. Nuclear plants of IVth generation have to respond to several constraints, as safety improvements, fuel breeding and radioactive waste minimization. For this purpose, it seems promising to use Thorium Cycle in Molten Salt Reactors. Studies on this domain have already been carried out. However, the final concept suffered from serious issues and was discontinued. A new reflection on this...

Catalysis by Design: Well-Defined Single-Site Heterogeneous Catalysts

KAUST Repository

Pelletier, Jeremie

2016-03-09

support taken as a X, L ligands in the Green formalism, the catalyst can be designed and generated by grafting the organometallic precursor containing the functional group(s) suitable to target a given transformation (surface organometallic fragments (SOMF)). The choice of these SOMF is based on the elementary steps known in molecular chemistry applied to the desired reaction. The coordination sphere necessary for any catalytic reaction involving paraffins, olefins, and alkynes also can thus be predicted. Only their most complete understanding can allow development of catalytic reactions with the highest possible selectivity, activity, and lifetime. This Account will examine the results of SOMC for hydrocarbon transformations on oxide surfaces bearing metals of group 4-6. The silica-supported catalysts are exhibiting remarkable performances for Ziegler-Natta polymerization and depolymerization, low temperature hydrogenolysis of alkanes and waxes, metathesis of alkanes and cycloalkanes, olefins metathesis, and related reactions. In the case of reactions involving molecules that do not contain carbon (water-gas shift, NH3 synthesis, etc.) this single site approach is also valid but will be considered in a later review. © 2016 American Chemical Society.

Organometallic chemical vapor deposition and characterization of ZnGe(1-x)Si(x)P2-Ge alloys on GaP substrates

Science.gov (United States)

Xing, G. C.; Bachmann, Klaus J.; Posthill, J. B.; Timmons, M. L.

1993-01-01

The epitaxial growth of ZnGe(1-x)Si(x)P2-Ge alloys on GaP substrates by open tube organometallic chemical vapor deposition (OMCVD) is reported. The chemical composition of the alloys characterized by energy dispersive X-ray spectroscopy shows that alloys with x up to 0.13 can be deposited on (001) GaP. Epitaxial growth with mirror smooth surface morphology was achieved for x less than or equal to 0.05. Transmission electron microscopy (TEM) micrographs of these alloys show specular epitaxy and the absence of microstructural defects indicating a defect density of less than 10(exp 7) cm(sup -2). Selected area electron diffraction pattern of the alloy shows that the epitaxial layer crystallizes in the chalcopyrite structure with relatively weak superlattice reflections indicating certain degree of randomness in the cation sublattice. Hall measurements show that the alloys are p-type, like the unalloyed films; the carrier concentration, however, dropped about 10 times from 2 x 10(exp 18) to 2 x 10(exp 17) cm(sup -3). Absorption measurements indicate that the band tailing in the absorption spectra of the alloy was shifted about 0.04 eV towards shorter wavelength as compared to the unalloyed material. Diodes fabricated from the n(+)-GaP/p-ZnSiP2-ZnGeP2-Ge heterostructure at x = 0.05 have a reverse break-down voltage of -10.8 V and a reverse saturation current density of approximately 6 x 10(exp -8) A/sq cm.

Oriented Poly(dialkylstannane)s

DEFF Research Database (Denmark)

Choffat, Fabien; Fornera, Sara; Smith, Paul

2008-01-01

The inorganic (or 'organometallic') polymers poly(dibutylstannane), poly(dioctylstannane), and poly(didodecylstannane) have been oriented by shear forces, the tensile drawing of blends with polyethylene, and deposition from solution onto glass slides coated with all oriented, friction-deposited p......The inorganic (or 'organometallic') polymers poly(dibutylstannane), poly(dioctylstannane), and poly(didodecylstannane) have been oriented by shear forces, the tensile drawing of blends with polyethylene, and deposition from solution onto glass slides coated with all oriented, friction......-deposited poly(tetrafluoroethylene) (PTFE) layer. Orientation of the polystannanes has been examined by polarization microscopy, UV-vis spectroscopy with polarized light, and X-ray diffraction and their direction is found to depend on the length of the alkyl side groups and the method of orientation. Remarkably...

Mechanistic Insights on the Reductive Dehydroxylation Pathway for the Biosynthesis of Isoprenoids Promoted by the IspH Enzyme

KAUST Repository

Abdel-Azeim, Safwat

2015-06-22

Here, we report an integrated quantum mechanics/molecular mechanics (QM/MM) study of the bio-organometallic reaction pathway of the 2H+/2e- reduction of (E)-4-hydroxy-3-methylbut-2-enyl pyrophosphate (HMBPP) into the so called universal terpenoids precursors isopentenyl pyrophosphate (IPP) and dimethylallyl pyrophosphate (DMAPP), promoted by the IspH enzyme. Our results support the viability of the bio-organometallic pathway from rotation of the OH group of HMBPP away from the [Fe4S4] cluster at the core of the catalytic site, to be engaged in a H-bond with Glu126. This rotation is synchronous with π-coordination of the C2=C3 double bond of HMBPP to the apical Fe atom of the [Fe4S4] cluster. Dehydroxylation of HMBPP is triggered by a proton transfer from Glu126 to the OH group of HMBPP. The reaction pathway is completed by competitive proton transfer from the terminal phosphate group to the C2 or C4 atom of HMBPP.

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

Science.gov (United States)

Jover, Jesús

2017-11-08

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

Organometallic DNA-B12 Conjugates as Potential Oligonucleotide Vectors: Synthesis and Structural and Binding Studies with Human Cobalamin-Transport Proteins.

Science.gov (United States)

Mutti, Elena; Hunger, Miriam; Fedosov, Sergey; Nexo, Ebba; Kräutler, Bernhard

2017-11-16

The synthesis and structural characterization of Co-(dN) 25 -Cbl (Cbl: cobalamin; dN: deoxynucleotide) and Co-(dN) 39 -Cbl, which are organometallic DNA-B 12 conjugates with single DNA strands consisting of 25 and 39 deoxynucleotides, respectively, and binding studies of these two DNA-Cbl conjugates to three homologous human Cbl transporting proteins, transcobalamin (TC), intrinsic factor (IF), and haptocorrin (HC), are reported. This investigation tests the suitability of such DNA-Cbls for the task of eventual in vivo oligonucleotide delivery. The binding of DNA-Cbl to TC, IF, and HC was investigated in competition with either a fluorescent Cbl derivative and Co-(dN) 25 -Cbl, or radiolabeled vitamin B 12 ( 57 Co-CNCbl) and Co-(dN) 25 -Cbl or Co-(dN) 39 -Cbl. Binding of the new DNA-Cbl conjugates was fast and tight with TC, but poorer with HC and IF, which extends a similar original finding with the simpler DNA-Cbl, Co-(dN) 18 -Cbl. The contrasting affinities of TC versus IF and HC for the DNA-Cbl conjugates are rationalized herein by a stepwise mechanism of Cbl binding. Critical contributions to overall affinity result from gradual conformational adaptations of the Cbl-binding proteins to the DNA-Cbl, which is first bound to the respective β domains. This transition is fast with TC, but slow with IF and HC, with which weaker binding results. The invariably tight interaction of the DNA-Cbl conjugates with TC makes the Cbl moiety a potential natural vector for the specific delivery of oligonucleotide loads from the blood into cells. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Adventus Praesulis: Social Consensus and Power Rituals in the Urban World of the Late Antiquity

Directory of Open Access Journals (Sweden)

Pablo FUENTES HINOJO

2012-03-01

Full Text Available It is the purpose of this article to examine the emergence of the Christian rituals of power and his influence on the construction of the memory in the urban societies from the Ivth to VIIth centuries. The attention is focused concretely on the adventus praesulis , ceremony of arrival of the bishop to his seed, studing his origins, political and social function, and effects on the perception that the urban population had about his common past.

Krishnamurthy, Prof. Setharampattu Seshaiyer

Indian Academy of Sciences (India)

Specialization: Main Group Chemistry and Organometallic Chemistry Address: Department of Inorganic and Physical Chemistry, Indian Inst. of Science, Bengaluru 560 012, Karnataka Contact: ... The 29th Mid-year meeting of the Academy will be held from 29–30 June 2018 in Infosys, Mysuru ... 11 to 25 June, 2018

Hot heads and cold brains. Aristotle, Galen and the "radiator theory".

Science.gov (United States)

Longo, O

1996-01-01

The Author examines two similar theories about the functioning of human brain as a refrigerator: Falk's and Fialkowski's (1990) and Aristotle's (IVth century b.C.). There are surprising, although fortuitous, convergences between the two, with the remarkable difference, however, that Artistotle's doctrine (later severely criticized by Galen) thinks of the brain merely as an organ for the cooling of the body's (the heart's) heat, while according to the modern radiator theory the human brain developed starting as a refrigerator of itself.

Lethal mutation of internal irradiation brown planthopper (Nilaparvita lugens Stal)

International Nuclear Information System (INIS)

Wahid, R.A.

1988-01-01

The moulting IVth of BPH nympha were irradiated internally with radiophosphorous 32-P 1 uCi/ml, 10 uCi/ml, 50 uCi/ml, 100 uCi/ml, and 500 uCi/ml concentrations respectivelly. An observation was carried out to determines heredity of hopper sterilities from the mating groups of R male x N female, R male x R female, and N male x R female. The 32-P concentration below of 50 uCi/ml seemed to be the substerile dose, however, the dominant lethal mutation has been visually shown by R male x R female F1 mating group. The hereditary lines of F1, F2, F3, and F4 of the hopper sterilities wich were indicated by the nympha hatch ability have some significant correlations (r1= -0.77, r2= -0.92, r3= -0.93 and r4= -0.85). Thus, the resesif lethal mutations visually showed by F3 and F4 from all of the 100 uCi/ml and 50 uCi/ml treated groups. (author). 10 refs, 2 figs, 2 tabs

Catalysis by Design: Well-Defined Single-Site Heterogeneous Catalysts

KAUST Repository

Pelletier, Jeremie; Basset, Jean-Marie

2016-01-01

concepts and tools of surface organometallic chemistry (SOMC). This approach operates by reacting organometallic compounds with surfaces of highly divided oxides (or of metal nanoparticles). This strategy has a solid track record to reveal structure

Study of the role of the ligands coordinated at the surface of pure Wuestite nanoparticles prepared following a room temperature organometallic method: Evidence of ferromagnetic - in shell- and antiferromagnetic - in core magnetic behaviors

Energy Technology Data Exchange (ETDEWEB)

Glaria, Arnaud [CNRS, LCC (Laboratoire de Chimie de Coordination), 205, route de Narbonne, F-31077 Toulouse (France); Universite de Toulouse, UPS, INPT, LCC, F-31077 Toulouse (France); Kahn, Myrtil L., E-mail: myrtil.kahn@lcc-toulouse.fr [CNRS, LCC (Laboratoire de Chimie de Coordination), 205, route de Narbonne, F-31077 Toulouse (France); Universite de Toulouse, UPS, INPT, LCC, F-31077 Toulouse (France); Chaudret, Bruno [CNRS, LCC (Laboratoire de Chimie de Coordination), 205, route de Narbonne, F-31077 Toulouse (France); Universite de Toulouse, UPS, INPT, LCC, F-31077 Toulouse (France); Lecante, Pierre; Casanove, Marie-Jose [CNRS, CEMES (Centre d' Elaboration des Materiaux et d' Etudes Structurales), 29 rue Jeanne Marvig, BP 4347, 31055 Toulouse Cedex (France); Barbara, Bernard, E-mail: bernard.barbara@grenoble.cnrs.fr [Institut Louis Neel, CNRS, 25 Av. des martyrs, BP 166, 38042 Grenoble Cedex 09 (France)

2011-09-15

Highlights: {yields} Pure Wuestite (Fe{sub 1-y}O) nanoparticles synthesized by organometallic chemistry. {yields} The influence of the surface ligands on the magnetic properties. {yields} Ferromagnetic core-antiferromagnetic shell magnetic nanoparticles. - Abstract: Wuestite particles (Fe{sub 1-y}O) are synthesized using controlled hydrolysis at room temperature of [Fe(N(SiMe{sub 3}){sub 2}){sub 2}] and stabilized by amine ligands. This method leads to 5 nm pure wuestite particles. This phase is clearly identified by transmission electron microscopy and wide angle X-ray scattering. Distortion in the crystallographic structure has been demonstrated. Particular attention is paid on the Fe(III) formation. Moreover, a combination of Moessbauer spectroscopy and SQuID measurements, revealed that the particles are composed of an antiferromagnetic core surrounded by a ferromagnetic shell. According to the Neel theory, the Fe(III) and Fe(II) ions present in the particles are ferromagnetically coupled and the proportion of Fe(III) ions varies from 3.9 to 7.1% as a function of the amine ligand.

Determination of Trajectories for a Gliding Parachute System

Science.gov (United States)

1975-04-01

use of such items. Destroy this report when no longer needed. Do not return it to the originator. * jiT >T^>’TyT>’V’v,>T>’*.y^jrw\\gwJ^ "-’ v*»’v -*iv...The terminal error serves as a penalty function which penalizes undesirable terminal states by the extent to which they deviate from the desired...the open-loop control becomes, in effect , feedback control with the sequence of initial conditions serving as the current state. The major advantage

A structurally characterized organometallic plutonium(IV) complex

Energy Technology Data Exchange (ETDEWEB)

Apostolidis, Christos; Walter, Olaf [European Commission, Joint Research Centre, Directorate G - Nuclear Safety and Security, Karlsruhe (Germany); Vogt, Jochen; Liebing, Phil; Edelmann, Frank T. [Chemisches Institut, Otto-von-Guericke-Universitaet Magdeburg (Germany); Maron, Laurent [Laboratoire de Physique et Chimie des Nanoobjets (LPCNO), Universite de Toulouse/INSA/CNRS (UMR5215), Toulouse (France)

2017-04-24

The blood-red plutonocene complex Pu(1,3-COT'')(1,4-COT'') (4; COT''=η{sup 8}-bis(trimethylsilyl)cyclooctatetraenyl) has been synthesized by oxidation of the anionic sandwich complex Li[Pu(1,4-COT''){sub 2}] (3) with anhydrous cobalt(II) chloride. The first crystal structure determination of an organoplutonium(IV) complex revealed an asymmetric sandwich structure for 4 where one COT'' ring is 1,3-substituted while the other retains the original 1,4-substitution pattern. The electronic structure of 4 has been elucidated by a computational study, revealing a probable cause for the unexpected silyl group migration. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Synthesis, characterization and emission properties of quinolin-8 ...

Indian Academy of Sciences (India)

Unknown

chelated ruthenium organometallics. BIKASH KUMAR PANDA. Department of Inorganic ... Ruthenium organometallics; quinolin-8-olato chelation; emission properties; trivalent ruthenium. 1. Introduction. There is continuing ... chem.istry of orthometallated ruthenium compounds is of current interest in the context of synthesis ...

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

Energy Technology Data Exchange (ETDEWEB)

Clavaud, C

2006-02-15

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

Size-regulated group separation of CoFe2O4 nanoparticles using centrifuge and their magnetic resonance contrast properties

Science.gov (United States)

Kang, Jongeun; Lee, Hyunseung; Kim, Young-Nam; Yeom, Areum; Jeong, Heejeong; Lim, Yong Taik; Hong, Kwan Soo

2013-09-01

Magnetic nanoparticle (MNP)-based magnetic resonance imaging (MRI) contrast agents (CAs) have been the subject of extensive research over recent decades. The particle size of MNPs varies widely and is known to influence their physicochemical and pharmacokinetic properties. There are two commonly used methods for synthesizing MNPs, organometallic and aqueous solution coprecipitation. The former has the advantage of being able to control the particle size more effectively; however, the resulting particles require a hydrophilic coating in order to be rendered water soluble. The MNPs produced using the latter method are intrinsically water soluble, but they have a relatively wide particle size distribution. Size-controlled water-soluble MNPs have great potential as MRI CAs and in cell sorting and labeling applications. In the present study, we synthesized CoFe2O4 MNPs using an aqueous solution coprecipitation method. The MNPs were subsequently separated into four groups depending on size, by the use of centrifugation at different speeds. The crystal shapes and size distributions of the particles in the four groups were measured and confirmed by transmission electron microscopy and dynamic light scattering. Using X-ray diffraction analysis, the MNPs were found to have an inverse spinel structure. Four MNP groups with well-selected semi-Gaussian-like diameter distributions were obtained, with measured T2 relaxivities ( r 2) at 4.7 T and room temperature in the range of 60 to 300 mM-1s-1, depending on the particle size. This size regulation method has great promise for applications that require homogeneous-sized MNPs made by an aqueous solution coprecipitation method. Any group of the CoFe2O4 MNPs could be used as initial base cores of MRI T2 CAs, with almost unique T2 relaxivity owing to size regulation. The methodology reported here opens up many possibilities for biosensing applications and disease diagnosis.

Improved synthesis of carbon nanotubes with junctions and of single ...

Indian Academy of Sciences (India)

Unknown

Abstract. Pyrolysis of thiophene over nickel nanoparticles dispersed on silica is shown to yield Y- junction carbon nanotubes with smaller diameters than those obtained by the pyrolysis of organometallic- thiophene mixtures. In the presence of water vapour, the pyrolysis of organometallic-hydrocarbon mixtures.

Approach to the human diet of the punic population of Can Marines (Ibiza. C an N stable isotope analysis on bone collagen

Directory of Open Access Journals (Sweden)

Domingo Carlos Salazar García

2012-09-01

Full Text Available We report here on the results of carbon and nitrogen stable isotope analysis on bone collagen of humans from the Punic site of Can Marines (V-IVth BC from the island of Ibiza (Spain. To date, there are few isotopic studies for this period from the Mediterranean. This article reports new isotopic data from a Western Mediterranean Punic rural settlement. The results show a terrestrial based diet with no isotopic evidence of marine or freshwater protein input, and suggest the presence of C4 resources in it.

Catalysis by Design Using Surface Organometallic Nitrogen-Containing Fragments

KAUST Repository

Hamzaoui, Bilel

2016-06-14

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

Organometallic Reactions Development, Mechanistic Studies and Synthetic Applications

DEFF Research Database (Denmark)

Dam, Johan Hygum

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

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

KAUST Repository

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

2018-01-01

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

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

KAUST Repository

Alshareef, Reem Abdul aziz Hamed

2018-04-25

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

Synthesis and characterization of a liquid Eu precursor (EuCppm2) allowing for valence control of Eu ions doped into GaN by organometallic vapor phase epitaxy

International Nuclear Information System (INIS)

Mitchell, Brandon; Koizumi, Atsushi; Nunokawa, Takumi; Wakamatsu, Ryuta; Lee, Dong-gun; Saitoh, Yasuhisa; Timmerman, Dolf; Kuboshima, Yoshinori; Mogi, Takayuki; Higashi, Shintaro; Kikukawa, Kaoru; Ofuchi, Hironori; Honma, Tetsuo; Fujiwara, Yasufumi

2017-01-01

A liquid Eu precursor, bis(normal-propyl-tetramethylcyclopentadienyl)europium has been synthesized. This precursor exists as a liquid at temperatures higher than 49 °C, has a moderately high vapor pressure, contains no oxygen in its molecular structure, and can be distilled to high purity. These properties make it ideal for doping using a chemical vapor or atomic layer deposition method, and provide a degree of control previously unavailable. As a precursor the Eu exists in the divalent valance state, however, once doped into GaN by organometallic vapor phase epitaxy, the room-temperature photoluminescence of the Eu-doped GaN exhibited the typical red emission due to the intra-4f shell transition of trivalent Eu. After variation of the growth temperature, it was found that divalent Eu could be stabilized in the GaN matrix. By tuning the Fermi level through donor doping, the ratio of Eu 2+ to Eu 3+ could be controlled. The change in valence state of the Eu ions was confirmed using X-ray absorption near-edge structure. - Highlights: • A liquid Eu precursor was synthesized and its properties were characterized. • Precursor has a low melting point and a moderately high vapor pressure. • Does not contain oxygen in its molecular structure. • Eu can changed its valance state when incorporated into GaN. • Valence state of Eu in GaN can be controlled by donor doping.

Recent progress of ordered mesoporous silica-supported chiral metallic catalysts

Directory of Open Access Journals (Sweden)

LIU Rui

2013-02-01

Full Text Available Recently,ordered silica-based mesoporous chiral organometallics-functionalized heterogeneous catalysts have attracted extensive research interest due to their excellent properties,such as easy preparation,high activity and convenient recycle.This review mainly summarizesthe generally prepared strategy and the silica-based organometallics-functionalized heterogeneous catalysts reported in the literatures.

IVth scientific congress of Central society of balneologists of Austria in Opatija, 1904.

Science.gov (United States)

Fischinger, Aleš; Fischinger, Janez; Fischinger, Duša

2017-12-01

The authors were interested in the lectures' themes, organisation, the course, and the accompanied activities at the balneology congress in Opatija in 1904. The congress was organised by the principle of the health resort at the time Professor Dr Julius Glax, and consisted of two separate parts. The first part was held in Opatija from October 13 until 15, 1904. There were lectures, auto-papers, summaries, reports, discussions, and the afternoon expert trip to Crikvenica by boat. In Opatija the participants were shown the spa park, the rehabilitation paths for patients with heart difficulties, marine baths Angiolona and Slatina, the covered spa Erzherzog Ludwig Viktor Bad, and of the health institution Zander Institute. At the accompanying exhibition the Austrian and German companies represented their products, among them still recognised Bayer, C. Reichert in Karl Zeiß. Additionally, the owner of the Zanderinstitut in Opatija Dr Isor Stein presented his own therapeutic aid exerciteur there. The first part of the congress concluded on October 15, 1904 with the great banquet in the hotel Stephanie.The second part of the congress was held from October 16 until 20, 1904. The expert trip was organised to the Austrian Riviera on the Pannonia ship. The participants visited attractions and health institutions in Mali Lošinj, Pula, Brijuni, Rovinj, Grado, Aquileia and Trieste, where they also had expert lectures. The closing ceremony of the second part of the congress was in Trieste, from where the participants returned to Vienna by the special train.

Optical spectroscopy of f-element compounds

International Nuclear Information System (INIS)

Carnall, W.T.

1978-01-01

It is noted that the energies and intensities of transitions observed in the optical spectra of lanthanide (Ln) and actinide (An) compounds can typically be measured with a high degree of accuracy. The observed transitions can then be directly represented as upper state energy levels where the structure is induced by the environment. A discussion is presented of the systematic theoretical interpretation of these transitions both in terms of energy level structure and transition probability. Particularly for the trivalent lanthanides and actinides, the detail to which the interpretation can be carried is unique in the periodic table. The electronic structure of organometallic lanthanides and actinides is emphasized in the discussion. It is made clear that this type of ligand does not present any unique interpretive problems. The basic framework of the interpretation is not dependent upon the specific ionic environment. On the other hand, organometallic compounds represent a particularly interesting group in which to study excited state relaxation

Novel ruthenium methylcyclopentadienyl complex bearing a bipyridine perfluorinated ligand shows strong activity towards colorectal cancer cells.

Science.gov (United States)

Teixeira, Ricardo G; Brás, Ana Rita; Côrte-Real, Leonor; Tatikonda, Rajendhraprasad; Sanches, Anabela; Robalo, M Paula; Avecilla, Fernando; Moreira, Tiago; Garcia, M Helena; Haukka, Matti; Preto, Ana; Valente, Andreia

2018-01-01

Three new compounds have been synthesized and completely characterized by analytical and spectroscopic techniques. The new bipyridine-perfluorinated ligand L1 and the new organometallic complex [Ru(η 5 -MeCp)(PPh 3 ) 2 Cl] (Ru1) crystalize in the centrosymmetric triclinic space group P1¯. Analysis of the phenotypic effects induced by both organometallic complexes Ru1 and [Ru(η 5 -MeCp)(PPh 3 )(L1)][CF 3 SO 3 ] (Ru2), on human colorectal cancer cells (SW480 and RKO) survival, showed that Ru2 has a potent anti-proliferative activity, 4-6 times higher than cisplatin, and induce apoptosis in these cells. Data obtained in a noncancerous cell line derived from normal colon epithelial cells (NCM460) revealed an intrinsic selectivity of Ru2 for malignant cells at low concentrations, showing the high potential of this compound as a selective anticancer agent. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

Cluster-derived Ir-Sn/SiO2 catalysts for the catalytic dehydrogenation of propane: A spectroscopic study

KAUST Repository

Gallo, Alessandro; Psaro, Rinaldo; Guidotti, Matteo; Dal Santo, Vladimiro; Pergola, Roberto Della; Masih, Dilshad; Izumi, Yasuo

2013-01-01

Ir-Sn bimetallic silica-based materials have been prepared via deposition of the molecular organometallic clusters (NEt4)2[Ir 4(CO)10(SnCl3)2] and NEt 4[Ir6(CO)15(SnCl3)] or via deposition of Sn organometallic precursor Sn(n-C4H9) 4 onto pre

Recent advances in carbocupration of α-heterosubstituted alkynes

Directory of Open Access Journals (Sweden)

Ahmad Basheer

2010-07-01

Full Text Available Carbocupration of α-heterosubstituted alkynes leads to the formation of stereodefined functionalized vinyl copper species as single isomer. Recent advances in the field show that a simple pre-association of the organometallic derivative with an additional polar functional group in the vicinity of the reaction center may completely change the stereochemical outcome of the reaction. Representative examples are given in this mini-review.

Demonstrating the utility of boron based precursor molecules for selective area deposition in a scanning tunneling microscope

International Nuclear Information System (INIS)

Perkins, F.K.; Onellion, M.; Lee, S.; Bowben, T.A.

1992-01-01

The scanning tunneling microscope (STM) can be used to selectively deposit material from a gaseous precursor compound. Ultrasmall (less than a 100 nm across) spatial dimensions for selective area deposition may be achieved by this means. In this paper the authors outline a scheme foreselecting and designing main group cluster compounds and organometallics for this type of selective area deposition using nido-decaborane(14) as an example

EFFICACY OF SOME COMMON AQUARIUM FISHES AS BIOCONTROL AGENT OF PREADULT MOSQUITOES

Directory of Open Access Journals (Sweden)

A. Ghosh

2012-10-01

Full Text Available Predation experiment using Betta splendens, Pseudotropheus tropheops, Osphronemus gorami and Pterophyllum scalare   were conducted against IVth instar Anopheline larvae and pupae with varying prey and predator densities. Ranking of individual predatory efficacy showed the sequence: P. tropheops > B. splendens > O. gorami > P. scalare against larva/form and B. splendens > O. gorami > P. tropheops > P. scalare against pupal form of Anopheles stephensi during 24 hours experiment in laboratory condition. Predation under co-existence in interspecific and intraspecific combinations revealed the significance of predatory efficacy with reference to prey density and water volume (search area.

Pentafluorosulfanyl Substituents in Polymerization Catalysis.

Science.gov (United States)

Kenyon, Philip; Mecking, Stefan

2017-10-04

Highly electron-withdrawing pentafluorosulfanyl groups were probed as substituents in an organometallic catalyst. In Ni(II) salicylaldiminato complexes as an example case, these highly electron-withdrawing substituents allow for polymerization of ethylene to higher molecular weights with reduced branching due to significant reductions in β-hydrogen elimination. Combined with the excellent functional group tolerance of neutral Ni(II) complexes, this suppression of β-hydrogen elimination allows for the direct polymerization of ethylene in water to nanocrystal dispersions of disentangled, ultrahigh-molecular-weight linear polyethylene.

Tailored Organometallic Polymers

Science.gov (United States)

1993-01-31

Webster, W. R. Herder, D. Y. Sogah, W. B. Farnham, T. V. ajan Babu, J. Am. Chem. soL • J105~. 5706-5708. [101 A. Boudin, (. Cerveau , C. Chuit, R.J. P...mngli,. 7., 237. [12] A. Boudin, G. Cerveau , C. Chuit, R. J. P. Corriu, C. Reyd, . o isj=, 7, 1165. [13] C. Brelire, R. J. P. Corriu, G. Royo, W. W. C...M.aa, J. Zwecker, Qrgg.omtaffic_ 9M 2, 2633-2635. [14] R. Tacke, J. Sperlich, C. Strohman, G. MatternU Ch 4 3.B=r 1 , 124., 1491-1496. [15] G. Cerveau

Lanthanide alkyl and silyl compounds: Synthesis, reactivity and catalysts for green

Energy Technology Data Exchange (ETDEWEB)

Pindwal, Aradhana [Iowa State Univ., Ames, IA (United States)

2016-01-01

The last few decades have witnessed enormous research in the field of organometallic lanthanide chemistry. Our research group has developed a few rare earth alkyl compounds containing tris(dimethylsilyl)methyl ligand and explored their reactivity. This thesis focusses on extending the study of lanthanide alkyl and silyl compounds to develop strategies for their synthesis and explore their reactivity and role as catalysts in processes such as hydrosilylation and cross-dehydrocoupling.

Fulltext PDF

Indian Academy of Sciences (India)

Aparna K, Kamalesh Babu R P, McDonald R and Cavell. R G 2001 Angew. Chem. Int. Ed. 40 4400. 26. Kasani A, Kamalesh Babu R P, McDonald R and Cavell. R G 1999 Organometallics 18 3775. 27. Aparna K, McDonald R, Fuerguson M and Cavell R G. 1999 Organometallics 18 4241. 28. Edelmann F T 1996 Top. Curr.

Expedient multi-step synthesis of organometallic complexes of Tc and Re in high effective specific activity. A new platform for the production of molecular imaging and therapy agents.

Science.gov (United States)

Causey, Patrick W; Besanger, Travis R; Schaffer, Paul; Valliant, John F

2008-09-15

For over thirty years, instant labeling kits which involve no purification steps have been the only method used to prepare (99m)Tc radiopharmaceuticals for clinical studies. To address the limitations imposed by instant kits, which is hindering the development of molecularly targeted Tc- and Re-based imaging and therapy agents, a new strategy for the rapid multistep synthesis and purification of organometallic technetium-based molecular probes and corresponding rhenium-based therapeutic analogues was developed. Beginning with MO4(-) (M = (99m)Tc, (186/188)Re), the carbonyl precursor [M(CO)3(H2O)3](+) was synthesized in 3 min in quantitative yield in a microwave reactor. A dipicolyl ligand was added and the chelate complex was formed in high yield in 2 min using microwave heating at 150 degrees C. This was followed by a new purification strategy to remove unlabeled ligand which entailed using a copper resin/C18 solid phase extraction protocol giving the desired product in greater than 78% decay corrected yield (dcy). Conversion to the corresponding succinimidyl active ester was achieved following a 5 min microwave irradiation at 120 degrees C and C18 solid phase extraction purification in 60% dcy. A series of amides were prepared subsequently by microwave heating at 120 degrees C for 5 min producing the desired targets in greater than 86% dcy. The reported method represents a move away from traditional instant kits toward more versatile platform synthesis and purification technologies that are better suited for producing modern molecular imaging and therapy agents.

Synthesis, spectroscopic characterization and in vitro cytotoxicities of new organometallic palladium complexes with biologically active β-diketones; Biological evaluation probing of the interaction mechanism with DNA/Protein and molecular docking

Science.gov (United States)

Karami, Kazem; Rafiee, Mina; Lighvan, Zohreh Mehri; Zakariazadeh, Mostafa; Faal, Ali Yeganeh; Esmaeili, Seyed-Alireza; Momtazi-Borojeni, Amir Abbas

2018-02-01

[Pd{(C,N)sbnd C6H4CH (CH3)NH}(CUR)] (3) and [Pd2{(C,N)sbnd C6H4CH(CH3)NH2}2(μ-N3CS2)] (4) [cur = 1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dion] novel organometallic complexes with biologically active ligands have been prepared and characterized via elemental analysis, multinuclear spectroscopic techniques (1H, and 13C NMR and IR) and their biological activities, including antitumoral activity and DNA-protein interactions have been investigated. Fluorescence spectroscopy used to study the interaction of the complexes with BSA have shown the affinity of the complexes for these proteins with relatively high binding constant values and the changed secondary structure of BSA in the presence of the complexes. In the meantime, spectroscopy and competitive titration have been applied to investigate the interaction of complexes with Warfarin and Ibuprofen site markers for sites I and II, respectively, with BSA. The results have suggested that the locations of complexes 3 and 4 are sites II and I, respectively. UV-Vis spectroscopy, emission titration and helix melting methods have been used to study the interaction of these complexes with CT-DNA, indicating that complexes are bound to CT-DNA by intercalation binding mode. In addition, good cytotoxic activity against MCF-7 (human breast cancer) and JURKAT (human leukemia) cell line has been shown by both complexes whereas low cytotoxicity was exerted on normal peripheral blood mononuclear cells.

Synthesis and characterization of a liquid Eu precursor (EuCp{sup pm}{sub 2}) allowing for valence control of Eu ions doped into GaN by organometallic vapor phase epitaxy

Energy Technology Data Exchange (ETDEWEB)

Mitchell, Brandon, E-mail: bmitchell@wcupa.edu [Department of Physics, West Chester University, West Chester, PA, 19383 (United States); Division of Materials and Manufacturing Science, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka, 565-0871 (Japan); Koizumi, Atsushi; Nunokawa, Takumi; Wakamatsu, Ryuta; Lee, Dong-gun; Saitoh, Yasuhisa; Timmerman, Dolf [Division of Materials and Manufacturing Science, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka, 565-0871 (Japan); Kuboshima, Yoshinori; Mogi, Takayuki; Higashi, Shintaro; Kikukawa, Kaoru [Kojundo Chemical Laboratory Co., Ltd., 5-1-28 Chiyoda, Sakado, Saitama, 350-0284 (Japan); Ofuchi, Hironori; Honma, Tetsuo [Japan Synchrotron Radiation Research Institute (JASRI/SPring-8), 1-1-1 Kouto, Sayo-cho, Sayo-gun, Hyogo, 679-5198 (Japan); Fujiwara, Yasufumi, E-mail: fujiwara@mat.eng.osaka-u.ac.jp [Division of Materials and Manufacturing Science, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka, 565-0871 (Japan)

2017-06-01

A liquid Eu precursor, bis(normal-propyl-tetramethylcyclopentadienyl)europium has been synthesized. This precursor exists as a liquid at temperatures higher than 49 °C, has a moderately high vapor pressure, contains no oxygen in its molecular structure, and can be distilled to high purity. These properties make it ideal for doping using a chemical vapor or atomic layer deposition method, and provide a degree of control previously unavailable. As a precursor the Eu exists in the divalent valance state, however, once doped into GaN by organometallic vapor phase epitaxy, the room-temperature photoluminescence of the Eu-doped GaN exhibited the typical red emission due to the intra-4f shell transition of trivalent Eu. After variation of the growth temperature, it was found that divalent Eu could be stabilized in the GaN matrix. By tuning the Fermi level through donor doping, the ratio of Eu{sup 2+} to Eu{sup 3+} could be controlled. The change in valence state of the Eu ions was confirmed using X-ray absorption near-edge structure. - Highlights: • A liquid Eu precursor was synthesized and its properties were characterized. • Precursor has a low melting point and a moderately high vapor pressure. • Does not contain oxygen in its molecular structure. • Eu can changed its valance state when incorporated into GaN. • Valence state of Eu in GaN can be controlled by donor doping.

Trends in metallo-organic chemistry of scandium, yttrium, and the lanthanides

International Nuclear Information System (INIS)

Singh, A.

1994-01-01

Several interesting aspects of the metallo-organic chemistry of group 3 and the lanthanides have been highlighted, which include: (a) the chemistry of a few notable organolanthanide compounds, alkoxo and aryloxo derivatives derived from sterically demanding ligands, (b) new trends in the chemistry of lanthanide heterometallic alkoxides, (c) an account of zero valent organometallics of yttrium and the lanthanides, and (d) aspects of agostic interactions in the lanthanide metallo-organic compounds. (author). 49 refs

Dependence of the sacroiliac indices of the X-ray stage of ankylosing spondylitis (Behterev's disease)

International Nuclear Information System (INIS)

Mlychkov, Kh.

1983-01-01

A total of 241 patients (482 sacroiliac indices) in different X-ray stage of the disease were studied and the data obtained were correlated with the sacroiliac indices in a control group of 104 normal subjects (208 sacroiliac indices). Sacroiliac indices were obtained by quantitative examination of the zones of interest of the sacroiliac joints and the sacrum, 3 hours after intravenous injection of 99 sup(m)Tc-pyrophosphate in indicator activities of 1.85 MBq/kg. The sacroiliac index levels increased with advancing X-ray stage of the disease within the I-III stage span; in the IV-th X-ray stage there was obvious decrease in these values. There appeared to exist statistically significant differences in the sacroiliac index values during all X-ray stages of the disease, as compared to the data obtained in the control group of healthy individuals (P<0.001). The significance level of the differences between neighbouring stages was low. Peak percentage of negative findings was observed in the zero stage (14.3) and in stage IV (11.7). The high percentage of positive findings in zero stage patients (15.7 per cent) is an evidence of the major sensitivity of quantitative scintigraphy in comparison with X-ray method of examination. (author)

Measurement of neutron yield by 62 MeV proton beam on a thick Beryllium target

International Nuclear Information System (INIS)

Alba, R; Cosentino, G; Zoppo, A Del; Pietro, A Di; Figuera, P; Finocchiaro, P; Maiolino, C; Santonocito, D; Schillaci, M; Barbagallo, M; Colonna, N; Boccaccio, P; Esposito, J; Celentano, A; Osipenko, M; Ricco, G; Ripani, M; Viberti, C M; Kostyukov, A

2013-01-01

In the framework of research on IVth generation reactors and high intensity neutron sources a low-power prototype neutron amplifier was recently proposed by INFN. It is based on a low-energy, high current proton cyclotron, whose beam, impinging on a thick Beryllium converter, produces a fast neutron spectrum. The world database on the neutron yield from thick Beryllium target in the 70 MeV proton energy domain is rather scarce. The new measurement was performed at LNS, covering a wide angular range from 0 to 150 degrees and an almost complete neutron energy interval. In this contribution the preliminary data are discussed together with the proposed ADS facility.

Synthesis and labelling of organo-metallic prosthetic groups used for indirect radioiodination of peptides and proteins

International Nuclear Information System (INIS)

Pozzi, Oscar R.; Castiglia, Silvia G.

1999-01-01

In the framework of an IAEA co-ordinated research programme the prosthetic compound ATE [N-succidinimil 3-(tri-n-butylstannyl) benzoate] has been synthesized and it has been labelled with 131 I and 125 I. Its structure has been confirmed by NMR and mass spectrometry. The labelled ATE has been conjugated with human immunoglobulin G with a yield of 41%-57%. Indirect radioiodination of peptides is currently prepared. (author)

La genèse de la première organisation prochinoise au Pérou (1963-1964. Idéologie et acteurs de la IVème conférence nationale du Parti Communiste péruvien (janvier 1964

Directory of Open Access Journals (Sweden)

1998-01-01

Full Text Available La création de la première organisation prochinoise au Pérou à l’issue de la IVème conférence nationale du Parti Communiste Péruvien marque-t-elle la victoire de la majorité des militants attachés à la pureté du marxisme-léninisme sur le “révisionnisme” des partisans de Moscou comme l’affirment les historiographes maoïstes ? L’analyse de l’articulation de la polémique idéologique sino-soviétique sur la lutte interne du P.C.P. démontre que l’idéologie est davantage un moyen pour justifier l’expulsion d’un ennemi commun - la “vieille garde” qui accapare la direction du Parti - qu’un trait d’union entre partisans de la IVème conférence nationale. GENESIS DE LA PRIMERA ORGANIZACIÓN PROCHINA EN EL PERÚ (1963-1964. IDEOLOGÍA Y ACTORES DE LA IVA CONFERENCIA NACIONAL DEL PARTIDO COMUNISTA PERUANO (ENERO DE 1964. La primera organización pro-china que nace en el Perú con la IVa conferencia nacional del Partido Comunista Peruano sería, como lo afirman los historiógrafos maoístas, el desenlace victorioso de la lucha que la mayoría de los militantes peruanos han desarrollado contra el “revisionismo” de los partidarios de Moscú en su afán de preservar la pureza del marxismo-leninismo. La manera cómo la polémica china-soviética se incorpora a la lucha interna que divide al P.C.P. nos demuestra que la ideología sirve más para justificar la expulsión de la “vieja guardia” de la dirección del Partido que para unificar a los partidarios de la IVa conferencia nacional mismos. THE GENESIS OF THE FIRST PRO-CHINESE ORGANIZATION IN PERU (1963-1964. IDEOLOGY AND ACTORS OF THE IVTH NATIONAL CONFERENCE OF THE PERUVIAN COMMUNIST PARTY (JANUARY 1964. Does the birth of the first pro-Chinese organization at the Peruvian Communist Party’s IVth conference mark, as Maoists historiographers assert the victory of the majority of the Peruvian communists over the “revisionists” pledged to Moscow in order to preserve the

Grafting heterogeneous catalyst with gamma radiation

International Nuclear Information System (INIS)

Garnett, J.L.; Long, M.A.; Levot, R.G.

1984-01-01

A process for the production of a heterogeneous catalyst comprises the steps of: irradiating an organic macromolecular substrate or a metal substrate with ionising or ultra violet radiation in the presence of a monomer selected from the group consisting of o-, m-, or p- styryl diphenyl phosphine and o-, m- or p- phenyl acrylyl diphenyl phosphine, to graft the monomer to the substrate; and reacting the graft copolymer with a homogeneous catalyst selected from the group consisting of catalytic metal salts and catalytic organometallic complexes such that the graft copolymer conjugate becomes a ligand of the catalyst

Air-stable compact of cobalt-rare earth alloy particles and method

International Nuclear Information System (INIS)

Smeggil, J.C.; Charles, R.J.

1975-01-01

A process is described for producing novel air-stable magnetic products. An organometallic compound which decomposes at a temperature below 500 0 C is mixed with particles of a transition metal-rare earth alloy. The resulting mixture is pressed to form a green body, which is then heated to decompose the organometallic compound to produce a metal vapor that deposits an interconnecting metal coating on the exposed surfaces of the pressed particles. (U.S.)

[(≢SiO)TaVCl2Me2]: A well-defined silica-supported tantalum(V) surface complex as catalyst precursor for the selective cocatalyst-free trimerization of ethylene

KAUST Repository

Chen, Yin; Callens, Emmanuel; Abou-Hamad, Edy; Merle, Nicolas; White, Andrew J P; Taoufik, Mostafa; Copé ret, Christophe; Le Roux, Erwan; Basset, Jean-Marie

2012-01-01

On the surface of it: In the absence of co-catalyst, a well-defined silica-supported surface organometallic complex [(≢SiO)Ta VCl2Me2] selectively catalyzes the oligomerization of ethylene. The use of surface organometallic species allows three different pathways to be determined for the reduction of TaV to TaIII species under pressure of ethylene. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

[(≢SiO)TaVCl2Me2]: A well-defined silica-supported tantalum(V) surface complex as catalyst precursor for the selective cocatalyst-free trimerization of ethylene

KAUST Repository

Chen, Yin

2012-10-22

On the surface of it: In the absence of co-catalyst, a well-defined silica-supported surface organometallic complex [(≢SiO)Ta VCl2Me2] selectively catalyzes the oligomerization of ethylene. The use of surface organometallic species allows three different pathways to be determined for the reduction of TaV to TaIII species under pressure of ethylene. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Modeling minor actinide multiple recycling in a lead-cooled fast reactor to demonstrate a fuel cycle without long-lived nuclear waste

Directory of Open Access Journals (Sweden)

Stanisz Przemysław

2015-09-01

Full Text Available The concept of closed nuclear fuel cycle seems to be the most promising options for the efficient usage of the nuclear energy resources. However, it can be implemented only in fast breeder reactors of the IVth generation, which are characterized by the fast neutron spectrum. The lead-cooled fast reactor (LFR was defined and studied on the level of technical design in order to demonstrate its performance and reliability within the European collaboration on ELSY (European Lead-cooled System and LEADER (Lead-cooled European Advanced Demonstration Reactor projects. It has been demonstrated that LFR meets the requirements of the closed nuclear fuel cycle, where plutonium and minor actinides (MA are recycled for reuse, thereby producing no MA waste. In this study, the most promising option was realized when entire Pu + MA material is fully recycled to produce a new batch of fuel without partitioning. This is the concept of a fuel cycle which asymptotically tends to the adiabatic equilibrium, where the concentrations of plutonium and MA at the beginning of the cycle are restored in the subsequent cycle in the combined process of fuel transmutation and cooling, removal of fission products (FPs, and admixture of depleted uranium. In this way, generation of nuclear waste containing radioactive plutonium and MA can be eliminated. The paper shows methodology applied to the LFR equilibrium fuel cycle assessment, which was developed for the Monte Carlo continuous energy burnup (MCB code, equipped with enhanced modules for material processing and fuel handling. The numerical analysis of the reactor core concerns multiple recycling and recovery of long-lived nuclides and their influence on safety parameters. The paper also presents a general concept of the novel IVth generation breeder reactor with equilibrium fuel and its future role in the management of MA.

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

Science.gov (United States)

Madix, Robert J.

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

Studies in group IV organometallic chemistry XXX. Synthesis of compounds containing tin---titanium and tin---zirconium bonds

NARCIS (Netherlands)

Creemers, H.M.J.C.; Verbeek, F.; Noltes, J.G.

1968-01-01

Starting from the tetrakis(diethylamino) derivatives of titanium and zirconium and pheyltin hydrides six intermetalic compounds contianing up to nine tin and titanium(or zirconium) atoms have been obtained by hydrostannolysis type reactions.

[Medical students' sexuality--development and fulfilment of sexual needs].

Science.gov (United States)

Müldner-Nieckowski, Łukasz; Klasa, Katarzyna; Sobański, Jerzy A; Rutkowski, Krzysztof; Dembińska, Edyta

2012-01-01

Education in human sexual physiology and pathology, as well as own sexual health of medical doctors determines in a large proportion the ability to talk with patients about their sexual disorders. Therefore the authors considered important to collect and assess data regarding sexual health and development of Medical Faculty students. Analysis of selected aspects of psychosexual development and sex life of IVth grade medical students. We applied the self-report Questionnaire of Satisfaction with Sexual Life (KSS2), an instrument created to assess sexual problems in patients treated with group psychotherapy. Medical students filled the questionnaire when attending the courses of Psychopathology of neurotic disorders or Psychotherapy. Analysis of the collected data revealed a relatively high differentiation of the studied group in regard of satisfaction and experiences with sexual life, attitudes towards masturbation, relationships and sexual activity. Regarding some aspects, significant differences between women and men occurred. A set of factors were identified, some of them may negatively influence medical doctor's competencies in the domain of sexual health. These are not having sexual debut or even lack of any erotic experiences and lack of sexual satisfaction. The results indicate a significant prevalence of factors, which may impede students education as well as taking into consideration the sexual issues during the medical interview. Assessment of influence of students' and doctors' own sexuality on their competencies in diagnostics and treatment requires further studies.

Development of a large volume injection method using a programmed temperature vaporization injector - gas chromatography hyphenated to ICP-MS for the simultaneous determination of mercury, tin and lead species at ultra-trace levels in natural waters.

Science.gov (United States)

Terán-Baamonde, J; Bouchet, S; Tessier, E; Amouroux, D

2018-04-27

The current EU legislation lays down Environmental Quality Standards (EQS) for 45 priority substances in surface waters; among them levels for (organo)metallic species of Hg, Sn and Pb are set between ng L -1 (for Hg and Sn) and μg L -1 (for Pb). To date, only a few analytical methods can reach these very restrictive limits and there is thus a need for comprehensive methods able to analyze these species down to these levels in natural waters. The aim of this work was to develop an online automated pre-concentration method using large volume injections with a Programmed Temperature Vaporization (PTV) injector fitted with a sorbent packed liner coupled to GC-ICP-MS to further improve the detection limits associated to this well-established method. The influence of several parameters such as the PTV transfer temperature and time, carrier gas flow rate and amount of packing material was investigated. Finally, the maximum volume injected through single or multiple injection modes was optimized to obtain the best compromise between chromatographic resolution and sensitivity. After optimization, very satisfactory results in terms of absolute and methodological detection limits were achieved, down to the pg L -1 level for all species studied. The potential of the method was exemplified by determining the concentrations of organometallic compounds in unpolluted river waters samples from the Adour river basin (SW France) and results were compared with conventional (splitless) GC-ICP-MS. The strength of this analytical method lies in the low detection limits reached for the simultaneous analysis of a wide group of organometallic compounds, and the potential to transfer this method to other gas chromatographic applications with inherent lower sensitivity. Copyright © 2018 Elsevier B.V. All rights reserved.

Synthesis and reactivity of triscyclopentadienyl uranium (III) and (IV) complexes

International Nuclear Information System (INIS)

Berthet, J.C.

1992-01-01

The reactions of (RC 5 H 4 ) 3 U with R=trimethylsilylcyclopentadienyl or tertiobutylcyclopentadienyl are studied for the synthesis of new uranium organometallic compounds. Reactions with sodium hydride are first described uranium (III) anionic hydrides obtained are oxidized for synthesis of stable uranium (IV) organometallic hydrides. Stability of these compounds is discussed. Reactivity of these uranium (III) and (IV) hydrides are studied. Formation of new binuclear compounds with strong U-O and U-N bonds is examined and crystal structure are presented. Monocyclooctatetraenylic uranium complexes are also investigated

Influence of the growth parameters on TiO2 thin films deposited using the MOCVD method

Directory of Open Access Journals (Sweden)

Bernardi M. I. B.

2002-01-01

Full Text Available In this work we report the synthesis of TiO2 thin films by the Organometallic Chemical Vapor Deposition (MOCVD method. The influence of deposition parameters used during the growth in the obtained structural characteristics was studied. Different temperatures of the organometallic bath, deposition time, temperature and type of the substrate were combined. Using Scanning Electron Microscopy associated to Electron Dispersive X-Ray Spectroscopy, Atomic Force Microscopy and X-ray Diffraction, the strong influence of these parameters in the thin films final microstructure was verified.

OMVPE growth of GaInAsSb in the 2 to 2.4 microm range

International Nuclear Information System (INIS)

Charache, G.W.; Wang, C.A.

1997-12-01

Ga 1-x In x As y Sb 1-y epilayers were grown lattice matched to GaSb substrates by organometallic vapor phase epitaxy using all organometallic precursors, which include triethylgallium, trimethylindium, tertiarybutylarsine, and trimethylantimony. Layers were grown over a temperature range between 525 and 575 C, a V/III ratio range between 0.9 and 1.7, x 15 cm -3 and hole mobility of ∼ 430 to 560 cm 2 /V-s. The n- and p-type doping of GaInAsSb with diethyltellurium and dimethylzinc, respectively, are also reported

Artificial Metalloenzymes Based on the Biotin-Streptavidin Technology: Challenges and Opportunities.

Science.gov (United States)

Heinisch, Tillmann; Ward, Thomas R

2016-09-20

The biotin-streptavidin technology offers an attractive means to engineer artificial metalloenzymes (ArMs). Initiated over 50 years ago by Bayer and Wilchek, the biotin-(strept)avidin techonology relies on the exquisite supramolecular affinity of either avidin or streptavidin for biotin. This versatile tool, commonly referred to as "molecular velcro", allows nearly irreversible anchoring of biotinylated probes within a (strept)avidin host protein. Building upon a visionary publication by Whitesides from 1978, several groups have been exploiting this technology to create artificial metalloenzymes. For this purpose, a biotinylated organometallic catalyst is introduced within (strept)avidin to afford a hybrid catalyst that combines features reminiscent of both enzymes and organometallic catalysts. Importantly, ArMs can be optimized by chemogenetic means. Combining a small collection of biotinylated organometallic catalysts with streptavidin mutants allows generation of significant diversity, thus allowing optimization of the catalytic performance of ArMs. Pursuing this strategy, the following reactions have been implemented: hydrogenation, alcohol oxidation, sulfoxidation, dihydroxylation, allylic alkylation, transfer hydrogenation, Suzuki cross-coupling, C-H activation, and metathesis. In this Account, we summarize our efforts in the latter four reactions. X-ray analysis of various ArMs based on the biotin-streptavidin technology reveals the versatility and commensurability of the biotin-binding vestibule to accommodate and interact with transition states of the scrutinized organometallic transformations. In particular, streptavidin residues at positions 112 and 121 recurrently lie in close proximity to the biotinylated metal cofactor. This observation led us to develop a streamlined 24-well plate streptavidin production and screening platform to optimize the performance of ArMs. To date, most of the efforts in the field of ArMs have focused on the use of purified

Molecular geometry

CERN Document Server

Rodger, Alison

1995-01-01

Molecular Geometry discusses topics relevant to the arrangement of atoms. The book is comprised of seven chapters that tackle several areas of molecular geometry. Chapter 1 reviews the definition and determination of molecular geometry, while Chapter 2 discusses the unified view of stereochemistry and stereochemical changes. Chapter 3 covers the geometry of molecules of second row atoms, and Chapter 4 deals with the main group elements beyond the second row. The book also talks about the complexes of transition metals and f-block elements, and then covers the organometallic compounds and trans

Chemical Sciences Division: Annual report 1992

International Nuclear Information System (INIS)

1993-10-01

The Chemical Sciences Division (CSD) is one of twelve research Divisions of the Lawrence Berkeley Laboratory, a Department of Energy National Laboratory. The CSD is composed of individual groups and research programs that are organized into five scientific areas: Chemical Physics, Inorganic/Organometallic Chemistry, Actinide Chemistry, Atomic Physics, and Physical Chemistry. This report describes progress by the CSD for 1992. Also included are remarks by the Division Director, a description of work for others (United States Office of Naval Research), and appendices of the Division personnel and an index of investigators. Research reports are grouped as Fundamental Interactions (Photochemical and Radiation Sciences, Chemical Physics, Atomic Physics) or Processes and Techniques (Chemical Energy, Heavy-Element Chemistry, and Chemical Engineering Sciences)

New insights about antibiotic production by Pseudomonas aeruginosa: a gene expression analysis

Science.gov (United States)

Gionco, Bárbara; Tavares, Eliandro R.; de Oliveira, Admilton G.; Yamada-Ogatta, Sueli F.; do Carmo, Anderson O.; Pereira, Ulisses de Pádua; Chideroli, Roberta T.; Simionato, Ane S.; Navarro, Miguel O. P.; Chryssafidis, Andreas L.; Andrade, Galdino

2017-09-01

The bacterial resistance for antibiotics is one of the most important problems in public health and only a small number of new products are in development. Antagonistic microorganisms from soil are a promising source of new candidate molecules. Products of secondary metabolism confer adaptive advantages for their producer, in the competition for nutrients in the microbial community. The biosynthesis process of compounds with antibiotic activity is the key to optimize their production and the transcriptomic study of microorganisms is of great benefit for the discovery of these metabolic pathways. Pseudomonas aeruginosa LV strain growing in the presence of copper chloride produces a bioactive organometallic compound, which has a potent antimicrobial activity against various microorganisms. The objective of this study was to verify overexpressed genes and evaluate their relation to the organometallic biosynthesis in this microorganism. P. aeruginosa LV strain was cultured in presence and absence of copper chloride. Two methods were used for transcriptomic analysis, genome reference-guided assembly and de novo assembly. The genome referenced analysis identified nine upregulated genes when bacteria were exposed to copper chloride, while the De Novo Assembly identified twelve upregulated genes. Nineteen genes can be related to an increased microbial metabolism for the extrusion process of exceeding intracellular copper. Two important genes are related to the biosynthesis of phenazine and tetrapyrroles compounds, which can be involved in the bioremediation of intracellular copper and biosynthesis of the organometallic compound. Additional studies are being carried out to further prove the function of the described genes and relate them to the biosynthetic pathway of the organometallic compound.

Synthesis of LDPE-g-AA-M [M=Cu(1), Fe(II) and Ni(II)] copolymers via gamma ray-radiation and their use as catalysts and support for poly aniline formation

International Nuclear Information System (INIS)

Urena N, F.; Sanchez M, V.; Lopez C, R.

2009-01-01

Coordination polymers have many current and potential uses as electrical materials, colorants, medical agents, among others. One of the most vigorously studied areas of application is the use of polymer supports for homogeneous catalysis of organic reactions as hydrogenation, carbonylation and hydroformylation. This kind of catalyst support show clear advantages as their chemical inert character, they can be easily functionalized and prepared with a wide range of properties. A common method to prepare organometallic polymers is the grafting of functionalized polymers onto a main polymer chain in order to fix subsequently electro attractive groups (metals in this case). The functionalized polymer may be grafted using UV, γ-radiation or high energy electrons. In this chapter, the preparation of a series of low density polyethylene (LDPE) grafted with acrylic acid is presented. The grafting reactions were initiated by different doses of γ-radiation. Subsequently, the LDPE-g-AA copolymers were coordinated with different metals such a cooper, iron and nickel. Finally, the organometallic polymers were supported with poly aniline. Samples were characterized by infrared spectroscopy, atomic absorption, scanning electron microscopy, X-ray diffraction, thermogravimetric analysis and differential scanning calorimetry. The electric conductivity of the supported poly aniline was determined by using an indirect method. (Author)

Novel bimetallic dispersed catalysts for temperature-programmed coal liquefaction

Energy Technology Data Exchange (ETDEWEB)

Chunshan, Song; Kirby, S.; Schmidt, E. [Pennsylvania State Univ., University Park, PA (United States)] [and others

1995-12-31

The objective of this project is to explore bimetallic dispersed catalysts for more efficient coal liquefaction. Coal liquefaction involves cleavage of methylene, dimethylene and ether bridges connecting various aromatic units and the reactions of various oxygen functional groups. This paper describes recent results on (1) hydrodeoxygenation of O-containing polycyclic model compounds using novel organometallic catalyst precursors; and (2) activity and selectivity of dispersed Fe catalysts from organometallic and inorganic precursors for hydrocracking of 4-(1-naphthylmethyl) bibenzyl. The results showed that some iron containing catalysts have higher activity in the sulfur-free form, contrary to conventional wisdom. Adding sulfur to Fe precursors with Cp-ligands decreased the activity of the resulting catalyst. This is in distinct contrast to the cases with iron pentacarbonyl and superfine Fe{sub 2}O{sub 3}, where S addition increased their catalytic activity substantially. A positive correlation between sulfur addition and increased activity can be seen, but a reversed trend between Fe cluster size and hydrocracking conversion could be observed, for carbonyl-type Fe precursors. It is apparent that the activity and selectivity of Fe catalysts for NMBB conversion depends strongly on both the type of ligand environment, the oxidation state and the number of intermetal bonds in the molecular precursor.

Modification of the estrogenic properties of diphenols by the incorporation of ferrocene. Generation of antiproliferative effects in vitro.

Science.gov (United States)

Vessières, Anne; Top, Siden; Pigeon, Pascal; Hillard, Elizabeth; Boubeker, Leila; Spera, Daniela; Jaouen, Gérard

2005-06-16

We report here the synthesis and the strong and unexpected antiproliferative effect of the organometallic diphenolic compound 1,1-bis(4'-hydroxyphenyl)-2-ferrocenyl-but-1-ene (4) on both hormone-dependent (MCF7) and -independent (MDA-MB231) breast cancer cells (IC(50) = 0.7 and 0.6 microM). Surprisingly, 6 [1,2-bis(4'-hydroxyphenyl)-2-ferrocenyl-but-1-ene], the regioisomer of 4, shows only a modest effect on these cell lines. This pertinent organometallic modification seems to trigger an intracellular oxidation of the structurally favorable compound 4, leading to the generation of a potent cytotoxic compound.

Formation of ferric flocks for the removal of Zn and Cu from dockyard wastewater

DEFF Research Database (Denmark)

Ottosen, Lisbeth M.; Arevalo, Edurado; Stichnothe, Heinz

2006-01-01

Wastewater from wash down of boat hulls contains typically Cu, Zn and organometallic biocides, e.g. tributyltin (TBT). In some cases this wastewater is led directly into the marine system. In the present paper a cheap flocculation method (iron flocculants) for removal of Cu and Zn from the wastew......Wastewater from wash down of boat hulls contains typically Cu, Zn and organometallic biocides, e.g. tributyltin (TBT). In some cases this wastewater is led directly into the marine system. In the present paper a cheap flocculation method (iron flocculants) for removal of Cu and Zn from...

Moessbauer spectroscopic characterisation of catalysts obtained by interaction between tetra-n-butyl-tin and silica or silica supported rhodium

International Nuclear Information System (INIS)

Millet, J.M.M.; Toyir, J.; Didillon, B.; Candy, J.P.; Nedez, C.; Basset, J.M.

1997-01-01

Moessbauer spectroscopy at 78 K was used to study the interaction between tetra-n-butyl-tin and the surfaces of silica or silica supported rhodium. At room temperature, the tetra-n-butyl-tin was physically adsorbed on the surfaces. After reaction under hydrogen at 373 K, the formation of grafted organometallic fragments on the Rh surface was confirmed whereas with pure silica, ≡SiO-Sn(n-C 4 H 9 ) 3 moieties were observed. After treatment at 523 K, the rhodium grafted organometallic species was completely decomposed and there was formation of a defined bimetallic RhSn compound

The characteristics of internet addiction adolescents and their families

Directory of Open Access Journals (Sweden)

Dukanac Vesna

2015-01-01

Full Text Available The goal of the study was to identify specific personality characteristics of adolescents who have a problem with 'internet addiction', as well as the characteristics of their parents' personalities and of thefunctioning of their families. The sample consisted of 60 adolescents of both genders, agedbetween 15 and18. There were 30'internet addicts' belonging to the clinical group and 30 participants from the general population as the control group. Also, 120 parentswere examined; there were 30 parent couples of eachof the two groups of adolescents. The following measures were used in the research: Young's Internet Addiction Test -IAT, the Belgrade Adolescent Personality Inventory - BAPI, the Temperament and Character Inventory-Revisited -TCI-R (for the assessment of parental personality and the Family Adaptability and Cohesion Evaluation Scale -FACES IV.The results indicate that adolescents with internet addiction difficulties exhibit a high degree of impulsiveness, low persistence, and immaturity in the personality domains which regulate responsible, goal-directed and co-operative behaviour. The fathers of adolescents from the clinical group were highly ambitious and less available to their children, while their mothers were more impulsive and prone to change versus continuity, which means that they were also less accessible to their children, albeit in a different way than the fathers. All dimensions associated with the positive aspects of family functioning, such as Cohesiveness, Flexibility, Communication and Satisfaction were lower in the clinical group, while the dimension of Chaotic relations was higher. The results have shownthat the parents of adolescents from the clinical group have formed a specific kindof disengaged and distant parenting style that has resultedin avoiding behaviours of adolescents and their withdrawal into the 'virtual world'. These findings could have a significant role in understanding the originsof internet

Systematic Studies on Anharmonicity of Rattling Phonons in Type I Clathrates by Low Temperature Heat Capacity Measurements

Science.gov (United States)

Tanigaki, Katsumi; Wu, Jiazhen; Tanabe, Yoichi; Heguri, Satoshi; Shiimotani, Hidekazu; Tohoku University Collaboration

2014-03-01

Clathrates are featured by cage-like polyhedral hosts mainly composed of the IVth group elements of Si, Ge, or Sn and alkali metal or alkaline-earth metal elements can be accommodated inside as a guest atom. One of the most intriguing issues in clathrates is their outstanding high thermoelectric performances thanks to the low thermal conductivity. Being irrespective of good electric conductivity σ, the guest atom motions provide a low-energy lying less-dispersive phonons and can greatly suppress thermal conductivity κ. This makes clathrates close to the concept of ``phonon glass electron crystal: PGEC'' and useful in thermoelectric materials from the viewpoint of the figure of merit. In the present study, we show that the local phonon anharmonicity indicated by the tunneling-term of the endohedral atoms (αT) and the itinerant-electron term (γeT), both of which show T-linear dependences in specific heat Cp, can successfully be separated by employing single crystals with various carrier concentrations in a wide range of temperture experimennts. The factors affecting on the phonon anharmonicity as well as the strength of electron-phonon interactions will be discussed based on our recent experiments. The research was financially supported by Ministry of Education, Science, Sports and Culture, Grant in Aid for Science, and Technology of Japan.

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

Science.gov (United States)

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

2017-08-01

0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 CHCD 3 , using [Rh(Cy 2 PCH 2 CH 2 PCy 2 )(η 2 η 2 -NBA)][BAr F 4 ] scrambles the D-label into all possible positions of the propene, as shown by isotopic perturbation of equilibrium measurements for the agostic interaction. Periodic DFT calculations show a low barrier to H/D exchange (10.9 kcal mol -1 , PBE-D3 level), and GIPAW chemical shift calculations guide the assignment of the experimental data. When synthesized using solution routes a bis-propene complex, [Rh(Cy 2 PCH 2 CH 2 PCy 2 )(propene) 2 ][BAr F 4 ] , is formed. [Rh(Cy 2 PCH 2 CH 2 PCy 2 )(butene)][BAr F 4 ] ( x = 1) is characterized as having 2-butene bound as the cis -isomer and a single Rh···H 3 C agostic interaction. In the solid-state two low-energy fluxional processes are proposed. The first is a simple libration of the 2-butene that exchanges the agostic interaction, and the second is a butene isomerization process that proceeds via an allyl-hydride intermediate with a low computed barrier of 14.5 kcal mol -1 . [Rh(Cy 2 PCH 2 CH 2 PCy 2 )(η 2 η 2 -NBA)][BAr F 4 ] and the polymorphs of [Rh(Cy 2 PCH 2 CH 2 PCy 2 )(ethene) 2 ][BAr F 4 ] are shown to be effective in solid-state molecular organometallic catalysis (SMOM-Cat) for the isomerization of 1-butene to a mixture of cis - and trans -2-butene at 298 K and 1 atm, and studies suggest that catalysis is likely dominated by surface-active species. [Rh(Cy 2 PCH 2 CH 2 PCy 2 )(η 2 η 2 -NBA

Inorganic, coordination and organometallic compounds

International Nuclear Information System (INIS)

Jursik, F.

1978-01-01

Separation of cations and anions of inorganic, coordination and metalloorganic compounds by the method of liquid column chromatography is considered. Common scheme of multicomponent cation mixture is suggesteed. Separation conditions, adsrbents, eluents, pH value solution concenstration, elution rate are also suggested. Separation of rare earth elements Cs, Be, Cd, Te, Th, U, Mo, Re, V, Ru, Zr, In compounds is considered as an example of liquid column chromatography application. Data on column chromatography application are summarized in a table

New Insights about Antibiotic Production by Pseudomonas aeruginosa: A Gene Expression Analysis

Directory of Open Access Journals (Sweden)

Bárbara Gionco

2017-09-01

Full Text Available The bacterial resistance for antibiotics is one of the most important problems in public health and only a small number of new products are in development. Antagonistic microorganisms from soil are a promising source of new candidate molecules. Products of secondary metabolism confer adaptive advantages for their producer, in the competition for nutrients in the microbial community. The biosynthesis process of compounds with antibiotic activity is the key to optimize their production and the transcriptomic study of microorganisms is of great benefit for the discovery of these metabolic pathways. Pseudomonas aeruginosa LV strain growing in the presence of copper chloride produces a bioactive organometallic compound, which has a potent antimicrobial activity against various microorganisms. The objective of this study was to verify overexpressed genes and evaluate their relation to the organometallic biosynthesis in this microorganism. P. aeruginosa LV strain was cultured in presence and absence of copper chloride. Two methods were used for transcriptomic analysis, genome reference-guided assembly and de novo assembly. The genome referenced analysis identified nine upregulated genes when bacteria were exposed to copper chloride, while the De Novo Assembly identified 12 upregulated genes. Nineteen genes can be related to an increased microbial metabolism for the extrusion process of exceeding intracellular copper. Two important genes are related to the biosynthesis of phenazine and tetrapyrroles compounds, which can be involved in the bioremediation of intracellular copper and we suggesting that may involve in the biosynthesis of the organometallic compound. Additional studies are being carried out to further prove the function of the described genes and relate them to the biosynthetic pathway of the organometallic compound.

Bis-ligated Ti and Zr complexes of chelating N-heterocyclic carbenes

KAUST Repository

El-Batta, Amer

2011-07-01

In this communication we report the synthesis of novel titanium and zirconium complexes ligated by bidentate "salicylaldimine-like" N-heterocyclic carbenes (NHC). Double addition of the NHC chelate to either TiCl4(thf)2 or ZrCl4 forms bis-ligated organometallic fragments with a distorted octahedral geometry. These complexes are rare examples of group IV transition-metal NHC adducts. Preliminary catalytic tests demonstrate that in the presence of methylaluminoxane (MAO) these complexes are useful initiators for the polymerization of ethylene and the copolymerization of ethylene with norbornene and 1-octene. © 2011 Elsevier B.V. All rights reserved.

Chemical Sciences Division annual report 1994

Energy Technology Data Exchange (ETDEWEB)

NONE

1995-06-01

The division is one of ten LBL research divisions. It is composed of individual research groups organized into 5 scientific areas: chemical physics, inorganic/organometallic chemistry, actinide chemistry, atomic physics, and chemical engineering. Studies include structure and reactivity of critical reaction intermediates, transients and dynamics of elementary chemical reactions, and heterogeneous and homogeneous catalysis. Work for others included studies of superconducting properties of high-{Tc} oxides. In FY 1994, the division neared completion of two end-stations and a beamline for the Advanced Light Source, which will be used for combustion and other studies. This document presents summaries of the studies.

Complexes carbéniques nucléophiles de l'uranium

OpenAIRE

Tourneux , Jean-Christophe

2012-01-01

The only stable f-metal carbene complexes (excluding NHC) metals f present R2C(2-) groups having one or two phosphorus atoms in the central carbon in alpha position. The objective of this work was to develop the chemistry of carbenes for uranium (metal 5f) with the dianion C{Ph2P(=S)}2(2-) (SCS(2-)) to extend the organometallic chemistry of this element in its various oxidation states (+3-6), and to reveal the influence of the 5f orbitals on the nature and reactivity of the double bond C=U.We...

Synthesis and reactivity of uranium (III) cyclopentadienyl complexes

International Nuclear Information System (INIS)

Foyentin, M.

1987-01-01

New uranium organometallic complexes are synthetized from the addition compound Cp U (THF). Reactions with lithium compounds, chlorides, alkynes and borohydrides. Oxidizing addition reactions are evidenced with alkyl halogenides. With a strong reducing agent, the complex Cp-UCH-Li allows the fixation and the reduction of nitrogen into ammonia. Lability of ligands bound to U (III) is evidenced, giving very reactive species and hence catalytic properties for these compounds. Catalytic hydrogenation of olefins is studied. Substitution reactions of alkyl groups of these complexes with olefins in presence or not of hydrogen or with alkyllithium are original [fr

Metals on graphene and carbon nanotube surfaces: From mobile atoms to atomtronics to bulk metals to clusters and catalysts

KAUST Repository

Sarkar, Santanu C.

2014-01-14

In this Perspective, we present an overview of recent fundamental studies on the nature of the interaction between individual metal atoms and metal clusters and the conjugated surfaces of graphene and carbon nanotube with a particular focus on the electronic structure and chemical bonding at the metal-graphene interface. We discuss the relevance of organometallic complexes of graphitic materials to the development of a fundamental understanding of these interactions and their application in atomtronics as atomic interconnects, high mobility organometallic transistor devices, high-frequency electronic devices, organometallic catalysis (hydrogen fuel generation by photocatalytic water splitting, fuel cells, hydrogenation), spintronics, memory devices, and the next generation energy devices. We touch on chemical vapor deposition (CVD) graphene grown on metals, the reactivity of its surface, and its use as a template for asymmetric graphene functionalization chemistry (ultrathin Janus discs). We highlight some of the latest advances in understanding the nature of interactions between metals and graphene surfaces from the standpoint of metal overlayers deposited on graphene and SWNT thin films. Finally, we comment on the major challenges facing the field and the opportunities for technological applications. © 2013 American Chemical Society.

Synthesis and structures of bimetallic titanium and chromium carbene complexes of the type Cp/sub 2/Ti(Cl)O(CH/sub 3/)CCr(CO)/sub 5/

Energy Technology Data Exchange (ETDEWEB)

Anslyn, E.V.; Santarsiero, B.D.; Grubbs, R.H.

1988-10-01

Insertion reactions are some of the most common and important reactions in organometallic chemistry. Aside from being mechanistically interesting, they have proven useful in organic synthesis and have been postulated in catalytic cycles. A subset of the broad group of insertion reactions is the insertion of carbon monoxides of group VIB metal carbonyl complexes into early-transition-metal alkyl, aryl and hydride bonds. Although the coupling of metal alkylidenes with metal carbonyl complexes is rare in monometallic systems, such coupling is frequently postulated in heterogeneous Fischer-Tropsch systems to yield surface-bound ketene fragments. The formation of bound ketene in bimetallic and cluster complexes has been documented. Herein the authors report the coupling of titanocene methylidene with Cr(CO)/sub 6/ to yield a titanocene ketene complex.

Polyhalogenated hydrocarbon refrigerants and refrigerant oils colored with fluorescent dyes and method for their use as leak detectors

Energy Technology Data Exchange (ETDEWEB)

Parekh, M.

1988-07-19

A leak detectable refrigeration composition is described comprising: (A) a refrigeration liquid selection from the group consisting of: (1) a polyhalogenated hydrocarbon refrigerant; (2) a refrigeration oil selected from the group consisting of naphthenic oils, paraffinic oils, alkylated benzenes, silicones, polyglycols, diesters or triesters of dicarboxylic or tricarboxylic acids, and polyalkyl silicate oils, and (3) a mixture of A(1) and A(2), and (B) a fluorescent dye compound or composition comprising the dye selected from the group consisting of: (1) a fluorescent dye selected from the group consisting of perylene, naphthoxanthene, monocyclic aromatic compounds having an organometallic compound, (2) a solution of fluorescent dye in a solvent, and (3) a mixture of B(1) and B(2). The fluorescent dye compound or composition is soluble in the refrigeration liquid. The concentration of the dye being at least 0.001 grams per 100 grams of the refrigeration liquid.

Current organic chemistry

National Research Council Canada - National Science Library

1997-01-01

Provides in depth reviews on current progress in the fields of asymmetric synthesis, organometallic chemistry, bioorganic chemistry, heterocyclic chemistry, natural product chemistry, and analytical...

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

KAUST Repository

Samantaray, Manoja; Dey, Raju; Kavitake, Santosh Giridhar; Basset, Jean-Marie

2015-01-01

In this chapter we describe the recent applications of well-defined oxidesupported metal alkyls/alkylidenes/alkylidynes and hydrides of group IV, V, and VI transition metals in the field of C–H and C–C bond activation. The activation of ubiquitous C

Group Flow and Group Genius

Science.gov (United States)

Sawyer, Keith

2015-01-01

Keith Sawyer views the spontaneous collaboration of group creativity and improvisation actions as "group flow," which organizations can use to function at optimum levels. Sawyer establishes ideal conditions for group flow: group goals, close listening, complete concentration, being in control, blending egos, equal participation, knowing…

[Height and weight growth delay and protein-energy malnutrition in children with chronic dialysis].

Science.gov (United States)

Perţea, L; Diaconeasa, Lavinia; Burlea, M; Munteanu, Mihaela; Brumariu, O

2010-01-01

Growth retardation is an important problem in children with chronic renal disease, and malnutrition is a determinative factor. The study intends to assess the relationship between protein-energy malnutrition and stature-weight retardation in children enrolled in chronic dialysis program. The study group was composed of 16 children (5 boys and 11 girls--sex ratio of 2.2) hospitalized in the IVth Nephrology Clinic at Clinical Emergency Hospital "St. Maria" Iaşi, 13 rural and 3 urban, aged between 9 and 17 years, with chronic dialysis program. This was a follow-up study during a period of 4 years (2006-2009), resulting in correlations between anthropometric paremeters, biochemical, BIA and DEXA data. The stature-weight deficiency of the 16 patients was as follows: after an average period of 61.7 months of HD and 32.7 months of PD, in children older than 12 years (mean age 15.27 years), 7 of 10 had stature-weight deficits higher than (-3DS) or (-4DS). The group with less than (-2DS) stature-weight deficits showed the same mean age of 15.2 years, the protein energy-malnutrition was present in 2 cases (33%) and was attributed to a dialysis period shorter than 13.8 months. The late diagnosis of the disease (at an average age of 13 years), the long period of chronic dialysis program (over 39.5 months on average) and the early debut of malnutrition are favoring or worsening factors of stature-weight retardation. After correlating ESG with biochemical, BIA and DEXA data, in our group were identified 4 cases of moderate malnutrition and 9 cases of severe malnutrition.

Juvenile wood volume and its proportion to stem volume vs. selected biometric features of Scots pine (Pinus sylvestris L. trees

Directory of Open Access Journals (Sweden)

Arkadiusz Tomczak

2011-01-01

Full Text Available The aim of the study was to determine whether there is a correlation between breast height diameter, tree height and stem total volume of Scots pines, on the one hand, and volume and proportion of juvenile wood, on the other. The investigations comprised pure pine stands of the IInd, IIIrd, IVth and Vth age classes developed in conditions of fresh mixed coniferous forest. A distinct curvilinear correlation was found between volume and proportion of juvenile wood in tree stems and breast height diameter, height and stem total volume. Because of high values of determination coefficients (R2, which characterised the above-mentioned correlations, it seems appropriate to use these regularities to assess the quality of the timber raw material regarding the proportions of its volume and juvenile wood in stems of Scots pine trees.

Total body irradiation as a form of preparation for bone marrow transplantation

International Nuclear Information System (INIS)

Inoue, Toshihiko

1987-01-01

The history of total body irradiation and bone marrow transplantation is surprisingly old. Following the success of Thomas et al. in the 1970s, bone marrow transplantation appeared to be the sole curative treatment modality for high-risk leukemia. A supralethal dose of total body irradiation was widely accepted as a form of preparation for bone marrow transplantation. In this paper, I described the present status of bone marrow transplantation for leukemia patients in Japan based on the IVth national survey. Since interstitial pneumonitis was one of the most life threatening complications after bone marrow transplantation, I mentioned the dose, dose-rate and fraction of total body irradiation in more detail. In addition, I dealt with some problems of the total body irradiation, such as dose prescription, compensating contour as well as inhomogeneity, and shielding for the highrisk organs. (author) 82 refs

Presidential Green Chemistry Challenge: 2007 Academic Award

Science.gov (United States)

Presidential Green Chemistry Challenge 2007 award winner, Professor Michael J. Krische, developed selective C-C bond-forming hydrogenation without organometallic reagents, eliminating hazardous reagents and hazardous waste.

Well-defined silica supported bipodal molybdenum oxo alkyl complexes: a model of the active sites of industrial olefin metathesis catalysts

KAUST Repository

Merle, Nicolas

2017-09-25

A well-defined, silica-supported molybdenum oxo alkyl species, ([triple bond, length as m-dash]SiO-)2Mo([double bond, length as m-dash]O)(CH2tBu)2, was prepared by the selective grafting of Mo([double bond, length as m-dash]O)(CH2tBu)3Cl onto a silica partially dehydroxylated at 200 °C using a rigorous surface organometallic chemistry approach. The immobilized bipodal surface species, partly resembling the active species of industrial MoO3/SiO2 olefin metathesis catalysts, exhibited excellent functional group tolerance in conjunction with its high activity in homocoupling, self and ring closing olefin metathesis.

The importance of environmental factors and matrices in the adsorption, desorption, and toxicity of butyltins

DEFF Research Database (Denmark)

Fang, Liping; Xu, Cuihong; Li, Ji

2017-01-01

detrimental effects on humans and aquatic organisms. This work provides a critical review of recent studies on the adsorption, desorption, bioaccumulation, and toxicity of BTs that can notably influence the distribution of BTs in the environment. Influence of environmental factors (e.g., pH and salinity......Butyltins (BTs) are considered as a group of the most important organometallic compounds in industry and agriculture. Due to their widespread use, large amounts of BTs including tributyltin (TBT), dibutyltin (DBT), and monobutyltin (MBT) have entered into the environment, and subsequently causing......) and adsorbents in the matrices (e.g., minerals, organic carbons, and quartz) on the adsorption, desorption, and toxicity of BTs is particularly addressed....

α-Imino Esters in Organic Synthesis: Recent Advances.

Science.gov (United States)

Eftekhari-Sis, Bagher; Zirak, Maryam

2017-06-28

α-Imino esters are useful precursors for the synthesis of a variety of types of natural and unnatural α-amino acid derivatives, with a wide range of biological activities. Due to the adjacent ester group, α-imino esters are more reactive relative to other types of imines and undergo different kinds of reactions, including organometallics addition, metal catalyzed vinylation and alkynylation, aza-Henry, aza-Morita-Baylis-Hillman, imino-ene, Mannich-type, and cycloaddition reactions, as well as hydrogenation and reduction. This review discusses the mechanism, scope, and applications of the reactions of α-imino esters and related compounds in organic synthesis, covering the literature from the last 12 years.

Well-defined silica supported bipodal molybdenum oxo alkyl complexes: a model of the active sites of industrial olefin metathesis catalysts

KAUST Repository

Merle, Nicolas; Le Qué mé ner, Fré dé ric; Barman, Samir; Samantaray, Manoja; Szeto, Kai C.; De Mallmann, Aimery; Taoufik, Mostafa; Basset, Jean-Marie

2017-01-01

A well-defined, silica-supported molybdenum oxo alkyl species, ([triple bond, length as m-dash]SiO-)2Mo([double bond, length as m-dash]O)(CH2tBu)2, was prepared by the selective grafting of Mo([double bond, length as m-dash]O)(CH2tBu)3Cl onto a silica partially dehydroxylated at 200 °C using a rigorous surface organometallic chemistry approach. The immobilized bipodal surface species, partly resembling the active species of industrial MoO3/SiO2 olefin metathesis catalysts, exhibited excellent functional group tolerance in conjunction with its high activity in homocoupling, self and ring closing olefin metathesis.

Delayed replantation of rat teeth after use of reconstituted powdered milk as a storage medium.

Science.gov (United States)

dos Santos, Cláudia Letícia Vendrame; Sonoda, Celso Koogi; Poi, Wilson Roberto; Panzarini, Sônia Regina; Sundefeld, Maria Lúcia Marçal Mazza; Negri, Márcia Regina

2009-02-01

Minimal extraoral dry storage period and moist storage for the avulsed tooth are identified as key steps for the treatment protocol of tooth replantation. Among the possible moist storage media, bovine milk has stood out because of its capacity of preserving the integrity of the periodontal ligament (PDL) fibers. This condition has attracted the attention to investigate the use of powdered milk, which is one of the presentation forms of bovine milk, as a feasible storage medium in cases of delayed tooth replantation. The aim of this study was to evaluate the healing process after delayed replantation of rat teeth stored in reconstituted powdered milk and long shelf-life (ultra high temperature) whole milk. Forty maxillary right rat incisors were assigned to four groups (n = 10): group I--the teeth were extracted and immediately replanted into theirs sockets; group II--the teeth were stored for 60 min in 200 ml of freshly reconstituted powdered milk; group III--the teeth were stored for 60 min in 200 ml of long shelf-life whole milk; group IV--the teeth were kept dry for the same time. All procedures were performed at room temperature. Next, the root canals of teeth in groups II, III, and IV were instrumented, filled with a calcium hydroxide-based paste, and replanted into their sockets. All animals received systemic antibiotic therapy and were killed by anesthetic overdose 60 days after replantation. The pieces containing the replanted teeth were removed, fixed, decalcified, and paraffin-embedded. Semi-serial 6-microm-thick sections were obtained and stained with hematoxylin and eosin for histomorphological analysis. There was statistically significant difference (P < 0.05) between groups I and IV regarding the presence of replacement resorption and PDL remnants on root surface. The powdered milk and long shelf-life whole milk presented similar results to each other and may be indicated as storage media for avulsed teeth.

Organolanthanoid compounds

International Nuclear Information System (INIS)

Schumann, H.

1984-01-01

Up to little more than a decade ago organolanthanoid compounds were still a curiosity. Apart from the description of an isolated number of cyclopentadienyl and indenyl derivatives, very few significant contributions had been made to this interesting sector of organometallic chemistry. However, subsequent systematic studies using modern preparative and analytical techniques, together with X-ray single crystal structure determinations, enabled the isolation and characterization of a large number of very interesting homoleptic and heteroleptic compounds in which the lanthanoid is bound to hydrogen, to substituted or unsubstituted cyclopentadienyl groups, to allyl or alkynyl groups, or even to phosphorus ylides, trimethylsilyl, and carbonylmetal groups. These compounds, which are all extremely sensitive to oxygen and water, open up new possibilities in the field of catalysis and have great potential in organic synthesis - as recent studies with pentamethylcyclopentadienyl derivatives, organolanthanoid(II) compounds, and hexamethyllanthanoid complexes have already shown. (orig.) [de

Particulate Sol-Gel Synthesis and Characterization of LiMO2 (M=Ni, Ni(0.75)Co(0.25) Using the Thermal and Mass Spectrometry Analyses Work-Station

National Research Council Canada - National Science Library

Chang, Chun-Chieh

2000-01-01

.... Four different processes: (a)rotary evaporation (b)gelation (c)spray drying and (d)spray decomposition have been developed and studied using inorganic and organometallic precursors other than metal alkoxides...

The processing of CdSe/Polymer nanocomposites via solution organometallic chemistry

International Nuclear Information System (INIS)

Khanna, P.K.; Singh, Narendra; Charan, Shobhit; Lonkar, Sunil P.; Reddy, A. Satyanarayana; Patil, Yogesh; Viswanath, A. Kasi

2006-01-01

This paper presents in situ preparation of CdSe nanoparticles using poly(vinyl alcohol) [PVA] and polymethylmethacrylate [PMMA] as matrices by use of organoselenium compound. Reaction of cadmium metal salt and 1,2,3-selenadiazole (the source of selenium) enabled formation of CdSe nanoparticles. Use of selenadiazole in the present work with polymer is first of its kind. The radical polymerization of methycrylate monomer with benzoyl peroxide followed by reaction of respective reagents have been successfully employed to synthesize CdSe/PMMA nanocomposite. Similarly, reaction between selenadiazole and cadmium metal salt in aq. PVA yielded polymer coated or mixed CdSe nanoparticles. The UV-vis absorption spectra showed blue shift of about 200 nm with respect to band-gap energy of bulk CdSe, due to size quantization effect in CdSe particles. An emission band was observed at 530 nm in photoluminescence spectrum (PL) of CdSe/PMMA. IR spectra indicated shifts in the values of the polymer functional group due to nanoparticles. X-ray measurement of CdSe/Polymer nano-composites showed broad pattern for cubic CdSe and particle size of CdSe was estimated to be <10 nm. TGA revealed gradual weight loss between 200 and 400 deg. C indicating increased thermal stability of the polymer

Group devaluation and group identification

NARCIS (Netherlands)

Leach, C.W.; Rodriguez Mosquera, P.M.; Vliek, M.L.W.; Hirt, E.

2010-01-01

In three studies, we showed that increased in-group identification after (perceived or actual) group devaluation is an assertion of a (preexisting) positive social identity that counters the negative social identity implied in societal devaluation. Two studies with real-world groups used order

Chalcogenide glasses for device application modified by high-energy irradiation

International Nuclear Information System (INIS)

Kavetskyy, T.; Shpotyuk, O.

2006-01-01

Full text: Chalcogenide glasses (ChG) or chemical compounds of chalcogen atoms (S, Se or Te, but not O) with some elements from IV-th and V-th groups of the Periodic Table (typically As, Ge, Sb, Bi, etc. ) obtained by melt quenching, are a perspective for application in modern optoelectronics, photonics, telecommunications, acoustic-optics, xerography, lithography, etc. This uniqueness is due to extremely high sensitivity of ChG to external influences, associated, presumably, with high steric flexibility proper to glassy-like network with low average atomic coordination (chalcogen atoms are typically two-fold coordinated in a glassy-like network), relatively large internal free volume and specific lp-character of electronic states localized at a valence-band top. However, at present, the further possibilities for conventional chemical/technological methods to prepare ChG are fully exhausted. One of the steps to resolve this problem is post-technological modification of ChG using possibilities of high-energy irradiation. This work is focused on new advanced radiation-modified ChG for device application in optoelectronics. The attractive practical use of these non-crystalline materials is tightly connected with radiation-induced defect formation processes. For the first time, we consider the possibilities of Raman scattering along with X-ray diffraction and positron annihilation lifetime spectroscopy to characterize microstructural mechanisms of radiation-induced effects in ChG. (authors)

Lie groups and algebraic groups

Indian Academy of Sciences (India)

We give an exposition of certain topics in Lie groups and algebraic groups. This is not a complete ... of a polynomial equation is equivalent to the solva- bility of the equation ..... to a subgroup of the group of roots of unity in k (in particular, it is a ...

REACTIONS OF 5-[1-(2-PHENYL)METHYLIDENE

African Journals Online (AJOL)

4-DIONES WITH SOME ORGANOMETALLIC REAGENTS. ... KEY WORDS: Imidazolidine-2,4-diones, a,b-Unsaturated carbonyl compounds, 1,2-Addition, conjugate addition, Grignard reagents, Lithium dibutylcuprate. Bull. Chem. Soc. Ethiop.

Nitrogen-based catalysts for the electrochemical reduction of CO2 to CO.

Science.gov (United States)

Tornow, Claire E; Thorson, Michael R; Ma, Sichao; Gewirth, Andrew A; Kenis, Paul J A

2012-12-05

The synthesis and application of carbon-supported, nitrogen-based organometallic silver catalysts for the reduction of CO(2) is studied using an electrochemical flow reactor. Their performance toward the selective formation of CO is similar to the performance achieved when using Ag as the catalyst, but comparatively at much lower silver loading. Faradaic efficiencies of the organometallic catalyst are higher than 90%, which are comparable to those of Ag. Furthermore, with the addition of an amine ligand to Ag/C, the partial current density for CO increases significantly, suggesting a possible co-catalyst mechanism. Additional improvements in activity and selectivity may be achieved as greater insight is obtained on the mechanism of CO(2) reduction and on how these complexes assemble on the carbon support.

Biocompatible Polymer Nanoformulation To Improve the Release and Safety of a Drug Mimic Molecule Detectable via ICP-MS.

Science.gov (United States)

Ferrari, Raffaele; Talamini, Laura; Violatto, Martina Bruna; Giangregorio, Paola; Sponchioni, Mattia; Morbidelli, Massimo; Salmona, Mario; Bigini, Paolo; Moscatelli, Davide

2017-01-03

Fluorescent poly(ε-caprolactone)-based nanoparticles (NPs) have been synthesized and successfully loaded with a titanium organometallic compound as a mimic of a water-insoluble drug. The nature of this nanovector enabled us to combine the quantification of the metal in tissues after systemic administration in healthy immunocompetent mice by inductively coupled plasma mass spectroscopy (ICP-MS) followed by the visualization of NPs in organ sections by confocal microscopy. This innovative method of nanodrug screening has enabled us to elucidate the crucial parameters of their kinetics. The organometallic compound is a good mimic of most anticancer drugs, and this approach is an interesting starting point to design the relevance of a broad range of nanoformulations in terms of safety and targeted delivery of the cargoes.

Bhattacharya, Prof. Samaresh

Indian Academy of Sciences (India)

ordination Chemistry and Organometallic Chemistry Address: Professor, Inorganic Chemistry Section, Department of Chemistry, Jadavpur University, Kolkata 700 032, W.B.. Contact: Office: (033) 2414 6223. Residence: (033) 2431 0998. Mobile: ...

Potential for biodegradation of polycyclic aromatic hydrocarbons by ...

African Journals Online (AJOL)

WiTT

2012-05-08

May 8, 2012 ... Full Length Research Paper. Biodegradation of ... organic compounds, including some organometallic ... is a major source of toxic PAHs that contributes signi- ficantly to ... microorganisms for bioremediation of hydrocarbon-.

Group Cohesion in Experiential Growth Groups

Science.gov (United States)

Steen, Sam; Vasserman-Stokes, Elaina; Vannatta, Rachel

2014-01-01

This article explores the effect of web-based journaling on changes in group cohesion within experiential growth groups. Master's students were divided into 2 groups. Both used a web-based platform to journal after each session; however, only 1 of the groups was able to read each other's journals. Quantitative data collected before and…

Highly Potent Antibacterial Organometallic Peptide Conjugates

NARCIS (Netherlands)

Albada, Bauke; Metzler-Nolte, Nils

2017-01-01

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

Physical organic studies of organometallic reactions

Energy Technology Data Exchange (ETDEWEB)

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

1981-01-01

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

Organo-metallic structures for spintronic applications

NARCIS (Netherlands)

Tiba, M.V.

2005-01-01

The revolution in (semi)conducting organic materials has been one of the highlights in physics over the past decade. Molecular and polymeric thin films are projected to be used as active elements in a wide range of electronic and optoelectronic applications. Among the main driving forces for such

Advances in organometallic and protein chemistry

OpenAIRE

Ryan, C. P.

2010-01-01

This thesis describes two areas of scientific investigation. The first contains a description of a study on the synthesis of biotinylated and fluoresceinylated bromomaleimide based reagents. Upon synthesis, the ability of these reagents to add reversibly to cysteine containing proteins is investigated by a series of LCMS experiments. A single point mutant (L111C) of the SH2 domain of the Grb2 adaptor protein, containing a single cysteine residue, is chosen as an ideal protein for study. Thus ...

Organometallic Half-Sandwich Iridium Anticancer Complexes

Czech Academy of Sciences Publication Activity Database

Liu, Z.; Habtemariam, A.; Pizarro, A.M.; Fletcher, S.A.; Kisová, Anna; Vrána, Oldřich; Salassa, L.; Bruijnincx, P.C.A.; Clarkson, G.J.; Brabec, Viktor; Sadler, P. J.

2011-01-01

Roč. 54, č. 8 (2011), 3011-3026 ISSN 0022-2623 R&D Projects: GA ČR(CZ) GPP303/11/P047; GA ČR(CZ) GAP301/10/0598 Keywords : RUTHENIUM(II) ARENE COMPLEXES * CANCER-CELL CYTOTOXICITY * DNA-BINDING PROPERTIES Subject RIV: BO - Biophysics Impact factor: 5.248, year: 2011

Stereochemistry of organometallic and inorganic compounds

CERN Document Server

2012-01-01

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

Periasamy, Prof. Mariappan

Indian Academy of Sciences (India)

D. (IISc), FNA. Date of birth: 6 October 1952. Specialization: Organometallics, Chiral Reagents, Organic Molecules, Solar Energy Harvesting Address: Emeritus Professor, School of Chemistry, University of Hyderabad, Hyderabad 500 046, A.P.

Versatile cell for in-situ spectroelectrochemical and ex-situ nanomorphological characterization of both water soluble and insoluble phthalocyanine compounds

Czech Academy of Sciences Publication Activity Database

Mansfeldová, Věra; Klusáčková, Monika; Tarábková, Hana; Janda, Pavel; Nesměrák, K.

2016-01-01

Roč. 147, č. 8 (2016), s. 1393-1400 ISSN 0026-9247 Institutional support: RVO:61388955 Keywords : organometallic compounds * electrochemistry * cyclic voltammetry Subject RIV: CG - Electrochemistry Impact factor: 1.282, year: 2016

Sc, Y, the lanthanoids and the actinoids

International Nuclear Information System (INIS)

Miller, J.D.

1985-01-01

Highlights of work published in 1984 are given. Solid state, studies in solution, coordination chemistry and organometallic chemistry aspects of scandium, yttrium, the rare earths and actinide compounds are covered. (U.K.)

Which finite simple groups are unit groups?

DEFF Research Database (Denmark)

Davis, Christopher James; Occhipinti, Tommy

2014-01-01

We prove that if G is a finite simple group which is the unit group of a ring, then G is isomorphic to either (a) a cyclic group of order 2; (b) a cyclic group of prime order 2^k −1 for some k; or (c) a projective special linear group PSLn(F2) for some n ≥ 3. Moreover, these groups do all occur a...

Prediction of T-cell Epitopes for Therapeutic and Prophylactic Vaccines

DEFF Research Database (Denmark)

Larsen, Mette Voldby

2007-01-01

: The bacteria Mycobacterium tuberculosis, Influenza A virus, HIV, Yellow fever virus, and West Nile virus. For each of the above-mentioned viruses, a number of predicted CTL epitopes was subsequently selected in such a way that they together constitute a broad coverage of the available viral strains. Part IV......The spread of existing infectious diseases and the emergence of new ones call for efficient methods for vaccine development. Some of the important players in conferring immunity against pathogens are the Cytotoxic T Lymphocytes (CTL), which eliminate infected cells. Due to their deleterious effects...... vaccine design as well as for diagnostic purposes and is the centre of focus of this thesis: Part I of the thesis is an introduction to the field. In part II, I describe how we generated a method, NetCTL, for predicting CTL epitopes by integrating existing methods for predicting proteasomal cleavage, TAP...

The Influence of Marine Microfouling on the Corrosion Behaviour of Passive Materials and Copper Alloys

National Research Council Canada - National Science Library

Little, Brenda J; Lee, Jason S; Ray, Richard I

2008-01-01

...) of passive alloys exposed in marine environments. Ennoblement in marine waters has been ascribed to depolarization of the oxygen reduction reaction due to organometallic catalysis, acidification of the electrode surface, the combined effects...

Cyclic Soft Groups and Their Applications on Groups

Directory of Open Access Journals (Sweden)

Hacı Aktaş

2014-01-01

Full Text Available In crisp environment the notions of order of group and cyclic group are well known due to many applications. In this paper, we introduce order of the soft groups, power of the soft sets, power of the soft groups, and cyclic soft group on a group. We also investigate the relationship between cyclic soft groups and classical groups.

Surface functionalization of mesoporous antimony doped tin oxide by metalorganic reaction

Czech Academy of Sciences Publication Activity Database

Müller, V.; Haase, F.; Rathouský, Jiří; Fattakhova-Rohlfing, D.

2012-01-01

Roč. 137, č. 1 (2012), s. 207-212 ISSN 0254-0584 Institutional support: RVO:61388955 Keywords : oxides * organometallic compounds * chemical synthesis Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.072, year: 2012

Dosimetric properties of new formulation of PRESAGE® with tin organometal catalyst: Development of sensitivity and stability to megavoltage energy

Directory of Open Access Journals (Sweden)

Davood Khezerloo

2018-01-01

Conclusions: Tin organometallic catalyst in very low concentration can be used in fabrication of radiochromic polymer gel to achieve high sensitivity and stability as well as good radiological properties in the megavoltage photon beam.

Group typicality, group loyalty and cognitive development.

Science.gov (United States)

Patterson, Meagan M

2014-09-01

Over the course of childhood, children's thinking about social groups changes in a variety of ways. Developmental Subjective Group Dynamics (DSGD) theory emphasizes children's understanding of the importance of conforming to group norms. Abrams et al.'s study, which uses DSGD theory as a framework, demonstrates the social cognitive skills underlying young elementary school children's thinking about group norms. Future research on children's thinking about groups and group norms should explore additional elements of this topic, including aspects of typicality beyond loyalty. © 2014 The British Psychological Society.

The tinker, tailor, soldier in intracellular B12 trafficking.

Science.gov (United States)

Banerjee, Ruma; Gherasim, Carmen; Padovani, Dominique

2009-10-01

The recognition of eight discrete genetic complementation groups among patients with inherited cobalamin disorders provided early insights into the complexity of a cofactor-processing pathway that supports only two known B(12)-dependent enzymes in mammals. With the identification of all eight genes now completed, biochemical interrogations of their functions have started and are providing novel insights into a trafficking pathway involving porters that tinker with and tailor the active cofactor forms and editors that ensure the fidelity of the cofactor loading process. The principles of sequestration and escorted delivery of a rare and reactive organometallic cofactor that are emerging from studies on B(12) might be of general relevance to other cofactor trafficking pathways.

Boron in nuclear medicine: New synthetic approaches to PET and SPECT

International Nuclear Information System (INIS)

Kabalka, G.W.

1994-02-01

New methods based on reactive organometallic precursors containing organic functional groups that are generally responsible for physiologic responses are being exploited for preparation of radiopharmaceutials. This program focuses on the design of new chemistry (molecular architecture) and technology as opposed to the application of known reactions to the synthesis of specific radiopharmaceutical. The new technology which is often based on organoborane chemistry is then utilized in nuclear medicine research at the UT Biomedical Imaging Center and in collaboration with colleagues at other DOE. facilities such as Brookhaven National Laboratory and Oak Ridge National Laboratory. New radiopharmaceutical are evaluated preclinically by colleagues at UT, Emory University and The University of Pennsylvania, and by Nova Screen

Growth, optical, electrical and photoconductivity studies of a novel nonlinear optical single crystal: Mercury cadmium chloride thiocyanate

Science.gov (United States)

Kumar, S. M. Ravi; Selvakumar, S.; Sagayaraj, P.; Anbarasi, A.

2015-02-01

SCN- ligand based organometallic non-linear optical mercury cadmium chloride thiocyanate (MCCTC) crystals are grown from water plus methanol mixed solvent by slow evaporation technique. The grown crystals are confirmed by single crystal X-ray diffraction analysis which reveals that the MCCTC belongs to rhombohedral system with R3c space group. MCCTC exhibits a SHG efficiency which is nearly 17 times more than that of KDP. The dielectric constant, dielectric loss measurements of the sample have been carried out for different frequencies (100 Hz to 5 MHz) and, temperatures (308 to 388 K) and the results are discussed. Photoconductivity study confirms that the title compound possesses negative photoconducting nature. The surface morphology of MCCTC was also investigated

Ionic Liquids as Solvents for Rhodium and Platinum Catalysts Used in Hydrosilylation Reaction

Directory of Open Access Journals (Sweden)

Witold Zielinski

2016-08-01

Full Text Available A group of imidazolium and pyridinium based ionic liquids has been synthetized, and their ability to dissolve and activate the catalysts used in hydrosilylation reaction of 1-octane and 1,1,1,3,5,5,5-heptamethyltrisiloxane was investigated. An organometallic catalyst as well as inorganic complexes of platinum and rhodium dissolved in ionic liquids were used, forming liquid solutions not miscible with the substrates or with the products of the reaction. The results show that application of such a simple biphasic catalytic system enables reuse of ionic liquid phase with catalysts in multiple reaction cycles reducing the costs and decreasing the amount of catalyst needed per mole of product.

In silico evaluation of highly efficient organic light-emitting materials

Science.gov (United States)

Kwak, H. Shaun; Giesen, David J.; Hughes, Thomas F.; Goldberg, Alexander; Cao, Yixiang; Gavartin, Jacob; Dixon, Steve; Halls, Mathew D.

2016-09-01

Design and development of highly efficient organic and organometallic dopants is one of the central challenges in the organic light-emitting diodes (OLEDs) technology. Recent advances in the computational materials science have made it possible to apply computer-aided evaluation and screening framework directly to the design space of organic lightemitting diodes (OLEDs). In this work, we will showcase two major components of the latest in silico framework for development of organometallic phosphorescent dopants - (1) rapid screening of dopants by machine-learned quantum mechanical models and (2) phosphorescence lifetime predictions with spin-orbit coupled calculations (SOC-TDDFT). The combined work of virtual screening and evaluation would significantly widen the design space for highly efficient phosphorescent dopants with unbiased measures to evaluate performance of the materials from first principles.

The preparation of HfC/C ceramics via molecular design.

Science.gov (United States)

Inzenhofer, Kathrin; Schmalz, Thomas; Wrackmeyer, Bernd; Motz, Günter

2011-05-07

Polymer derived ceramics have received lots of attention throughout the last few decades. Unfortunately, only a few precursor systems have been developed, focusing on silicon based polymers and ceramics, respectively. Herein, the synthesis of novel hafnium containing organometallic polymers by two different approaches is reported. Dialkenyl substituted hafnocene monomers were synthesized and subsequently polymerized via a free radical mechanism. Salt metathesis reactions of hafnocene dichloride with bifunctional linkers led to the formation of polymeric materials. NMR spectroscopic methods--in solution as well as in the solid state--were used to characterize the organometallic polymers. Ceramics were finally obtained after cross-linking and thermal treatment under argon (T(max) = 1800 °C). SEM investigations, elemental analyses, Raman spectroscopy and XRD investigations identified the pyrolyzed products as partially crystalline HfC/C mixed phases.

Insights into the deactivation mechanism of supported tungsten hydride on alumina (W-H/Al2O3) catalyst for the direct conversion of ethylene to propylene

KAUST Repository

Mazoyer, Etienne; Szeto, Kaï Chung; Merle, Nicolas; Thivolle-Cazat, Jean; Boyron, Olivier; Basset, Jean-Marie; Nicholas, Christopher P.; Taoufik, Mostafa

2014-01-01

Tungsten hydride supported on alumina prepared by the surface organometallic chemistry method is an active precursor for the direct conversion of ethylene to propylene at low temperature and pressure. An extensive contact time study revealed

Vapor pressures of (3-(Dimethylamino)propyl)dimethylindium, (tert-Butylimino)bis(diethylamino)cyclopentadienyltantalum, and (tert-Butylimino)tris(ethylmethylamino)tantalum

Czech Academy of Sciences Publication Activity Database

Morávek, Pavel; Pangrác, Jiří; Fulem, Michal; Hulicius, Eduard; Růžička, K.

2014-01-01

Roč. 59, č. 12 (2014), s. 4179-4183 ISSN 0021-9568 Institutional support: RVO:68378271 Keywords : vapor pressure * static method * organometallics Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.037, year: 2014

Ir/Sn dual-reagent catalysis towards highly selective alkylation of ...

Indian Academy of Sciences (India)

Wintec

Organometallic; bimetallic; catalysis; alkylation; benzyl alcohol; iridium, tin. 1. Introduction ... cording to our proposal, the oxidative addition of tin(IV) halides across a ..... 33. 4. Conclusion. In summary, we have demonstrated here an Ir/Sn.

Ordered groups and infinite permutation groups

CERN Document Server

1996-01-01

The subjects of ordered groups and of infinite permutation groups have long en­ joyed a symbiotic relationship. Although the two subjects come from very different sources, they have in certain ways come together, and each has derived considerable benefit from the other. My own personal contact with this interaction began in 1961. I had done Ph. D. work on sequence convergence in totally ordered groups under the direction of Paul Conrad. In the process, I had encountered "pseudo-convergent" sequences in an ordered group G, which are like Cauchy sequences, except that the differences be­ tween terms of large index approach not 0 but a convex subgroup G of G. If G is normal, then such sequences are conveniently described as Cauchy sequences in the quotient ordered group GIG. If G is not normal, of course GIG has no group structure, though it is still a totally ordered set. The best that can be said is that the elements of G permute GIG in an order-preserving fashion. In independent investigations around that t...

CORRELATION BETWEEN GROUP LOCAL DENSITY AND GROUP LUMINOSITY

Energy Technology Data Exchange (ETDEWEB)

Deng Xinfa [School of Science, Nanchang University, Jiangxi 330031 (China); Yu Guisheng [Department of Natural Science, Nanchang Teachers College, Jiangxi 330103 (China)

2012-11-10

In this study, we investigate the correlation between group local number density and total luminosity of groups. In four volume-limited group catalogs, we can conclude that groups with high luminosity exist preferentially in high-density regions, while groups with low luminosity are located preferentially in low-density regions, and that in a volume-limited group sample with absolute magnitude limit M{sub r} = -18, the correlation between group local number density and total luminosity of groups is the weakest. These results basically are consistent with the environmental dependence of galaxy luminosity.

What Is a Group? Young Children's Perceptions of Different Types of Groups and Group Entitativity.

Directory of Open Access Journals (Sweden)

Maria Plötner

Full Text Available To date, developmental research on groups has focused mainly on in-group biases and intergroup relations. However, little is known about children's general understanding of social groups and their perceptions of different forms of group. In this study, 5- to 6-year-old children were asked to evaluate prototypes of four key types of groups: an intimacy group (friends, a task group (people who are collaborating, a social category (people who look alike, and a loose association (people who coincidently meet at a tram stop. In line with previous work with adults, the vast majority of children perceived the intimacy group, task group, and social category, but not the loose association, to possess entitativity, that is, to be a 'real group.' In addition, children evaluated group member properties, social relations, and social obligations differently in each type of group, demonstrating that young children are able to distinguish between different types of in-group relations. The origins of the general group typology used by adults thus appear early in development. These findings contribute to our knowledge about children's intuitive understanding of groups and group members' behavior.

Use of [SbF.sub.6./sub.] .sup.-./sup. to isolate cationic copper and silver adducts with more than one ethylene on the metal center

Czech Academy of Sciences Publication Activity Database

Fianchini, M.; Campana, C.F.; Chilukuri, B.; Cundari, T.R.; Petříček, Václav; Dias, H.V.

2013-01-01

Roč. 32, č. 10 (2013), s. 3034-3041 ISSN 0276-7333 Institutional support: RVO:68378271 Keywords : organometallic compounds * X-ray structure analysis Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 4.253, year: 2013

Between-group competition elicits within-group cooperation in children

Science.gov (United States)

Majolo, Bonaventura; Maréchal, Laëtitia

2017-02-01

Aggressive interactions between groups are frequent in human societies and can bear significant fitness costs and benefits (e.g. death or access to resources). During between-group competitive interactions, more cohesive groups (i.e. groups formed by individuals who cooperate in group defence) should out-perform less cohesive groups, other factors being equal (e.g. group size). The cost/benefit of between-group competition are thought to have driven correlated evolution of traits that favour between-group aggression and within-group cooperation (e.g. parochial altruism). Our aim was to analyse whether the proximate relationship between between-group competition and within-group cooperation is found in 3-10 years old children and the developmental trajectory of such a relationship. We used a large cohort of children (n = 120) and tested whether simulated between-group competition increased within-group cooperation (i.e. how much of a resource children were giving to their group companions) in two experiments. We found greater within-group cooperation when groups of four children were competing with other groups then in the control condition (no between-group competition). Within-group cooperation increased with age. Our study suggests that parochial altruism and in-group/out-group biases emerge early during the course of human development.

Catalyst retention in continuous flow with supercritical carbon dioxide

NARCIS (Netherlands)

Stouten, S.C.; Noel, T.; Wang, Q.; Hessel, V.

2014-01-01

This review discusses the retention of organometallic catalysts in continuous flow processes utilizing supercritical carbon dioxide. Due to its innovative properties, supercritical carbon dioxide offers interesting possibilities for process intensification. As a result of safety and cost

Fellowship | Indian Academy of Sciences

Indian Academy of Sciences (India)

Date of birth: 28 June 1947. Specialization: Medicinal Chemistry, Drug Design & Discovery, Organometallic Chemistry and Catalysis Address: Chairman, Cosmic Therapeutics, 48, Villa Greens, Gandipet, Hyderabad 500 075, A.P.. Contact: Residence: (040) 2419 3132. Mobile: 98497 99444

EFFECTS OF DIETARY COPPER, ZINC, LEAD, CADMIUM, AND ARSENIC ON GROWTH AND SURVIVAL OF JUVENILE FISH USING LIVE FOOD ORGANISMS

Science.gov (United States)

Except for certain organometallic compounds, dietary exposures of aquatic organisms to metal/metalloids have received little regulatory attention. However, various studies have suggested that dietary exposure could be important, especially in areas where current water column conc...

A Density Functional Theory Study

KAUST Repository

Lim, XiaoZhi

2011-12-11

Complexes with pincer ligand moieties have garnered much attention in the past few decades. They have been shown to be highly active catalysts in several known transition metal-catalyzed organic reactions as well as some unprecedented organic transformations. At the same time, the use of computational organometallic chemistry to aid in the understanding of the mechanisms in organometallic catalysis for the development of improved catalysts is on the rise. While it was common in earlier studies to reduce computational cost by truncating donor group substituents on complexes such as tertbutyl or isopropyl groups to hydrogen or methyl groups, recent advancements in the processing capabilities of computer clusters and codes have streamlined the time required for calculations. As the full modeling of complexes become increasingly popular, a commonly overlooked aspect, especially in the case of complexes bearing isopropyl substituents, is the conformational analysis of complexes. Isopropyl groups generate a different conformer with each 120 ° rotation (rotamer), and it has been found that each rotamer typically resides in its own potential energy well in density functional theory studies. As a result, it can be challenging to select the most appropriate structure for a theoretical study, as the adjustment of isopropyl substituents from a higher-energy rotamer to the lowest-energy rotamer usually does not occur during structure optimization. In this report, the influence of the arrangement of isopropyl substituents in pincer complexes on calculated complex structure energies as well as a case study on the mechanism of the isomerization of an iPrPCP-Fe complex is covered. It was found that as many as 324 rotamers can be generated for a single complex, as in the case of an iPrPCP-Ni formato complex, with the energy difference between the global minimum and the highest local minimum being as large as 16.5 kcalmol-1. In the isomerization of a iPrPCP-Fe complex, it was found

Organometallic Polyelectrolytes: Synthesis, Characterization and Layer-By-Layer Deposition of Cationic Poly (ferrocenyl (3-ammoniumpropyl)-methylsilane)

NARCIS (Netherlands)

Hempenius, Mark A.; Robins, Neil S.; Lammertink, Rob G.H.; Vancso, Gyula J.

2001-01-01

The water soluble poly(ferrocenylsilane) polycation, poly(ferrocenyl(3-ammoniumpropyl)methylsilane), was synthesized by transition metal-catalyzed ring-opening polymerization of the novel [1]ferrocenophane Fe(-C5H4)2SiCH3(CH2)3Cl and by subsequent side group modification. Amination of the

Development of Advanced Materials for Electro-Ceramic Application Final Report CRADA No. TC-1331-96

Energy Technology Data Exchange (ETDEWEB)

Caplan, M. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Olstad, R. [General Atomics, San Diego, CA (United States); McMillan, L. [Symetrix International, Inc., Colorado Springs, CO (United States); Tulupov, A. [Soliton-NTT, Moscow (Russia)

2017-10-19

The goal of this project was to further develop and characterize the electrochemical methods originating in Russia for producing ultra high purity organometallic compounds utilized as precursors in the production of high quality electro-ceramic materials. Symetrix planned to use electro-ceramic materials with high dielectric constant for microelectronic memory circuit applications. General Atomics planned to use the barium titanate type ceramics with low loss tangent for producing a high power ferroelectric tuner used to match radio frequency power into their Dill-D fusion machine. Phase I of the project was scheduled to have a large number of organometallic (alkoxides) chemical samples produced using various methods. These would be analyzed by LLNL, Soliton and Symetrix independently to determine the level of chemical impurities thus verifying each other's analysis. The goal was to demonstrate a cost-effective production method, which could be implemented in a large commercial facility to produce high purity organometallic compounds. In addition, various compositions of barium-strontium-titanate ceramics were to be produced and analyzed in order to develop an electroceramic capacitor material having the desired characteristics with respect to dielectric constant, loss tangent, temperature characteristics and non-linear behavior under applied voltage. Upon optimizing the barium titanate material, 50 capacitor preforms would be produced from this material demonstrating the ability to produce, in quantity, the pills ultimately required for the ferroelectric tuner (approx 2000-3000 ceramic pills).

Trace Metals and Volatile Aromatic Hydrocarbon Content of ...

African Journals Online (AJOL)

Michael Horsfall

two months and five months were studied in an oil impacted soil at Ukpeliede in the Niger Delta area, Nigeria. This was ... disintegration of natural organometalic plant metabolites ... into mainly oxygen products (e.g. organic acids and phenol.

Comparison and systematic optimization of synthetic protocols for DOTA-hydrazide generation

NARCIS (Netherlands)

Fuge, F.; Weiler, M.; Gaetjens, J.; Lammers, Twan Gerardus Gertudis Maria

2013-01-01

DOTA-based organometallic complexes are extensively used in functional and molecular imaging studies, as well as in radioimmunotherapy. DOTA forms thermodynamically stable and kinetically inert complexes with various different diagnostic and therapeutic metals, such as gadolinium, gallium, yttrium

Cluster-derived Ir-Sn/SiO2 catalysts for the catalytic dehydrogenation of propane: A spectroscopic study

KAUST Repository

Gallo, Alessandro

2013-01-01

Ir-Sn bimetallic silica-based materials have been prepared via deposition of the molecular organometallic clusters (NEt4)2[Ir 4(CO)10(SnCl3)2] and NEt 4[Ir6(CO)15(SnCl3)] or via deposition of Sn organometallic precursor Sn(n-C4H9) 4 onto pre-formed Ir metal particles. These solids possess promising properties, in terms of selectivity, as catalysts for propane dehydrogenation to propene. Detailed CO-adsorption DRIFTS, XANES and EXAFS characterization studies have been performed on these systems in order to compare the structural and electronic evolution of systems in relation to the nature of the Ir-Sn bonds present in the precursor compounds and to propose a structural model of the Ir-Sn species present at the silica surface of the final catalyst. © 2013 The Royal Society of Chemistry.

200 years of lithium and 100 years of organolithium chemistry

International Nuclear Information System (INIS)

Wietelmann, Ulrich; Klett, Jan

2018-01-01

The element lithium has been discovered 200 years ago. Due to its unique properties it has emerged to play a vital role in industry, esp. for energy storage, and lithium-based products and processes support sustainable technological developments. In addition to the many uses of lithium in its inorganic forms, lithium has a rich organometallic chemistry. The development of organometallic chemistry has been hindered by synthetic problems from the start. When Wilhelm Schlenk developed the basic principles to handle and synthesize air- and moisture-sensitive compounds, the road was open to further developments. After more information was available about the stability and solubility of such compounds, they started to play an essential role in other fields of chemistry as alkyl or aryl transfer reagents. (copyright 2018 The Authors. Published by Wiley-VCH Verlag GmbH and Co. KGaA.)

Microcolumn high pressure liquid chromatography with a glass-frit nebulizer interface for plasma emission detection

International Nuclear Information System (INIS)

Ibrahim, M.; Nisamaneepong, W.; Caruso, J.

1985-01-01

Microcolumn high pressure liquid chromatography (micro-HPLC) is rapidly gaining recognition as a practical separation tool for organometallic compounds. The use of the inductively coupled plasma (ICP) as a detector for micro-HPLC is studied. Several miniaturized glass-frit nebulizers are investigated as interfaces between the output of the microbore column and the ICP torch. Their performance with aqueous and methanolic solutions is evaluated by direct nebulization and flow injection analysis. The most efficient of these nebulizers is used in the micro-HPLC/ICP study of some Cd, Pb, and Zn organometallic compounds. Detection limits of 1.92 ng of Pb for tetramethyllead and 5.01 ng of Pb for tetraethyllead are obtained and compared with regular HPLC/ICP of these same compounds. Approximately equivalent detection limits were obtained when using a microwave induced plasma as an alternate plasma source

200 years of lithium and 100 years of organolithium chemistry

Energy Technology Data Exchange (ETDEWEB)

Wietelmann, Ulrich [Albemarle Germany GmbH, Synthesis Solutions, Industriepark Hoechst, Frankfurt am Main (Germany); Klett, Jan [Institut fuer Anorganische Chemie und Analytische Chemie, Johannes Gutenberg-Universitaet Mainz (Germany)

2018-03-01

The element lithium has been discovered 200 years ago. Due to its unique properties it has emerged to play a vital role in industry, esp. for energy storage, and lithium-based products and processes support sustainable technological developments. In addition to the many uses of lithium in its inorganic forms, lithium has a rich organometallic chemistry. The development of organometallic chemistry has been hindered by synthetic problems from the start. When Wilhelm Schlenk developed the basic principles to handle and synthesize air- and moisture-sensitive compounds, the road was open to further developments. After more information was available about the stability and solubility of such compounds, they started to play an essential role in other fields of chemistry as alkyl or aryl transfer reagents. (copyright 2018 The Authors. Published by Wiley-VCH Verlag GmbH and Co. KGaA.)

Soldering of Nanotubes onto Microelectrodes

DEFF Research Database (Denmark)

Madsen, Dorte Nørgaard; Mølhave, Kristian; Mateiu, Ramona Valentina

2003-01-01

Suspended bridges of individual multiwalled carbon nanotubes were fabricated inside a scanning electron microscope by soldering the nanotube onto microelectrodes with highly conducting gold-carbon material. By the decomposition of organometallic vapor with the electron beam, metal-containing sold...... bonds were consistently found to be mechanically stronger than the carbon nanotubes.......Suspended bridges of individual multiwalled carbon nanotubes were fabricated inside a scanning electron microscope by soldering the nanotube onto microelectrodes with highly conducting gold-carbon material. By the decomposition of organometallic vapor with the electron beam, metal-containing solder...... bonds were formed at the intersection of the nanotube and the electrodes. Current-voltage curves indicated metallic conduction of the nanotubes, with resistances in the range of 9-29 kOmega. Bridges made entirely of the soldering material exhibited resistances on the order of 100 Omega, and the solder...

Preparation and surface functionalization of MWCNTs: study of the composite materials produced by the interaction with an iron phthalocyanine complex

Directory of Open Access Journals (Sweden)

Carter Jonathan

2011-01-01

Full Text Available Abstract Carbon nanotubes [CNTs] were synthesized by the catalytic vapor decomposition method. Thereafter, they were functionalized in order to incorporate the oxygen groups (OCNT and subsequently the amine groups (ACNT. All three CNTs (the as-synthesized and functionalized underwent reaction with an iron organometallic complex (FePcS, iron(III phthalocyanine-4,4",4",4""-tetrasulfonic acid, in order to study the nature of the interaction between this complex and the CNTs and the potential formation of nanocomposite materials. Transmission electronic microscopy, N2 adsorption at 77 K, thermogravimetric analysis, temperature-programmed desorption, and X-ray photoelectron spectroscopy were the characterization techniques employed to confirm the successful functionalization of CNTs as well as the type of interaction existing with the FePcS. All results obtained led to the same conclusion: There were no specific chemical interactions between CNTs and the fixed FePcS.

Preparation and surface functionalization of MWCNTs: study of the composite materials produced by the interaction with an iron phthalocyanine complex

Science.gov (United States)

Asedegbega-Nieto, Esther; Pérez-Cadenas, María; Carter, Jonathan; Anderson, James A.; Guerrero-Ruiz, Antonio

2011-04-01

Carbon nanotubes [CNTs] were synthesized by the catalytic vapor decomposition method. Thereafter, they were functionalized in order to incorporate the oxygen groups (OCNT) and subsequently the amine groups (ACNT). All three CNTs (the as-synthesized and functionalized) underwent reaction with an iron organometallic complex (FePcS), iron(III) phthalocyanine-4,4",4",4""-tetrasulfonic acid, in order to study the nature of the interaction between this complex and the CNTs and the potential formation of nanocomposite materials. Transmission electronic microscopy, N2 adsorption at 77 K, thermogravimetric analysis, temperature-programmed desorption, and X-ray photoelectron spectroscopy were the characterization techniques employed to confirm the successful functionalization of CNTs as well as the type of interaction existing with the FePcS. All results obtained led to the same conclusion: There were no specific chemical interactions between CNTs and the fixed FePcS.

What Is a Group? Young Children’s Perceptions of Different Types of Groups and Group Entitativity

Science.gov (United States)

Plötner, Maria; Over, Harriet; Carpenter, Malinda; Tomasello, Michael

2016-01-01

To date, developmental research on groups has focused mainly on in-group biases and intergroup relations. However, little is known about children’s general understanding of social groups and their perceptions of different forms of group. In this study, 5- to 6-year-old children were asked to evaluate prototypes of four key types of groups: an intimacy group (friends), a task group (people who are collaborating), a social category (people who look alike), and a loose association (people who coincidently meet at a tram stop). In line with previous work with adults, the vast majority of children perceived the intimacy group, task group, and social category, but not the loose association, to possess entitativity, that is, to be a ‘real group.’ In addition, children evaluated group member properties, social relations, and social obligations differently in each type of group, demonstrating that young children are able to distinguish between different types of in-group relations. The origins of the general group typology used by adults thus appear early in development. These findings contribute to our knowledge about children's intuitive understanding of groups and group members' behavior. PMID:27010484

Group X

Energy Technology Data Exchange (ETDEWEB)

Fields, Susannah

2007-08-16

This project is currently under contract for research through the Department of Homeland Security until 2011. The group I was responsible for studying has to remain confidential so as not to affect the current project. All dates, reference links and authors, and other distinguishing characteristics of the original group have been removed from this report. All references to the name of this group or the individual splinter groups has been changed to 'Group X'. I have been collecting texts from a variety of sources intended for the use of recruiting and radicalizing members for Group X splinter groups for the purpose of researching the motivation and intent of leaders of those groups and their influence over the likelihood of group radicalization. This work included visiting many Group X websites to find information on splinter group leaders and finding their statements to new and old members. This proved difficult because the splinter groups of Group X are united in beliefs, but differ in public opinion. They are eager to tear each other down, prove their superiority, and yet remain anonymous. After a few weeks of intense searching, a list of eight recruiting texts and eight radicalizing texts from a variety of Group X leaders were compiled.

AREVA group overview; Presentation du groupe AREVA

Energy Technology Data Exchange (ETDEWEB)

NONE

2002-02-08

This document presents the Group Areva, a world nuclear industry leader, from a financial holding company to an industrial group, operating in two businesses: the nuclear energy and the components. The structure and the market of the group are discussed, as the financial assets. (A.L.B.)

Synthesis and characterization of six-membered pincer ...

Indian Academy of Sciences (India)

0013167

SUPPORTING INFORMATION. REGULAR ARTICLE. Synthesis and characterization of six-membered pincer nickelacycles and application in alkylation of benzothiazole. †. HANUMANPRASAD PANDIRI,a DIPESH M SHARMA,a RAJESH G GONNADEb and. BENUDHAR PUNJI*,a. aOrganometallic Synthesis and Catalysis ...

Emerging Contaminants in the Environment

Science.gov (United States)

This chapter explores the use of mass spectrometry and its application to emerging contaminants (ECs) in the environment; such classes of compounds as organometallics, pharmaceuticals/drugs, nanomaterials, and dispersants (surfactants). Table 1 shows the variety of ECs that are...

Stimulus Responsive Poly(ferrocenylsilanes): Redox Chemistry of Iron in the Main Chain

NARCIS (Netherlands)

Giannotti, M.I.; Lv, H.; Ma, Y.; Steenvoorden, M.P.; Overweg, A.R.; Roerdink, M.; Hempenius, Mark A.; Vancso, Gyula J.

2006-01-01

Redox chemistry of organometallic poly(ferrocenylsilane) polymers (soluble in organic or aqueous environment) is discussed. Poly(ferrocenyldimethylsilane) (PFDMS) was oxidized in CH2Cl2 solution with different oxidants. Oxidation was accomplished with stepwise increasing amounts of ferric chloride

New Fellows and Honorary Fellow

Indian Academy of Sciences (India)

Elected: 1974 Section: Chemistry ... Date of death: 11 July 2004. Specialization: Inorganic & Organometallic Chemistry, Metal Alkoxides and Sol-Gel Chemistry ... The 29th Mid-year meeting of the Academy will be held from 29–30 June 2018 ...

BFCA for labeling with the M(CO)3 precursor (M = Re, 99mTc) : cysteine toward a tridentate complex

International Nuclear Information System (INIS)

Hong, Young Don; Choi, Ok Ja; Gwon, Hui Jeong; Choi, Sang Mu; Park, Sang Hyun; Park, Kyung Bae; Choi, Sun Ju

2004-01-01

Organometallic complexes of techneutium in its low oxidation states received little attention till the development of very stable water-soluble organometallic Tc(I) complexes using monodentate isonitrile ligands. The Tc(I) oxidation state is pratically advantegeous because of the kinetic inertness inherent in its low-spin d 6 configuration and good stability in aqueous media. That is, Tc(I) or Re(I) tricarbonyl complexes are ideal candidates for the radiolabeling of biomolecules which M(CO) 3 core allows the high efficient labelling with the retention of the biological affinity. To be used as a BFCA, it should possess not only both a strong metal-binding moiety and a group that binds to a biomolecules, but also the metal complex should maintain the high stability in vitro and in vivo. In this investigation, to estimate the usefulness of thiol modified L-cysteine as a new BFCA with M(CO)3 precursor for the conjugation to biomolecules while maintaining high stability, their non-carrier added and macroscopic level complexes of L-cycteine (L 1 ), S-methyl L-cysteine (L 2 ), L-methionine (L 3 ), and S-carboxymethyl-L-cysteine (L 4 ) were prepared for the evaluation of radiolabelling efficiency with 99m Tc(CO) 3 and macroscopic characteristics. Furthermore, in order to study in vivo pharmacokinetics, scintigraphic imaging scans using gamma camera were acquired after intravenous administration of each 99m Tc(CO) 3 complex and biodistribution study on 99m Tc(CO) 3 -L 4 was implemented using ICR mice

Interagency mechanical operations group numerical systems group

Energy Technology Data Exchange (ETDEWEB)

NONE

1997-09-01

This report consists of the minutes of the May 20-21, 1971 meeting of the Interagency Mechanical Operations Group (IMOG) Numerical Systems Group. This group looks at issues related to numerical control in the machining industry. Items discussed related to the use of CAD and CAM, EIA standards, data links, and numerical control.

Journal of Chemical Sciences | Indian Academy of Sciences

Indian Academy of Sciences (India)

Home; Journals; Journal of Chemical Sciences. Pakkirisamy Thilagar. Articles written in Journal of Chemical Sciences. Volume 118 Issue 6 November 2006 pp 455-462. Stannoxanes and phosphonates: New approaches in organometallic and transition metal assemblies · Vadapalli Chandrasekhar Kandasamy Gopal ...

Mechanistic Insights on the Reductive Dehydroxylation Pathway for the Biosynthesis of Isoprenoids Promoted by the IspH Enzyme

KAUST Repository

Abdel-Azeim, Safwat; Jedidi, Abdesslem; Cavallo, Luigi; Eppinger, Jö rg

2015-01-01

Here, we report an integrated quantum mechanics/molecular mechanics (QM/MM) study of the bio-organometallic reaction pathway of the 2H+/2e- reduction of (E)-4-hydroxy-3-methylbut-2-enyl pyrophosphate (HMBPP) into the so called universal terpenoids

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

National Research Council Canada - National Science Library

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

2000-01-01

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

Quantum catalysis : the modelling of catalytic transition states

NARCIS (Netherlands)

Hall, M.B.; Margl, P.; Naray-Szabo, G.; Schramm, Vern; Truhlar, D.G.; Santen, van R.A.; Warshel, A.; Whitten, J.L.; Truhlar, D.G.; Morokuma, K.

1999-01-01

A review with 101 refs.; we present an introduction to the computational modeling of transition states for catalytic reactions. We consider both homogeneous catalysis and heterogeneous catalysis, including organometallic catalysts, enzymes, zeolites and metal oxides, and metal surfaces. We summarize

Chandrasekaran, Prof. Srinivasan

Indian Academy of Sciences (India)

Specialization: Synthetic Organic Chemistry, Natural Products and Organometallic Chemistry Address: INSA Senior Scientist, Department of Organic Chemistry, Indian Institute of Science, Bengaluru 560 012, Karnataka Contact: Office: (080) 2360 2423, (080) 2293 2404. Residence: (080) 2351 2748. Mobile: 98860 88344

Jagirdar, Prof. Balaji Rao

Indian Academy of Sciences (India)

Fellow Profile. Elected: 2013 Section: Chemistry. Jagirdar, Prof. Balaji Rao Ph.D. (Kansas State). Date of birth: 9 September 1965. Specialization: Organometallic Chemistry, Materials Chemistry, Catalysis Address: Department of Inorganic & Physical Chemistry, Indian Institute of Science, Bengaluru 560 012, Karnataka

Overgroups of root groups in classical groups

CERN Document Server

Aschbacher, Michael

2016-01-01

The author extends results of McLaughlin and Kantor on overgroups of long root subgroups and long root elements in finite classical groups. In particular he determines the maximal subgroups of this form. He also determines the maximal overgroups of short root subgroups in finite classical groups and the maximal overgroups in finite orthogonal groups of c-root subgroups.

Group Milieu in systemic and psychodynamic group therapy

DEFF Research Database (Denmark)

Lau, Marianne Engelbrecht; Kristensen, Ellids

Objectives: A recent meta-analysis also concluded that psychotherapeutic approaches are beneficial for adult with a history of CSA and maintained for at least six months follow-up. The results suggest that different characteristics of therapy moderate the therapeutic outcome. We found in a random......Objectives: A recent meta-analysis also concluded that psychotherapeutic approaches are beneficial for adult with a history of CSA and maintained for at least six months follow-up. The results suggest that different characteristics of therapy moderate the therapeutic outcome. We found...... in a randomized study of systemic versus psychodynamic group therapy, that the short-term outcome for patients who received systemic group psychotherapy was significantly better than the outcome for patients who received psychodynamic group psychotherapy. The current study assessed the group milieu in both groups....... Methods: This randomized prospective study included 106 women: 52 assigned to psychodynamic group psychotherapy and 54 assigned to systemic group psychotherapy. The Group Environment Scale (GES) was filled in the mid phase of therapy and analysed in three dimensions and 10 subscales. Results: The systemic...

Observation of Significant enhancement in the efficiency of a DSSC by InN nanoparticles over TiO 2-nanoparticle films

Science.gov (United States)

Wang, Tsai-Te; Raghunath, P.; Lu, Yun-Fang; Liu, Yu-Chang; Chiou, Chwei-Huawn; Lin, M. C.

2011-06-01

We have studied the effect of InN deposited over TiO2 nanoparticle (NP) films on the performance of dye-sensitized solar cells (DSSCs) using N3 dye with I/I3- electrolyte. A 10-20% increase in efficiency was observed for InN deposited, N3 sensitized 5-8.5 μm thick TiO2 films as compared to similar non-treated films. The deposition of InN was carried out in the temperature range of 573-723 K organometallic chemical vapor deposition (OMCVD). Spectral shifts and DFT calculations with a model anchoring group (R‧COOH) both suggest binding of the N3 dye directly to both InN and the InN/TiO2 sites.

Group decision-making: Factors that affect group effectiveness

Directory of Open Access Journals (Sweden)

Juliana Osmani

2016-03-01

Full Text Available Organizations are operating in a dynamic and turbulent environment. In these conditions, they have to make decisions for new problems or situations. Most of decisions are therefore non-programmed and unstructured, accompanied by risk and uncertainty. Moreover, the problems and situations are complex. All organizations are oriented towards group decisionmaking processes, as useful tools to cope with uncertainty and complexity. Apart from the necessity, companies are turning towards participatory processes also to benefit from the important advantages that these processes offer. Organizations have realized the importance of group decision-making processes to contribute to the creation of sustainable competitive advantages. Main objective of this paper is to show that group decision-making processes do not offer guarantee for good decisions, because the effectiveness of group is affected by many factors. So, the first thing done in this paper is discussing about the benefits and limitations that accompany the use of groups with decision-making purpose. Afterwards, we stop on the different factors that influence the group’s ability to make good decisions. The aim is to emphasize that regardless of the many advantages of groups, some factors as group size, type of communication within the group, leadership style, the norms, the differentiation of roles and statuses, cohesion and compliance degree should be the main elements to keep into consideration because they affect the effectiveness of group. In this regard, is discussed how such factors influence the quality of decision and then we try to draw some conclusions that can improve and make better and easier group decision-making processes.

Secure Group Communications for Large Dynamic Multicast Group

Institute of Scientific and Technical Information of China (English)

Liu Jing; Zhou Mingtian

2003-01-01

As the major problem in multicast security, the group key management has been the focus of research But few results are satisfactory. In this paper, the problems of group key management and access control for large dynamic multicast group have been researched and a solution based on SubGroup Secure Controllers (SGSCs) is presented, which solves many problems in IOLUS system and WGL scheme.

Assessment of Group Preferences and Group Uncertainty for Decision Making

Science.gov (United States)

1976-06-01

the individ- uals. decision making , group judgments should be preferred to individual judgments if obtaining group judgments costs more. -26- -YI IV... decision making group . IV. A. 3. Aggregation using conjugate distribution. Arvther procedure for combining indivi(jai probability judgments into a group...statisticized group group decision making group judgment subjective probability Delphi method expected utility nominal group 20. ABSTRACT (Continue on

Thermopower switching by magnetic field: first-principles calculations

DEFF Research Database (Denmark)

Maslyuk, Volodymyr V.; Achilles, Steven; Sandratskii, Leonid

2013-01-01

We present first-principles studies of the thermopower of the organometallic V4Bz5 molecule attached between Co electrodes with noncollinear magnetization directions. Different regimes in the formation of the noncollinear magnetic state of the molecule lead to a remarkable nonmonotonous dependence...

Deposition of metal Islands, metal clusters and metal containing single molecules on self-assembled monolayers

NARCIS (Netherlands)

Speets, Emiel Adrianus

2005-01-01

The central topic of this thesis is the deposition of metals on Self-Assembled Monolayers (SAMs). Metals are deposited in the form of submicron scale islands, nanometer scale clusters, and as supramolecular, organometallic coordination cages. Several SAMs on various substrates were prepared and

The risk evaluation of difficult substances in USES 2.0 and EUSES. A decision tree for data gap filling of Kow, Koc and BCF

NARCIS (Netherlands)

Beelen P van; ECO

2000-01-01

This report presents a decision tree for the risk evaluation of the so-called "difficult" substances with the Uniform System for the Evaluation of Substances (USES). The decision tree gives practical guidelines for the regulatory authorities to evaluate notified substances like organometallic

CNA Seminar

Energy Technology Data Exchange (ETDEWEB)

Browne, Kevin Patrick [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

2015-10-16

Presentation that covers: an introduction to the field of high-nitrogen chemistry; aqueous chemistry of Th with the high-nitrogen ligand bis(tetrazolylamine) and BTA; and water-free, oxygen-free chemistry of Th, U with high-nitrogen ligands using organometallic actinide precursors

Research Article

African Journals Online (AJOL)

2018-01-01

Jan 1, 2018 ... ferrocene derivatives and potentially all analogous organometallic compounds. The results confirm the utility of use of square wave voltammetry techniques for measuring octanol-water partition coefficients of ferrocene derivatives. 5. ACKNOWLEDGEMENT. This research was financed by the laboratory of ...

Immobilization of nanoparticles by occlusion into microbial calcite

DEFF Research Database (Denmark)

Skuce, Rebecca L.; Tobler, Dominique Jeanette; MacLaren, Ian

2017-01-01

systems. In this study, the ureolytic bacteria Sporosarcina pasteurii was used to induce calcium carbonate precipitation in the presence of organo-metallic manufactured nanoparticles. As calcite crystals grew the nanoparticles in the solution became trapped inside these crystals. Capture of NPs within...

Direct catalytic cross-coupling of organolithium compounds

NARCIS (Netherlands)

Giannerini, Massimo; Fananas Mastral, Martin; Feringa, Ben L.

Catalytic carbon-carbon bond formation based on cross-coupling reactions plays a central role in the production of natural products, pharmaceuticals, agrochemicals and organic materials. Coupling reactions of a variety of organometallic reagents and organic halides have changed the face of modern

Microhydration Prevents Fragmentation of Uracil and Thymine by Low-Energy Electrons

Czech Academy of Sciences Publication Activity Database

Kočišek, Jaroslav; Pysanenko, Andriy; Fárník, Michal; Fedor, Juraj

2016-01-01

Roč. 7, AUG 2016 (2016), s. 3401-3405 ISSN 1948-7185 R&D Projects: GA ČR GJ16-10995Y Institutional support: RVO:61388955 Keywords : Microhydration * ionization * organometallics Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 9.353, year: 2016

Group heterogeneity increases the risks of large group size: a longitudinal study of productivity in research groups.

Science.gov (United States)

Cummings, Jonathon N; Kiesler, Sara; Bosagh Zadeh, Reza; Balakrishnan, Aruna D

2013-06-01

Heterogeneous groups are valuable, but differences among members can weaken group identification. Weak group identification may be especially problematic in larger groups, which, in contrast with smaller groups, require more attention to motivating members and coordinating their tasks. We hypothesized that as groups increase in size, productivity would decrease with greater heterogeneity. We studied the longitudinal productivity of 549 research groups varying in disciplinary heterogeneity, institutional heterogeneity, and size. We examined their publication and citation productivity before their projects started and 5 to 9 years later. Larger groups were more productive than smaller groups, but their marginal productivity declined as their heterogeneity increased, either because their members belonged to more disciplines or to more institutions. These results provide evidence that group heterogeneity moderates the effects of group size, and they suggest that desirable diversity in groups may be better leveraged in smaller, more cohesive units.

Representation Theory of Algebraic Groups and Quantum Groups

CERN Document Server

Gyoja, A; Shinoda, K-I; Shoji, T; Tanisaki, Toshiyuki

2010-01-01

Invited articles by top notch expertsFocus is on topics in representation theory of algebraic groups and quantum groupsOf interest to graduate students and researchers in representation theory, group theory, algebraic geometry, quantum theory and math physics

Transition Metal Complexes Coordinated by Water Soluble Phosphane Ligands: How Cyclodextrins Can Alter the Coordination Sphere?

Directory of Open Access Journals (Sweden)

Michel Ferreira

2017-01-01

Full Text Available The behaviour of platinum(II and palladium(0 complexes coordinated by various hydrosoluble monodentate phosphane ligands has been investigated by 31P{1H} NMR spectroscopy in the presence of randomly methylated β-cyclodextrin (RAME-β-CD. This molecular receptor can have no impact on the organometallic complexes, induce the formation of phosphane low-coordinated complexes or form coordination second sphere species. These three behaviours are under thermodynamic control and are governed not only by the affinity of RAME-β-CD for the phosphane but also by the phosphane stereoelectronic properties. When observed, the low-coordinated complexes may be formed either via a preliminary decoordination of the phosphane followed by a complexation of the free ligand by the CD or via the generation of organometallic species complexed by CD which then lead to expulsion of ligands to decrease their internal steric hindrance.

Thermal behavior and transformation kinetics of titanium dioxide nanocrystallites prepared by coupling agents

International Nuclear Information System (INIS)

Chen, W.C.; Wang, Y.T.; Shih, C.J.

2010-01-01

Coupling agents have been widely used to retard the sintering of silver paste and minimize co-firing defects due to densification mismatch between silver and dielectrics. The thermal-decomposition and crystallization behavior of the coupling agent is a subject of great concern. To elucidate what is responsible for the oxidation, Ti organometallic compounds were calcined at different temperatures (350, 400, 500, 600 o C) for 2 h and the crystallization behavior was determined by X-ray diffraction (XRD). The activation energy for crystallization of coupling agents was studied by using isothermal methods. According to the quantitative XRD method, the values calculated by the Johnson-Mehi-Avrami equation are 134.9 kJ mol -1 . The growth morphology parameters are 1.061, 0.915, 1.016 respectively. Combining the results of DTA, XRD and TEM, it is found that formation of nanocrystallized titania accompanies the combustion of organometallic compounds.

Thermal behavior and transformation kinetics of titanium dioxide nanocrystallites prepared by coupling agents

Energy Technology Data Exchange (ETDEWEB)

Chen, W.C. [School of Dentistry, Kaohsiung Medical University, 100 Shi-Chuan 1st Road, Kaohsiung 80708, Taiwan (China); Wang, Y.T. [Department of Medical Research and Education, Chen Hsin General Hospital, 45 Cheng-Hsin Street, Pai-Tou, Taipei 11220, Taiwan (China); Shih, C.J., E-mail: cjshih@kmu.edu.t [Department of Fragrance and Cosmetics Science, Kaohsiung Medical University, 100 Shi-Chuan1st Road, Kaohsiung 80708, Taiwan (China)

2010-02-04

Coupling agents have been widely used to retard the sintering of silver paste and minimize co-firing defects due to densification mismatch between silver and dielectrics. The thermal-decomposition and crystallization behavior of the coupling agent is a subject of great concern. To elucidate what is responsible for the oxidation, Ti organometallic compounds were calcined at different temperatures (350, 400, 500, 600 {sup o}C) for 2 h and the crystallization behavior was determined by X-ray diffraction (XRD). The activation energy for crystallization of coupling agents was studied by using isothermal methods. According to the quantitative XRD method, the values calculated by the Johnson-Mehi-Avrami equation are 134.9 kJ mol{sup -1}. The growth morphology parameters are 1.061, 0.915, 1.016 respectively. Combining the results of DTA, XRD and TEM, it is found that formation of nanocrystallized titania accompanies the combustion of organometallic compounds.

Linear deformations of discrete groups and constructions of multivalued groups

International Nuclear Information System (INIS)

Yagodovskii, Petr V

2000-01-01

We construct deformations of discrete multivalued groups described as special deformations of their group algebras in the class of finite-dimensional associative algebras. We show that the deformations of ordinary groups producing multivalued groups are defined by cocycles with coefficients in the group algebra of the original group and obtain classification theorems on these deformations. We indicate a connection between the linear deformations of discrete groups introduced in this paper and the well-known constructions of multivalued groups. We describe the manifold of three-dimensional associative commutative algebras with identity element, fixed basis, and a constant number of values. The group algebras of n-valued groups of order three (three-dimensional n-group algebras) form a discrete set in this manifold

Re-Examining Group Development in Adventure Therapy Groups.

Science.gov (United States)

DeGraaf, Don; Ashby, Jeff

1998-01-01

Small-group development is an important aspect of adventure therapy. Supplementing knowledge of sequential stages of group development with knowledge concerning within-stage nonsequential development yields a richer understanding of groups. Integrating elements of the individual counseling relationship (working alliance, transference, and real…

Thermodynamic analysis of volatile organometallic fission products

International Nuclear Information System (INIS)

Auxier II, J.D.; Hall, H.L.; Cressy, Derek

2016-01-01

The ability to perform rapid separations in a post nuclear weapon detonation scenario is an important aspect of national security. In the past, separations of fission products have been performed using solvent extraction, precipitation, etc. The focus of this work is to explore the feasibility of using thermochromatography, a technique largely employed in superheavy element chemistry, to expedite the separation of fission products from fuel components. A series of fission product complexes were synthesized and the thermodynamic parameters were measured using TGA/DSC methods. Once measured, these parameters were used to predict their retention times using thermochromatography. (author)

Organometallic Vapor-Phase Epitaxy theory and practice

CERN Document Server

Stringfellow, Gerald B

1999-01-01

This book describes the operation of a particular technique for the production of compound semiconductor materials. It describes how the technique works, how it can be used for the growth of particular materials and structures, and the application of these materials for specific devices. It contains not only a fundamental description of the operation of the technique but also contains lists of data useful for the everyday operation of OMVPE reactors. It also offers specific recipes that can be used to produce a wide range of specific materials, structures, and devices.Key Features* Updated wit

Luminescent Organometallic Nanomaterials with Aggregation-Induced Emission.

Science.gov (United States)

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

2018-07-04

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

Novel organometallic aromatic polyester based on ferrocene

Institute of Scientific and Technical Information of China (English)

Wei

2010-01-01

A novel polyester containing ferrocenyl was prepared by low-temperature interface polycondensation of 1,1'-ferrocenedi-carboxylic acid chloride with 4-(4-hydroxyphenyl)-2,3-phthalazin-l-one(DHPZ), which is a twisted non-coplanar heterocyclic bisphenol-like monomer. The newly generated polymer was evaluated based on characterization of its solubility, viscosity measurements, elemental analysis, FTIR spectroscopy, differential scanning calorimetric and thermogravimetric studies.

Role of cathode identity in liquid chromatography particle beam glow discharge mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Krishna, M.V. Balarama [Department of Chemistry, Biosystems Research Complex, Clemson University, Clemson, SC 29634-1905 (United States); Marcus, R.K. [Department of Chemistry, Biosystems Research Complex, Clemson University, Clemson, SC 29634-1905 (United States)], E-mail: marcusr@clemson.edu

2008-06-15

A detailed evaluation of the role of cathode identity on the analytical and spectral characteristics of various organic, organometallic and metal analytes using liquid chromatography-particle beam/glow discharge mass spectrometry (LC-PB/GDMS) has been carried out. A d.c. discharge, operating with argon as the support gas, was used throughout this work. In this study, Cu which has a relatively high sputtering rate, Ni which has moderate sputtering rate and Ta which has very low sputtering rate, are taken as cathode materials to study the ionization, fragmentation, and analytical characteristics of organic (caffeine, epigallocatechin gallate, peptide as representative compounds), organometallic (selenomethionine, triethyl lead chloride as representative compounds) and metal (Fe, La, Cs and Pb) species. A range of discharge gas pressures (26.6-106.4 Pa) and currents (0.2-1.5 mA) were investigated with the test cathodes to determine their influence on the spectral composition and overall analytical response for the various test species. Calibration plots were obtained for all of the species for each of the three cathodes to determine the respective limits of detection. Relative detection limits in the range of 0.02 to 15 ng mL{sup -1} (0.002-1.5 ng, absolute) for the test species were found to be in the order of Cu > Ni > Ta; which follows the order of the sputtering characteristics of the respective cathodes. These studies rendered information about the respective discharge parameters' role in choosing the most appropriate cathode identity in PB-GDMS for application in the areas of organic, organometallic and inorganic species analysis.

Linking self and group: cognitive routes to self-group overlap as driving forces of group phenomena

NARCIS (Netherlands)

van Veelen, Ruth; Otten, Sabine

2014-01-01

Group affiliation implies that there is overlap in the mental representations of seld and group. Combining research on social cognition and group processes, this symposium brings together various perspectives on self-group overlap and its consequences for intra- and intergroup phenomena.

Post-Disaster Social Justice Group Work and Group Supervision

Science.gov (United States)

Bemak, Fred; Chung, Rita Chi-Ying

2011-01-01

This article discusses post-disaster group counseling and group supervision using a social justice orientation for working with post-disaster survivors from underserved populations. The Disaster Cross-Cultural Counseling model is a culturally responsive group counseling model that infuses social justice into post-disaster group counseling and…

Nanostructured Thin Films Obtained from Fischer Aminocarbene Complexes

Directory of Open Access Journals (Sweden)

Rosa E. Lazo-Jiménez

2016-03-01

Full Text Available The synthesis of four amphiphilic organometallic complexes with the general formula RC = M(CO5NH(CH215CH3, where R is a ferrocenyl 2(a-b or a phenyl 4(a-b group as a donor moiety and a Fischer carbene of chromium (0 or tungsten (0 as an acceptor group, are reported. These four push-pull systems formed Langmuir (L monolayers at the air-water interface, which were characterized by isotherms of surface pressure versus molecular area and compression/expansion cycles (hysteresis curves; Brewster angle microscopic images were also obtained. By using the Langmuir–Blodgett (LB method, molecular monolayers were transferred onto glass substrates forming Z-type multilayers. LB films were characterized through ultraviolet-visible spectroscopy, atomic force microscopy and X-ray diffraction techniques. Results indicated that films obtained from 2b complex [(Ferrocenyl(hexadecylaminemethylidene] pentacarbonyl tungsten (0 are the most stable and homogeneous; due to their properties, these materials may be incorporated into organic electronic devices.

Nanostructured Thin Films Obtained from Fischer Aminocarbene Complexes

Science.gov (United States)

Lazo-Jiménez, Rosa E.; Ortega-Alfaro, M. Carmen; López-Cortés, José G.; Alvarez-Toledano, Cecilio; Chávez-Carvayar, José Á.; Ignés-Mullol, Jordi; González-Torres, Maykel; Carreón-Castro, Pilar

2016-01-01

The synthesis of four amphiphilic organometallic complexes with the general formula RC = M(CO)5NH(CH2)15CH3, where R is a ferrocenyl 2(a-b) or a phenyl 4(a-b) group as a donor moiety and a Fischer carbene of chromium (0) or tungsten (0) as an acceptor group, are reported. These four push-pull systems formed Langmuir (L) monolayers at the air-water interface, which were characterized by isotherms of surface pressure versus molecular area and compression/expansion cycles (hysteresis curves); Brewster angle microscopic images were also obtained. By using the Langmuir–Blodgett (LB) method, molecular monolayers were transferred onto glass substrates forming Z-type multilayers. LB films were characterized through ultraviolet-visible spectroscopy, atomic force microscopy and X-ray diffraction techniques. Results indicated that films obtained from 2b complex [(Ferrocenyl)(hexadecylamine)methylidene] pentacarbonyl tungsten (0) are the most stable and homogeneous; due to their properties, these materials may be incorporated into organic electronic devices. PMID:28773289

Feminist Principles in Survivor's Groups: Out-of-Group Contact.

Science.gov (United States)

Rittenhouse, JoAn

1997-01-01

Illustrates the value of theoretical concepts from Feminist Therapy in the group treatment of women survivors. Theoretical underpinnings are supported using data taken from clinical experience and by examining group themes and out-of-group contact developed from the case sample. Principles regarding feminist groups are proposed. (RJM)

Group as social microcosm: Within-group interpersonal style is congruent with outside group relational tendencies.

Science.gov (United States)

Goldberg, Simon B; Hoyt, William T

2015-06-01

The notion that individuals' interpersonal behaviors in the context of therapy reflects their interpersonal behaviors outside of therapy is a fundamental hypothesis underlying numerous systems of psychotherapy. The social microcosm hypothesis, in particular, claims the interpersonal therapy group becomes a reflection of group members' general tendencies, and can thus be used as information about members' interpersonal functioning as well as an opportunity for learning and behavior change. The current study tested this hypothesis using data drawn from 207 individuals participating in 22 interpersonal process groups. Ratings were made on 2 key interpersonal domains (Dominance and Affiliation) at baseline and at Weeks 2, 5, and 8 of the group. Two-level multilevel models (with participants nested within groups) were used to account for the hierarchical structure, and the social relations model (SRM; Kenny, 1994) was used to estimate peer ratings (target effects in SRM) unconfounded with rater bias. Participants showed consensus at all time points during the interpersonal process groups on one another's levels of dominance and affiliation. In addition, self- and peer ratings were stable across time and correlated with one another. Importantly, self-ratings made prior to group significantly predicted ratings (self- and peer) made within the group, with effect sizes within the medium range. Taken together, these results provide robust support for the social microcosm hypothesis and the conjecture that interpersonal style within-group therapy is reflective of broader interpersonal tendencies. (c) 2015 APA, all rights reserved).

Permutation groups

CERN Document Server

Passman, Donald S

2012-01-01

This volume by a prominent authority on permutation groups consists of lecture notes that provide a self-contained account of distinct classification theorems. A ready source of frequently quoted but usually inaccessible theorems, it is ideally suited for professional group theorists as well as students with a solid background in modern algebra.The three-part treatment begins with an introductory chapter and advances to an economical development of the tools of basic group theory, including group extensions, transfer theorems, and group representations and characters. The final chapter feature

Evaluation of Cytotoxic Activity of Titanocene Difluorides and Determination of Their Mechanism of Action in Ovarian Cancer Cells

Czech Academy of Sciences Publication Activity Database

Koubková, L.; Vyzula, R.; Karban, Jindřich; Pinkas, Jiří; Ondroušková, E.; Vojtěšek, B.; Hrstka, R.

2015-01-01

Roč. 33, č. 5 (2015), s. 1123-1132 ISSN 0167-6997 R&D Projects: GA ČR(CZ) GAP207/12/2368 Institutional support: RVO:67985858 ; RVO:61388955 Keywords : cisplatin * cytotoxicity * organometallic compounds Subject RIV: CA - Inorganic Chemistry Impact factor: 3.281, year: 2015

Organo-gallium and indium complexes with dithiolate and oxo ligands

Indian Academy of Sciences (India)

Page 1 ... of several of these com- plexes have been established by single crystal X-ray diffraction analyses. Complexes derived from oxo ligands ... diode) applications.8. Organometallic complexes derived from chelating ligands, such as substituted. 8-hydroxyqunoline and azomethine linkages, are emerging as potential ...

Associateship | Indian Academy of Sciences

Indian Academy of Sciences (India)

Home; Fellowship; Associateship. Associate Profile. Period: 2013–2016. Maiti, Dr Debabrata. Date of birth: 10 December 1980. Specialization: Organometallic Chemistry, Bioinspired Catalysis Address during Associateship: Dept. of Chemistry, IIT, Mumbai 400 076. Contact: Email: dmaiti@chem.iitb.ac.in. YouTube; Twitter ...

Bulletin of Materials Science | Indian Academy of Sciences

Indian Academy of Sciences (India)

Keywords. Organometallic compounds; chemical synthesis; luminescence. Abstract. Alq3 is known to emit bright green light under UV excitation. Blue shift of the emission was reported in recent literature. This was ascribed to the presence of various isomers/crystallographic modifications obtained through train sublimation.

The growth of various buffer layer structures and their influence on the quality of (CdHg)Te epilayers

CSIR Research Space (South Africa)

Gouws, GJ

1993-05-01

Full Text Available The suitability of various buffer layer structures on (100) GaAs for (CdHg)Te growth by organometallic vapour phase epitaxy (OMVPE) was investigated. The preferred epitaxial orientation of (100) GaAs/ (lll) CdTe was found to be unsuitable due...

Surface Catalytic Sites Prepared from [HRe(CO)5] and [H3Re3(CO)12]: Mononuclear, Trinuclear, and Metallic Rhenium Catalysts Supported on Magnesia.

NARCIS (Netherlands)

Koningsberger, D.C.; Kirlin, P.S.; Zon, F.B.M. van; Gates, B.C.

1990-01-01

MgO-supported catalysts were prepared from [HRe(CO)5] and [H,Re3(CO),,] and characterized by extraction of surface organometallics, infrared and ultraviolet/visible spectroscopy, and extended X-ray absorption fine structure (EXAFS) spectroscopy. The EXAFS analysis and other data show that

Ortho lithiation-in situ borylation of substituted morpholine benzamides

DEFF Research Database (Denmark)

Cederbalk, Anna; Lysén, Morten; Kehler, Jan

2017-01-01

Morpholine amides are cheap and safe alternative to Weinreb amides as acylating agents of organometallic species. Herein, the in-situ lithiation/borylation of 18 ortho- meta- and para-substituted morpholine benzamides has been investigated. 10 of the 18 substrates provided the desired boronic est...

Palladium-catalysed direct cross-coupling of secondary alkyllithium reagents

NARCIS (Netherlands)

Vila, Carlos; Giannerini, Massimo; Hornillos, Valentin; Fananas-Mastral, Martin; Feringa, Ben L.

2014-01-01

Palladium-catalysed cross-coupling of secondary C(sp(3)) organometallic reagents has been a long-standing challenge in organic synthesis, due to the problems associated with undesired isomerisation or the formation of reduction products. Based on our recently developed catalytic C-C bond formation

78 FR 15303 - Hazardous Materials; Miscellaneous Amendments (RRR)

Science.gov (United States)

2013-03-11

... previous rulemaking. Add the inadvertently omitted entries for ``Paint related material, flammable..., flammable, corrosive (including paint thinning or reducing compound)'' UN3469, PG II, and PG III to the Sec... the more appropriate generic entries for organometallic compounds and substances. Add the entries for...

Group identity and positive deviance in work groups.

Science.gov (United States)

Kim, Moon Joung; Choi, Jin Nam

2017-12-05

This study examines why and how identity cognitions, including group identification and individual differentiation, influence the positive deviance of employees. We identify the risk-taking intention of employees as a critical psychological mechanism to overcome stigma-induced identity threat of positive deviance. The analysis of data collected from 293 members comprising 66 work teams reveals that the relationship between individual differentiation and positive deviance is partially mediated by risk-taking intention. The indirect effect of group identification on positive deviance through risk-taking intention is also significant and positive in groups with low conformity pressure, whereas the same indirect effect is neutralized in groups with high conformity pressure. The current analysis offers new insights into the way the group context and the identity cognition of members explain the development of positive deviance and workplace creativity.

When are emotions related to group-based appraisals? A comparison between group-based emotions and general group emotions.

Science.gov (United States)

Kuppens, Toon; Yzerbyt, Vincent Y

2014-12-01

In the literature on emotions in intergroup relations, it is not always clear how exactly emotions are group-related. Here, we distinguish between emotions that involve appraisals of immediate group concerns (i.e., group-based emotions) and emotions that do not. Recently, general group emotions, measured by asking people how they feel "as a group member" but without specifying an object for these emotions, have been conceptualized as reflecting appraisals of group concerns. In contrast, we propose that general group emotions are best seen as emotions about belonging to a group. In two studies, general group emotions were closely related to emotions that are explicitly measured as belonging emotions. Two further studies showed that general group emotions were not related to appraisals of immediate group concerns, whereas group-based emotions were. We argue for more specificity regarding the group-level aspects of emotion that are tapped by emotion measures. © 2014 by the Society for Personality and Social Psychology, Inc.

Emotional collectives: How groups shape emotions and emotions shape groups.

Science.gov (United States)

van Kleef, Gerben A; Fischer, Agneta H

2016-01-01

Group settings are epicentres of emotional activity. Yet, the role of emotions in groups is poorly understood. How do group-level phenomena shape group members' emotional experience and expression? How are emotional expressions recognised, interpreted and shared in group settings? And how do such expressions influence the emotions, cognitions and behaviours of fellow group members and outside observers? To answer these and other questions, we draw on relevant theoretical perspectives (e.g., intergroup emotions theory, social appraisal theory and emotions as social information theory) and recent empirical findings regarding the role of emotions in groups. We organise our review according to two overarching themes: how groups shape emotions and how emotions shape groups. We show how novel empirical approaches break important new ground in uncovering the role of emotions in groups. Research on emotional collectives is thriving and constitutes a key to understanding the social nature of emotions.

Automorphism group of nonabelian groups of order p{sup 3}

Energy Technology Data Exchange (ETDEWEB)

Sarmin, Nor Haniza [Department of Mathematical Sciences, Faculty of Science, Universiti Teknologi Malaysia, 81310 UTM Johor Bahru (Malaysia); Barakat, Yasamin [Department of Mathematical Sciences, Faculty of Science, Universiti Teknologi Malaysia, 81310 UTM Johor Bahru, Malaysia and Islamic Azad University-Ahvaz Branch, Ahvaz (Iran, Islamic Republic of)

2014-06-19

Let G be a nonabelian group of order p{sup 3}, where p is a prime number. Then G is a two generated group that its commutator, centre and Frattini subgroup coincide and are of order p. Hence, the quotient group of G over its centre and also Frattini quotient group of G, both are of order p{sup 2}. However, the first mentioned quotient is isomorphic to the inner group of G, which is a normal subgroup of automorphism group of G. Whereas, Frattini quotient group of G is an abelian elementary group that can be considered as a vector space of dimension two over Z{sub p}, the field of integers modulo p. In this paper, we consider to apply these properties of G to characterize the automorphism group of G.

Group performance and group learning at dynamic system control tasks

International Nuclear Information System (INIS)

Drewes, Sylvana

2013-01-01

Proper management of dynamic systems (e.g. cooling systems of nuclear power plants or production and warehousing) is important to ensure public safety and economic success. So far, research has provided broad evidence for systematic shortcomings in individuals' control performance of dynamic systems. This research aims to investigate whether groups manifest synergy (Larson, 2010) and outperform individuals and if so, what processes lead to these performance advantages. In three experiments - including simulations of a nuclear power plant and a business setting - I compare the control performance of three-person-groups to the average individual performance and to nominal groups (N = 105 groups per experiment). The nominal group condition captures the statistical advantage of aggregated group judgements not due to social interaction. First, results show a superior performance of groups compared to individuals. Second, a meta-analysis across all three experiments shows interaction-based process gains in dynamic control tasks: Interacting groups outperform the average individual performance as well as the nominal group performance. Third, group interaction leads to stable individual improvements of group members that exceed practice effects. In sum, these results provide the first unequivocal evidence for interaction-based performance gains of groups in dynamic control tasks and imply that employers should rely on groups to provide opportunities for individual learning and to foster dynamic system control at its best.

How to conduct focus groups: researching group priorities through discussion.

Science.gov (United States)

1992-01-01

Focus groups serve to uncover priorities and beliefs of a target group, but health project designers do not always take the time to seek this information beforehand. Focus groups also allow various local subgroups to communicate their concerns before the project starts. Focus groups can also breed ideas and dialogue that individual interviews cannot and they provide baseline information so managers can determine if attitudes or priorities have resulted from the project. Diverse people have different beliefs, e.g., women who have young children view oral rehydration therapy differently from women with no children. Project designers can use these basic differences to arrive at some conclusions about general attitudes. Focus group facilitators should have a discussion outline to help keep the group on the topic of concern. They should limit sessions to 60-90 minutes. Each focus groups should include 8-10 people. It is important to have members of various community subgroups in each group. Yet group designers should be careful not to include within the same group, those who may intimidate other people in the group, e.g., in situations where farmers depend on middlemen, farmers may not be open if middlemen are also in the focus group. Facilitators should launch each session with an attempt to encourage the members to be open and to feel comfortable. For example, in Malawi, a facilitator leads her focus group discussions with songs. Stories are another icebreaker. It is important that all focus groups centering around a certain project discuss the same topics. Facilitators need to stress to the group that all discussions are to be kept confidential. The designers should also carefully word the questions so that facilitators will not impart their bias. Facilitators should not direct the group to certain conclusions, but instead keep the discussions focused.

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

International Nuclear Information System (INIS)

Huet-Dales, A.

2003-11-01

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

Structural features and electronic properties of group-III-, group-IV-, and group-V-doped Si nanocrystallites

International Nuclear Information System (INIS)

Ramos, L E; Degoli, Elena; Cantele, G; Ossicini, Stefano; Ninno, D; Furthmueller, J; Bechstedt, F

2007-01-01

We investigate the incorporation of group-III (B and Al), group-IV (C and Ge), and group-V (N and P) impurities in Si nanocrystallites. The structural features and electronic properties of doped Si nanocrystallites, which are faceted or spherical-like, are studied by means of an ab initio pseudopotential method including spin polarization. Jahn-Teller distortions occur in the neighborhood of the impurity sites and the bond lengths show a dependence on size and shape of the nanocrystallites. We find that the acceptor (group-III) and donor (group-V) levels become deep as the nanocrystallites become small. The energy difference between the spin-up and spin-down levels of group-III and group-V impurities decreases as the size of the Si nanocrystallite increases and tends to the value calculated for Si bulk. Doping with carbon introduces an impurity-related level in the energy gap of the Si nanocrystallites

NSF-RANN trace contaminants abstracts

International Nuclear Information System (INIS)

Copenhaver, E.D.; Harnden, D.S.

1976-10-01

Specific areas of interest of the Environmental Aspects of Trace Contaminants Program are organic chemicals of commerce, metals and organometallic compounds, air-borne contaminants, and environmental assay methodology. Fifty-three abstracts of literature on trace contaminants are presented. Author, keyword, and permuted title indexes are included

Aerogel nanoscale magnesium oxides as a destructive sorbent for toxic chemical agents

Czech Academy of Sciences Publication Activity Database

Štengl, Václav; Bakardjieva, Snejana; Maříková, Monika; Šubrt, Jan; Oplustil, F.; Olšanská, M.

2004-01-01

Roč. 2, č. 1 (2004), s. 16-33 ISSN 1644-3624 R&D Projects: GA MŠk LN00A028 Institutional research plan: CEZ:AV0Z4032918 Keywords : nanostructures * organometallic compounds * chemical synthesis Subject RIV: CA - Inorganic Chemistry Impact factor: 0.171, year: 2004

Author Details

African Journals Online (AJOL)

Quantification of Rhodium in a Series of Inorganic and Organometallic Compounds using Cobalt as Internal Standard Abstract PDF · Vol 63 (2010) - Articles Characterization and Oxidative Addition Reactions of Different Rhodium and Iridium Triazolato Complexes Abstract PDF PDF · Vol 64 (2011) - Articles Dissolution and ...

Molecular modeling of inorganic compounds

National Research Council Canada - National Science Library

Comba, Peter; Hambley, Trevor W; Martin, Bodo

2009-01-01

... mechanics to inorganic and coordination compounds. Initially, simple metal complexes were modeled, but recently the field has been extended to include organometallic compounds, catalysis and the interaction of metal ions with biological macromolecules. The application of molecular mechanics to coordination compounds is complicated by the numbe...

Bikash Kumar Panda

Indian Academy of Sciences (India)

Home; Journals; Journal of Chemical Sciences. Bikash Kumar Panda. Articles written in Journal of Chemical Sciences. Volume 116 Issue 5 August 2004 pp 245-250. Synthesis, characterization and emission properties of quinolin-8-olato chelated ruthenium organometallics · Bikash Kumar Panda · More Details Abstract ...

Geometric group theory

CERN Document Server

Druţu, Cornelia

2018-01-01

The key idea in geometric group theory is to study infinite groups by endowing them with a metric and treating them as geometric spaces. This applies to many groups naturally appearing in topology, geometry, and algebra, such as fundamental groups of manifolds, groups of matrices with integer coefficients, etc. The primary focus of this book is to cover the foundations of geometric group theory, including coarse topology, ultralimits and asymptotic cones, hyperbolic groups, isoperimetric inequalities, growth of groups, amenability, Kazhdan's Property (T) and the Haagerup property, as well as their characterizations in terms of group actions on median spaces and spaces with walls. The book contains proofs of several fundamental results of geometric group theory, such as Gromov's theorem on groups of polynomial growth, Tits's alternative, Stallings's theorem on ends of groups, Dunwoody's accessibility theorem, the Mostow Rigidity Theorem, and quasiisometric rigidity theorems of Tukia and Schwartz. This is the f...

ALIGNMENTS OF GROUP GALAXIES WITH NEIGHBORING GROUPS

International Nuclear Information System (INIS)

Wang Yougang; Chen Xuelei; Park, Changbom; Yang Xiaohu; Choi, Yun-Young

2009-01-01

Using a sample of galaxy groups found in the Sloan Digital Sky Survey Data Release 4, we measure the following four types of alignment signals: (1) the alignment between the distributions of the satellites of each group relative to the direction of the nearest neighbor group (NNG); (2) the alignment between the major axis direction of the central galaxy of the host group (HG) and the direction of the NNG; (3) the alignment between the major axes of the central galaxies of the HG and the NNG; and (4) the alignment between the major axes of the satellites of the HG and the direction of the NNG. We find strong signal of alignment between the satellite distribution and the orientation of central galaxy relative to the direction of the NNG, even when the NNG is located beyond 3r vir of the host group. The major axis of the central galaxy of the HG is aligned with the direction of the NNG. The alignment signals are more prominent for groups that are more massive and with early-type central galaxies. We also find that there is a preference for the two major axes of the central galaxies of the HG and NNG to be parallel for the system with both early central galaxies, however, not for the systems with both late-type central galaxies. For the orientation of satellite galaxies, we do not find any significant alignment signals relative to the direction of the NNG. From these four types of alignment measurements, we conclude that the large-scale environment traced by the nearby group affects primarily the shape of the host dark matter halo, and hence also affects the distribution of satellite galaxies and the orientation of central galaxies. In addition, the NNG directly affects the distribution of the satellite galaxies by inducing asymmetric alignment signals, and the NNG at very small separation may also contribute a second-order impact on the orientation of the central galaxy in the HG.

Monte Carlo simulations guided by imaging to predict the in vitro ranking of radiosensitizing nanoparticles.

Science.gov (United States)

Retif, Paul; Reinhard, Aurélie; Paquot, Héna; Jouan-Hureaux, Valérie; Chateau, Alicia; Sancey, Lucie; Barberi-Heyob, Muriel; Pinel, Sophie; Bastogne, Thierry

This article addresses the in silico-in vitro prediction issue of organometallic nanoparticles (NPs)-based radiosensitization enhancement. The goal was to carry out computational experiments to quickly identify efficient nanostructures and then to preferentially select the most promising ones for the subsequent in vivo studies. To this aim, this interdisciplinary article introduces a new theoretical Monte Carlo computational ranking method and tests it using 3 different organometallic NPs in terms of size and composition. While the ranking predicted in a classical theoretical scenario did not fit the reference results at all, in contrast, we showed for the first time how our accelerated in silico virtual screening method, based on basic in vitro experimental data (which takes into account the NPs cell biodistribution), was able to predict a relevant ranking in accordance with in vitro clonogenic efficiency. This corroborates the pertinence of such a prior ranking method that could speed up the preclinical development of NPs in radiation therapy.

Manipulating molecule-substrate exchange interactions via graphene

Science.gov (United States)

Bhandary, Sumanta; Eriksson, Olle; Sanyal, Biplab

2013-03-01

Organometallic molecules with a 3d metal center carrying a spin offers many interesting properties, e.g., existence of multiple spin states. A recent interest has been in understanding the magnetic exchange interaction between these organometallic molecules and magnetic substrates both from experiments and theory. In this work, we will show by calculations based on density functional theory how the exchange interaction is mediated via graphene in a geometry containing iron porphyrin(FeP)/graphene/Ni(111). The exchange interaction varies from a ferromagnetic to an antiferromagnetic one depending on the lattice site and type of defect in the graphene lattice along with the switching of spin state of Fe in FeP between S=1 and S=2, which should be detectable by x-ray magnetic circular dichroism experiments. This scenario of complex magnetic couplings with large magnetic moments may offer a unique spintronic logic device. We acknowledge financial support from the Swedish Research Council, KAW foundation and the ERC(project 247062 - ASD).

Theoretical study of the structure and the reactivity of lanthanides and actinides complexes: Activation of small molecules

International Nuclear Information System (INIS)

Castro, Ludovic

2012-01-01

This PhD thesis presents a theoretical study of the structure and the reactivity of organometallic complexes of lanthanides and actinides at the DFT level. After a general introduction of the methods of theoretical chemistry used for the modelling of organometallic reactivity, a study of the participation of 5f electrons in uranium(IV) reactivity is presented. The results show that the large core ECP can be used safely in order to treat the actinide and so that 5f electrons can be treated implicitly. Then, the reactivity of uranium(III) complexes with CO 2 and other analogous molecules is studied via multiple examples from the literature. These studies show that the steric nature of the ligands is very important and controls the reactivity. This study is then extended to samarium(II) complex. Eventually, the reactivity of a hydride complex of cerium(III) with MeOSO 2 Me is investigated and theoretical results are compared with experimental observations. (author) [fr

24 CFR 982.612 - Group home: State approval of group home.

Science.gov (United States)

2010-04-01

... 24 Housing and Urban Development 4 2010-04-01 2010-04-01 false Group home: State approval of group... Types Group Home § 982.612 Group home: State approval of group home. A group home must be licensed..., Retardation, or Social Services) as a group home for elderly persons or persons with disabilities. ...

Abelian groups

CERN Document Server

Fuchs, László

2015-01-01

Written by one of the subject’s foremost experts, this book focuses on the central developments and modern methods of the advanced theory of abelian groups, while remaining accessible, as an introduction and reference, to the non-specialist. It provides a coherent source for results scattered throughout the research literature with lots of new proofs. The presentation highlights major trends that have radically changed the modern character of the subject, in particular, the use of homological methods in the structure theory of various classes of abelian groups, and the use of advanced set-theoretical methods in the study of undecidability problems. The treatment of the latter trend includes Shelah’s seminal work on the undecidability in ZFC of Whitehead’s Problem; while the treatment of the former trend includes an extensive (but non-exhaustive) study of p-groups, torsion-free groups, mixed groups, and important classes of groups arising from ring theory. To prepare the reader to tackle these topics, th...

Clifford algebras, spinors, spin groups and covering groups

International Nuclear Information System (INIS)

Magneville, C.; Pansart, J.P.

1991-03-01

The Dirac equation uses matrices named Υ matrices which are representations of general algebraic structures associated with a metric space. These algebras are the Clifford algebras. In the first past, these algebras are studied. Then the notion of spinor is developed. It is shown that Majorana and Weyl spinors only exist for some particular metric space. In the second part, Clifford and spinor groups are studied. They may be interpreted as the extension of the notion of orthogonal group for Clifford algebras and their spaces for representation. The rotation of a spinor is computed. In the last part, the connexion between the spinor groups and the Universal Covering Groups is presented [fr

Growth and characterization of nonlinear optical bimetallic thiocyanate complex of MCCTC crystal

Science.gov (United States)

Ravi Kumar, S. M.; Melikechi, N.; Selvakumar, S.; Sagayaraj, P.

2009-04-01

An organometallic material of mercury cadmium chloride thiocyanate (MCCTC) was synthesized in water-methanol mixed solvent. Optically good grade crystal was grown by slow evaporation technique under optimized conditions. MCCTC belongs to rhombohedral system with R3c space group. The metal coordinations with (S with Hg and N with Cd) SCN - ion were confirmed in the sample by Fourier transform infrared (FT-IR) spectroscopic investigations. The transmission spectrum recorded from 200 to 2500 nm showed the UV transparency cutoff at 300 nm. MCCTC crystal exhibits a second-harmonic generation (SHG) efficiency which is nearly 17 times more than that of KDP. The microhardness study indicates the hard nature of the grown sample with a work hardening coefficient of 1.73. The thermal decomposition process was investigated by thermo gravimetric and differential thermal analyses.

A 3D visualization of the substituent effect : A brief analysis of two components of the operational formula of dual descriptor for open-shell systems.

Science.gov (United States)

Martínez-Araya, Jorge I; Yepes, Diana; Jaque, Pablo

2017-12-27

Six organometallic compounds coming from a basic Mo-based complex were analyzed from the perspective of the dual descriptor in order to detect subtle influences that a substituent group could exert on the reactive core at a long range. Since the aforementioned complexes are open-shell systems, the used operational formula for the dual descriptor is that one defined for those aforementioned systems, which was then compared with spin density. In addition, dual descriptor was decomposed into two terms, each of which was also applied on every molecular system. The obtained results indicated that components of dual descriptor could become more useful than the operational formula of dual descriptor because differences exerted by the substituents at the para position were better detected by components of dual descriptor rather than the dual descriptor by itself.

Quantum isometry groups

Indian Academy of Sciences (India)

Jyotishman Bhowmick

2015-11-07

Nov 7, 2015 ... Classical. Quantum. Background. Compact Hausdorff space. Unital C∗ algebra. Gelfand-Naimark. Compact Group. Compact Quantum Group. Woronowicz. Group Action. Coaction. Woronowicz. Riemannian manifold. Spectral triple. Connes. Isometry group. Quantum Isometry Group. To be discussed.

Perceptual grouping and attention: not all groupings are equal.

Science.gov (United States)

Kimchi, Ruth; Razpurker-Apfeld, Irene

2004-08-01

We examined grouping under inattention using Driver, Davis, Russell, Turatto, & Freeman's (2001) method. On each trial, two successive displays were briefly presented, each comprising a central target square surrounded by elements. The task was to judge whether the two targets were the same or different. The organization of the background elements stayed the same or changed, independently of the targets. In different conditions, background elements grouped into columns/rows by color similarity, a shape (a triangle/arrow, a square/cross, or a vertical/horizontal line) by color similarity, and a shape with no other elements in the background. We measured the influence of the background on the target same-different judgments. The results imply that background elements grouped into columns/rows by color similarity and into a shape when no segregation from other elements was involved and the shape was relatively "good." In contrast, no background grouping was observed when resolving figure-ground relations for segregated units was required, as in grouping into a shape by color similarity. These results suggest that grouping is a multiplicity of processes that vary in their attentional demands. Regardless of attentional demands, the products of grouping are not available to awareness without attention.

Group Work: How to Use Groups Effectively

Science.gov (United States)

Burke, Alison

2011-01-01

Many students cringe and groan when told that they will need to work in a group. However, group work has been found to be good for students and good for teachers. Employers want college graduates to have developed teamwork skills. Additionally, students who participate in collaborative learning get better grades, are more satisfied with their…

Working with Group-Tasks and Group Cohesiveness

Science.gov (United States)

Anwar, Khoirul

2016-01-01

This study aimed at exploring the connection between the use of group task and group cohesiveness. This study is very important because the nature of the learner's success is largely determined by the values of cooperation, interaction, and understanding of the learning objectives together. Subjects of this study are 28 students on the course…

Group Insight Versus Group Desensitization in Treating Speech Anxiety

Science.gov (United States)

Meichenbaum, Donald H.; And Others

1971-01-01

Results of this study indicated that the insight group was as effective as the desensitization group in significantly reducing speech anxiety over control group levels as assessed by behavioral, cognitive, and self-report measures given immediately after posttreatment and later at a three-month follow-up. (Author)

BODIPY-phosphane as a versatile tool for easy access to new metal-based theranostics

NARCIS (Netherlands)

Tasan, Semra; Zava, Olivier; Bertrand, Benoit; Bernhard, Claire; Goze, Christine; Picquet, Michel; Le Gendre, Pierre; Harvey, Pierre; Denat, Franck; Casini, Angela; Bodio, Ewen

2013-01-01

A new BODIPY-phosphane was synthesized and proved to be a versatile tool for imaging organometallic complexes. It also led to easy access to a new family of theranostics, featuring gold, ruthenium and osmium complexes. The compounds' cytotoxicity was tested on cancer cells, and their cell uptake was

Impact Assessment and Bioremediation of oil Contaminated Soil: A ...

African Journals Online (AJOL)

MICHAEL HORSFALL

remediation process was descriptive using denitrifying bacteria for 27 days at 7 days intervals. The results ... environmental degradation has also been witnessed in the Niger ... in which toxic waste was deposited in pretence of ... wrapped in a well labeled foil paper to avoid ... organometallic compounds that migrate with.

Synergy between Two Metal Catalysts: A Highly Active Silica Supported Bimetallic W/Zr Catalyst for Metathesis of n-Decane

KAUST Repository

Samantaray, Manoja; Dey, Raju; Kavitake, Santosh Giridhar; Abou-Hamad, Edy; Bendjeriou-Sedjerari, Anissa; Hamieh, Ali Imad Ali; Basset, Jean-Marie

2016-01-01

A well-defined, silica supported, bimetallic precatalyst [≡Si-O-W(Me)5 ≡Si-O-Zr(Np)3](4) has been synthesized for the first time via successively grafting two organometallic complexes [W(CH3)6 (1) followed by ZrNp4 (2)] on a single silica support

Small Group Research

Science.gov (United States)

McGrath, Joseph E.

1978-01-01

Summarizes research on small group processes by giving a comprehensive account of the types of variables primarily studied in the laboratory. These include group structure, group composition, group size, and group relations. Considers effects of power, leadership, conformity to social norms, and role relationships. (Author/AV)

Group Leader Development: Effects of Personal Growth and Psychoeducational Groups

Science.gov (United States)

Ohrt, Jonathan H.; Robinson, E. H., III; Hagedorn, W. Bryce

2013-01-01

The purpose of this quasi-experimental study was to compare the effects of personal growth groups and psychoeducational groups on counselor education students' (n = 74) empathy and group leader self-efficacy. Additionally, we compared the degree to which participants in each group valued: (a) cohesion, (b) catharsis, and (c) insight. There were no…

The Integration of Biology Into the Treatment of Diffuse Intrinsic Pontine Glioma: A Review of the North American Clinical Trial Perspective.

Science.gov (United States)

Clymer, Jessica; Kieran, Mark W

2018-01-01

Dramatic advances in the molecular analysis of diffuse intrinsic pontine glioma have occurred over the last decade and resulted in the identification of potential therapeutic targets. In spite of these advances, no significant improvement in the outcome has been achieved and median survival remains approximately 10 months. An understanding of the approaches that have been taken to date, why they failed, and how that information can lead the field forward is critical if we are to change the status quo . In this review, we will discuss the clinical trial landscape in North America with an overview of historical approaches that failed and what might account for this failure. We will then provide a discussion of how our understanding of the genotype of this disease has led to the development of a number of trials targeting the mutations and epigenome of diffuse intrinsic pontine gliomas and the issues related to these trials. Similarly, the introduction of methodologies to address penetration across the blood-brain barrier will be considered in the context of both targeted approaches, epigenetic modification, and immune surveillance of these tumors. The comprehensive analysis of these data, generated through cooperative groups, collaborative clinical trials, and pilot studies in North America will be the focus of the IVth Memorial Alicia Pueyo international symposium in Barcelona on March 12th, 2018 and will be compared and contrasted with a similar comprehensive analysis of the European data with the goal of bringing all of these data together to develop a uniform platform on which new rational trials can be based.

Group-analytic training groups for psychology students: A qualitative study

DEFF Research Database (Denmark)

Nathan, Vibeke Torpe; Poulsen, Stig

2004-01-01

This article presents results from an interview study of psychology students' experiences from group-analytic groups conducted at the University of Copenhagen. The primary foci are the significance of differences in themotivation participants'  personal aims of individual participantsfor particip......This article presents results from an interview study of psychology students' experiences from group-analytic groups conducted at the University of Copenhagen. The primary foci are the significance of differences in themotivation participants'  personal aims of individual participantsfor...... participation in the group, the impact of the composition of participants on the group process, and the professional learning through the group experience. In general the interviews show a marked satisfaction with the group participation. In particular, learning about the importance of group boundaries...

Spectroelectrochemistry: A valuable tool for the study of organometallic-alkyne, -vinylidene, -cumulene, -alkynyl and related complexes

International Nuclear Information System (INIS)

Low, Paul J.; Bock, Sören

2013-01-01

This review presents a highly selective summary of spectroelectrochemical methods used in the study of metal alkyne, acetylide, vinylidene and allenylidene complexes. The review is illustrated predominantly by the selected examples from the authors’ group that formed the basis of a lecture at the recent ISE Annual Meeting. Emphasis is placed on the use of spectroelectrochemical methods to study redox-induced ligand isomerisation reactions, and determination of molecular electronic structure, which complement the conventional tools available to the synthetic chemist for characterisation of molecular compounds. The role of computational studies in supporting the interpretation of spectroscopic data is also briefly discussed

Framing effects in group investment decision making: role of group polarization.

Science.gov (United States)

Cheng, Pi-Yueh; Chiou, Wen-Bin

2008-02-01

Prospect theory proposes that framing effects result in a preference for risk-averse choices in gain situations and risk-seeking choices in loss situations. However, in group polarization situations, groups show a pronounced tendency to shift toward more extreme positions than those they initially held. Whether framing effects in group decision making are more prominent as a result of the group-polarization effect was examined. Purposive sampling of 120 college students (57 men, 63 women; M age = 20.1 yr., SD = 0.9) allowed assessment of relative preference between cautious and risky choices in individual and group decisions. Findings indicated that both group polarization and framing effects occur in investment decisions. More importantly, group decisions in a gain situation appear to be more cautious, i.e., risk averse, than individual decisions, whereas group decisions in the loss situation appear to be more risky than individual decisions. Thus, group decision making may expand framing effects when it comes to investment choices through group polarization.

When are emotions related to group-based appraisals? : A comparison between group-based emotions and general group emotions

NARCIS (Netherlands)

Kuppens, Toon; Yzerbyt, Vincent Y.

2014-01-01

In the literature on emotions in intergroup relations, it is not always clear how exactly emotions are group-related. Here, we distinguish between emotions that involve appraisals of immediate group concerns (i.e., group-based emotions) and emotions that do not. Recently, general group emotions,

Cooperation during cultural group formation promotes trust towards members of out-groups.

Science.gov (United States)

Pan, Xiaofei Sophia; Houser, Daniel

2013-07-07

People often cooperate with members of their own group, and discriminate against members of other groups. Previous research establishes that cultural groups can form endogenously, and that these groups demonstrate in-group favouritism. Given the presence of cultural groups, the previous literature argues that cultural evolution selects for groups that exhibit parochial altruism. The source of initial variation in these traits, however, remains uninformed. We show here that a group's economic production environment may substantially influence parochial tendencies, with groups formed around more cooperative production (CP) displaying less parochialism than groups formed around more independent production (IP) processes. Participants randomized into CP and IP production tasks formed cultural groups, and subsequently played hidden-action trust games with in-group and out-group trustees. We found CP to be associated with significantly greater sharing and exchanging behaviours than IP. In trust games, significant parochial altruism (in-group favouritism combined with out-group discrimination) was displayed by members of IP groups. By contrast, members of CP groups did not engage in either in-group favouritism or out-group discrimination. Further, we found the absence of out-group discrimination in CP to persist even following 'betrayal'. Finally, belief data suggest that members of CP are not more intrinsically generous than IP members, but rather more likely to believe that out-group trustees will positively reciprocate. Our results have important implications for anyone interested in building cooperative teams, and shed new light on connections between culture and cooperation.

The Effects of Music and Group Stage on Group Leader and Member Behavior in Psychoeducational Groups for Children of Divorce

Science.gov (United States)

Cercone, Kristin; DeLucia-Waack, Janice

2012-01-01

This study examined the effects of music and group stage on group process and group leader and member behavior within 8-week psychoeducational groups for children of divorce. Audiotapes of group sessions were rated using the Interactional Process Analysis and the Group Sessions Ratings Scale. Both treatment groups were very similar in terms of…

Landscape Archaeology in the surrounding of «Lauro»: A micro-regional approach to Roman territorial shaping in a north-eastern sector of the Iberian Peninsula

Directory of Open Access Journals (Sweden)

Arnau GARCÍA MOLSOSA

2015-11-01

Full Text Available The link between the place-name Lauro and the ancient history of the eastern part of Vallès region (Barcelona is a constant throughout historiography. In this paper, this ancient Lauro serves as a guide to present the results of a research conducted in a small area, which due to archaeological data complexity has been of great interest to study the dynamics of territorial structuration in one of the first rural areas conquered by Rome outside the Italian peninsula.From Landscape Archaeology conceptual and methodological tools, extensive and intensive archaeological surveys have been developed. The collected materials and the documented structural remains have allowed us to define settlement and human occupation in a chronology ranging from the development of indigenous (Iberian societies to the consolidation of the Roman Empire –ivth bc-iith ad–.The results of these works set out the elements to analyse the impact of Roman conquest in settlement evolution at a micro-regional scale. The studied area may represent a model to contrast in other regions and to discuss in future works.

A likely late-Roman painted pottery workshop in Tarancuena (Soria | Un probable taller local de cerámica pintada tardorromana en Tarancueña (Soria

Directory of Open Access Journals (Sweden)

Juan Manuel Abascal Palazón

1986-12-01

Full Text Available The discovery of painted pottery in the Roman site of Tarancueña (Soria stand out because of its thematic and chronological homogeneity, and the meeting in only one site of the types which appear in the peripheric counties. The analysis of the material, combined with the information from the excavations, allows us to suggest the existence of a county factory which produced this type of pottery in the second half of the IVth Century A. D. and the first years of the Vth Century A. D. | Los hallazgos de cerámica pintada del yacimiento romano de Tarancueña (Soria, destacan por su homogeneidad temática y cronológica, así como por reunir en un solo enclave los tipos que aparecen en las regiones periféricas. El análisis del material, combinado con la información de las excavaciones, permite sugerir la existencia de un taller comarcal que produjo este tipo de piezas en la segunda mitad del siglo IV y los primeros años del siglo V. d. C.

E-groups training

CERN Multimedia

HR Department

2012-01-01

There will be an e-groups training course on 16 March 2012 which will cover the main e-groups functionalities i.e.: creating and managing e-groups, difference between static and dynamic e-groups, configuring posting restrictions and archives, examples of where e-groups can be used in daily work. Even if you have already worked with e-groups, this may be a good opportunity to learn about the best practices and security related recommendations when using e-groups. You can find more details as well as enrolment form for the training (it’s free) here. The number of places is limited, so enrolling early is recommended.   Technical Training Tel. 72844

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

Science.gov (United States)

Sibi, Mukund P; He, Liwen

2004-05-27

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

Periodic and Aperiodic Close Packing: A Spontaneous Hard-Sphere Model.

Science.gov (United States)

van de Waal, B. W.

1985-01-01

Shows how to make close-packed models from balloons and table tennis balls to illustrate structural features of clusters and organometallic cluster-compounds (which are of great interest in the study of chemical reactions). These models provide a very inexpensive and tactile illustration of the organization of matter for concrete operational…

Diversity and community composition of tributyltin-resistant bacteria under different conditions

International Nuclear Information System (INIS)

Lee, Y. H.; Park, S.; Park, H.; Choi, Y

2009-01-01

Tributyltin (TBT) is an organometallic compound used as anti fouling agent in marine paints. this compound is toxic not only for eukaryotes, but also for bacteria. Based on the literature review, a few researchers have reported evidence for the presence of TBT-resistant bacteria in natural seawater and marine sediment. (Author)

Diversity and community composition of tributyltin-resistant bacteria under different conditions

Energy Technology Data Exchange (ETDEWEB)

Lee, Y. H.; Park, S.; Park, H.; Choi, Y

2009-07-01

Tributyltin (TBT) is an organometallic compound used as anti fouling agent in marine paints. this compound is toxic not only for eukaryotes, but also for bacteria. Based on the literature review, a few researchers have reported evidence for the presence of TBT-resistant bacteria in natural seawater and marine sediment. (Author)

Bulletin of Materials Science | Indian Academy of Sciences

Indian Academy of Sciences (India)

Home; Journals; Bulletin of Materials Science. Anjum Qureshi. Articles written in Bulletin of Materials Science. Volume 29 Issue 6 November 2006 pp 605-609. Analysis of organometallics dispersed polymer composite irradiated with oxygen ions · N L Singh Anjum Qureshi A K Rakshit D K Avasthi · More Details Abstract ...

Studies of radiation and chemical toxicity. Progress report

International Nuclear Information System (INIS)

1986-01-01

Annual report for the Studies of Radiation and Chemical Toxicity Program at the University of Rochester is presented. Progress is reported on four projects: Neurobehavorial Toxicity of Organometallic Fuel Additives, Mechanisms of Permanent and Delayed Pathologic Effects of Ionizing Radiation, Solid State Radiation Chemistry of the DNA Backbone, and Pulmonary Biochemistry

short communication reaction of ethyl acetoacetate and 2

African Journals Online (AJOL)

Preferred Customer

These compounds and their analogs have been reported as specific inhibitors of the growth of endothelic cells and ... The Michael addition of active methylene compounds to chalcones is well documented [15-. 20]. On the basis of ..... Engelman, L.K.; Feng, Y.; Ison, E.A. Organometallics 2011, 30, 4572. 12. Sosnovskikh ...

with palladium (ii)

African Journals Online (AJOL)

Mgina

Mercury telluride is an important semi conductor with application in infra-red detection (Charlon 1982, Mullin & Irrine. 1985). Photolysis of mixture of the organometallic compounds RHgTeR and. RCdTeR can produce mercury cadmium telluride. Haris and Nissan (1987) prepared. (t-butyl)HgTe(t-butyl) and demonstrated that.

Definable Group Extensions and o-Minimal Group Cohomology via Spectral Sequences

OpenAIRE

BARRIGA, ELIANA

2013-01-01

We provide the theoretical foundation for the Lyndon-Hochschild-Serre spectral sequence as a tool to study the group cohomology and with this the group extensions in the category of definable groups. We also present various results on definable modules and actions, definable extensions and group cohomology of definable groups. These have applications to the study of non-definably compact groups definable in o-minimal theories (see [1]). Se presenta el fundamento teórico para las sucesiones...

Trajectory grouping structure

Directory of Open Access Journals (Sweden)

Maike Buchin

2015-03-01

Full Text Available The collective motion of a set of moving entities like people, birds, or other animals, is characterized by groups arising, merging, splitting, and ending. Given the trajectories of these entities, we define and model a structure that captures all of such changes using the Reeb graph, a concept from topology. The trajectory grouping structure has three natural parameters that allow more global views of the data in group size, group duration, and entity inter-distance. We prove complexity bounds on the maximum number of maximal groups that can be present, and give algorithms to compute the grouping structure efficiently. We also study how the trajectory grouping structure can be made robust, that is, how brief interruptions of groups can be disregarded in the global structure, adding a notion of persistence to the structure. Furthermore, we showcase the results of experiments using data generated by the NetLogo flocking model and from the Starkey project. The Starkey data describe the movement of elk, deer, and cattle. Although there is no ground truth for the grouping structure in this data, the experiments show that the trajectory grouping structure is plausible and has the desired effects when changing the essential parameters. Our research provides the first complete study of trajectory group evolvement, including combinatorial,algorithmic, and experimental results.

Inter-group and intra-group assertiveness: adolescents' social skills following cultural transition.

Science.gov (United States)

Korem, Anat; Horenczyk, Gabriel; Tatar, Moshe

2012-08-01

The goals of this study were to examine intra-group and inter-group assertiveness among adolescents, and to compare these two domains of assertiveness between cultural groups in Israel. Measures of intra-group and inter-group assertiveness were developed, and questionnaires were administrated to 441 immigrants from the Former Soviet Union (FSU), 242 immigrants from Ethiopia and 333 non-immigrants. Compared to non-immigrants, FSU and Ethiopian immigrants' inter-group assertiveness was lower. Girls reported higher levels of inter-group assertiveness than boys. Each of the immigrant groups rates itself as equally assertive as the non-immigrant group and more assertive than the other immigrant group. Also, a difference between inter-group and intra-group assertiveness was found among the FSU immigrants. It is argued that adolescents' assertiveness following cultural transition is associated with socio-cultural context, and the implications of this conclusion are discussed. Copyright © 2011 The Foundation for Professionals in Services for Adolescents. Published by Elsevier Ltd. All rights reserved.

Effectiveness of Group Supervision versus Combined Group and Individual Supervision.

Science.gov (United States)

Ray, Dee; Altekruse, Michael

2000-01-01

Investigates the effectiveness of different types of supervision (large group, small group, combined group, individual supervision) with counseling students (N=64). Analyses revealed that all supervision formats resulted in similar progress in counselor effectiveness and counselor development. Participants voiced a preference for individual…

The group-as-a-whole-object relations model of group psychotherapy.

Science.gov (United States)

Rosen, D; Stukenberg, K W; Saeks, S

2001-01-01

The authors review the theoretical basis of group psychotherapy performed at The Menninger Clinic and demonstrate how the theory has been put into practice on two different types of inpatient units. The fundamental elements of the theory and practice used can be traced to object relations theory as originally proposed by Melanie Klein. Her work with individuals was directly applied to working with groups by Ezriel and Bion, who focused on interpreting group tension. More modern approaches have reintegrated working with individual concerns while also attending to the group-as-a-whole. Historically, these principles have been applied to long-term group treatment. The authors apply the concepts from the group-as-a-whole literature to short- and medium-length inpatient groups with open membership. They offer clinical examples of the application of these principles in short-term inpatient settings in groups with open membership.

Group lending and the role of the group leader

OpenAIRE

Eijkel, van, R.; Hermes, N.; Lensink, B.W.

2011-01-01

This paper investigates strategic monitoring behavior within group lending. We show that monitoring efforts of group members differ in equilibrium due to the asymmetry between members in terms of future profits. In particular, we show that the entrepreneur with the highest future profits also puts in the highest monitoring effort. Moreover, monitoring efforts differ between group members due to free-riding: one member reduces her level of monitoring if the other increases her monitoring effor...

Citizens' action group

International Nuclear Information System (INIS)

Andritzky, W.

1978-01-01

For the first empirical study of citizens' action groups 331 such groups were consulted. Important information was collected on the following aspects of these groups: their self-image, areas and forms of activities, objectives and their extent, how long the group has existed, successes and failures and their forms of organisation. (orig.) [de

Facilitating Group Decision-Making: Facilitator's Subjective Theories on Group Coordination

Directory of Open Access Journals (Sweden)

Michaela Kolbe

2008-10-01

Full Text Available A key feature of group facilitation is motivating and coordinating people to perform their joint work. This paper focuses on group coordination which is a prerequisite to group effectiveness, especially in complex tasks. Decision-making in groups is a complex task that consequently needs to be coordinated by explicit rather than implicit coordination mechanisms. Based on the embedded definition that explicit coordination does not just happen but is purposely executed by individuals, we argue that individual coordination intentions and mechanisms should be taken into account. Thus far, the subjective perspective of coordination has been neglected in coordination theory, which is understandable given the difficulties in defining and measuring subjective aspects of group facilitation. We therefore conducted focused interviews with eight experts who either worked as senior managers or as experienced group facilitators and analysed their approaches to group coordination using methods of content analysis. Results show that these experts possess sophisticated mental representations of their coordination behaviour. These subjective coordination theories can be organised in terms of coordination schemes in which coordination-releasing situations are facilitated by special coordination mechanisms that, in turn, lead to the perception of specific consequences. We discuss the importance of these subjective coordination theories for effectively facilitating group decision-making and minimising process losses. URN: urn:nbn:de:0114-fqs0901287

Journal of Chemical Sciences | Indian Academy of Sciences

Indian Academy of Sciences (India)

Poly-imido analogues of various phosphorus oxo anions have gained recent attention in inorganic chemistry. Current methods to obtain these anions require strong organometallic deprotonating agents in reaction with phosphonium salt like [(NHPh)4P]Cl or phosphoramides such as [(RNH)3P=E] (E = NSiMe3, O, S or Se) ...

Synthesis and structure of organoantimony(III) compounds containing antimony−selenium and −tellurium terminal bonds

Czech Academy of Sciences Publication Activity Database

Dostál, L.; Jambor, R.; Růžička, A.; Lyčka, A.; Brus, Jiří; de Proft, F.

2008-01-01

Roč. 27, č. 23 (2008), s. 6059-6062 ISSN 0276-7333 Grant - others:GA ČR(CZ) GP203/07/P094; GA MŠk(CZ) LC523 Program:LC Institutional research plan: CEZ:AV0Z40500505 Keywords : organometallic compounds Subject RIV: CA - Inorganic Chemistry Impact factor: 3.815, year: 2008

Organosilicon thin films deposited by plasma enhanced CVD:Thermal changes of chemical structure and mechanical properties

Czech Academy of Sciences Publication Activity Database

Zajíčková, L.; Buršíková, V.; Kučerová, Z.; Franclová, J.; Siahel, P.; Peřina, Vratislav; Macková, Anna

2007-01-01

Roč. 68, 5-6 (2007), s. 1255-1259 ISSN 0022-3697 R&D Projects: GA ČR GA202/07/1669 Institutional research plan: CEZ:AV0Z10480505 Keywords : hin films * organometallic compounds * plasma deposition Subject RIV: BG - Nuclear, Atomic and Molecular Physics, Colliders Impact factor: 0.899, year: 2007

Cellulose sulphuric acid as a biodegradable catalyst for conversion ...

Indian Academy of Sciences (India)

important applications of these compounds are 1,3- dipolar cycloaddition to produce five-membered hetero- cycles2 and their ... Diazonium salts are multipurpose compounds in organic chemistry. However, their poor stability lim- ..... Organometallics 21 5549. 5. Liu Q and Tor Y 2003 Org. Lett. 5 2571. 6. Zhu W and Ma D ...

Author Details

African Journals Online (AJOL)

Chiweshe, TT. Vol 66 (2013) - Articles Quantification of Rhodium in a Series of Inorganic and Organometallic Compounds using Cobalt as Internal Standard Abstract PDF. ISSN: 0379-4350. AJOL African Journals Online. HOW TO USE AJOL... for Researchers · for Librarians · for Authors · FAQ's · More about AJOL · AJOL's ...

Combined experimental and theoretical mechanistic investigation of the Barbier allylation in aqueous media

DEFF Research Database (Denmark)

Dam, Johan Hygum; Fristrup, Peter; Madsen, Robert

2008-01-01

-determining step. For Zn, In, Sn, Sb, and Bi, an inverse secondary kinetic isotope effect was found (k(H)/k(D) = 0.75-0.95), which was compatible with the formation of a discrete organometallic species prior to allylation via a closed six-membered transition state. With Mg, a significantly larger build...

Any of them will do: In-group identification, out-group entitativity, and gang membership as predictors of group-based retribution.

Science.gov (United States)

Vasquez, Eduardo A; Wenborne, Lisa; Peers, Madeline; Alleyne, Emma; Ellis, Kirsty

2015-05-01

In non-gang populations, the degree of identification with an in-group and perceptions of out-group entitativity, the perception of an out-group as bonded or unified, are important contributors to group-based aggression or vicarious retribution. The link between these factors and group-based aggression, however, has not been examined in the context of street gangs. The current study assessed the relationship among in-group identification, perceptions of out-group entitativity, and the willingness to retaliate against members of rival groups who did not themselves attack the in-group among juvenile gang and non-gang members in London. Our results showed the predicted membership (gang/non-gang) × in-group identification × entitativity interaction. Decomposition of the three-way interaction by membership revealed a significant identification × entitativity interaction for gang, but not for non-gang members. More specifically, gang members who identify more strongly with their gang and perceived a rival group as high on entitativity were more willing to retaliate against any of them. In addition, entitativity was a significant predictor of group-based aggression after controlling for gender, in-group identification, and gang membership. Our results are consistent with socio-psychological theories of group-based aggression and support the proposal that such theories are applicable for understanding gang-related violence. Aggr. Behav. 41:242-252, 2015. © 2015 Wiley Periodicals, Inc. © 2015 Wiley Periodicals, Inc.

Introduction to Sporadic Groups

Directory of Open Access Journals (Sweden)

Luis J. Boya

2011-01-01

Full Text Available This is an introduction to finite simple groups, in particular sporadic groups, intended for physicists. After a short review of group theory, we enumerate the 1+1+16=18 families of finite simple groups, as an introduction to the sporadic groups. These are described next, in three levels of increasing complexity, plus the six isolated ''pariah'' groups. The (old five Mathieu groups make up the first, smallest order level. The seven groups related to the Leech lattice, including the three Conway groups, constitute the second level. The third and highest level contains the Monster group M, plus seven other related groups. Next a brief mention is made of the remaining six pariah groups, thus completing the 5+7+8+6=26 sporadic groups. The review ends up with a brief discussion of a few of physical applications of finite groups in physics, including a couple of recent examples which use sporadic groups.

Group learning

DEFF Research Database (Denmark)

Pimentel, Ricardo; Noguira, Eloy Eros da Silva; Elkjær, Bente

The article presents a study that aims at the apprehension of the group learning in a top management team composed by teachers in a Brazilian Waldorf school whose management is collective. After deciding to extend the school, they had problems recruiting teachers who were already trained based...... on the Steiner´s ideas, which created practical problems for conducting management activities. The research seeks to understand how that group of teachers collectively manage the school, facing the lack of resources, a significant heterogeneity in the relationships, and the conflicts and contradictions......, and they are interrelated to the group learning as the construction, maintenance and reconstruction of the intelligibility of practices. From this perspective, it can be said that learning is a practice and not an exceptional phenomenon. Building, maintaining and rebuilding the intelligibility is the group learning...

Is self-esteem predictor of in-group bias and out-group discrimination?

OpenAIRE

Jelić, Margareta

2009-01-01

Previous research has found that, in cases of intergroup conflict, people are likely to evaluate their groups more positively than the groups they do not belong to, but are also more ready to derogate the out-group. Two important factors need to be taken into consideration to explain these processes: self-esteem and group status. We explored the role of personal and social self-esteem in predicting in-group bias and out-group discrimination on two conflicted ethnic groups living in Vukovar. C...

Dreptul la oraș – generația a IV-a de drepturi ale omului metropolitan (The Right to city – the IVth generation of rights for the metropolitan man

Directory of Open Access Journals (Sweden)

Mădălina Virginia ANTONESCU

2016-03-01

Full Text Available The right to city begins to be recently consecrated by academic research, presenting several links with the “sustainable development” paradigm. UN documents see our contemporary world as an “urban global world”, confronted with issues as chronic poverty, lack of access to basic urban services, insufficient democratic participation to main decisions regarding the urban management. This new right can be regarded as derived from solidarity rights as the right to a healthy, clean, durable environment, as well as the right to continuous improvement of life quality, but also, it can be seen as a special, distinct kind of human right. Right to have clean, sustainable cities can be recognized, at national, regional, international levels, to individuals, to local groups (as the metropolitan inhabitants of one city or to nations (having at their disposal a collective new right to own prosperous, sustainable cities, as effect of their right to economic development. We consider the right to city as being a dynamic right, in full process of exploration and consecration within academic research, more than necessary for understanding an urban globalized world characterized by proliferation of metropolises, towns, cities, megalopolises that demand new juridical approaches.

[Social crisis, spontaneous groups and group order].

Science.gov (United States)

Edelman, Lucila; Kordon, Diana

2002-12-01

Argentina has gone through very difficult times during the last years and, in particularly, new kinds of social practices have emerged in order to cope with the crisis. This situation demands and urges a new type of reflection upon the double role of groups, as tools to transform reality and as a way to elaborate those processes regarding subjectivity. In this paper we analyse some topics regarding the groupal field (considering spontaneous groups as well as groupal devices that allow to elaborate the crisis). We consider social bond to be the condition of possibility for the existence of the psyche and of time continuity, and that it also makes possible personal and social elaboration of trauma, crisis and social catastrophe. We develop some aspects of an specific device (the reflection group), which we have already depicted in another moment, showing it's usefulness to cope with social crisis and to promote the subjective elaboration of crisis.

Reflection groups

International Nuclear Information System (INIS)

Eggermont, G.

2006-01-01

In 2005, PISA organised proactive meetings of reflection groups on involvement in decision making, expert culture and ethical aspects of radiation protection.All reflection group meetings address particular targeted audiences while the output publication in book form is put forward

Chemoselective Hydrogenation with Supported Organoplatinum(IV) Catalyst on Zn(II)-Modified Silica

Energy Technology Data Exchange (ETDEWEB)

Camacho-Bunquin, Jeffrey [Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 S Cass Avenue, Lemont, Illinois 60439, United States; Ferrandon, Magali [Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 S Cass Avenue, Lemont, Illinois 60439, United States; Sohn, Hyuntae [Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 S Cass Avenue, Lemont, Illinois 60439, United States; Yang, Dali [Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 S Cass Avenue, Lemont, Illinois 60439, United States; Liu, Cong [Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 S Cass Avenue, Lemont, Illinois 60439, United States; Ignacio-de Leon, Patricia Anne [Energy Sciences Division, Argonne National Laboratory, 9700 S Cass Avenue, Lemont, Illinois 60439, United States; Perras, Frédéric A. [Ames Laboratory, U.S. Department of Energy, Ames, Iowa 50010, United States; Pruski, Marek [Ames Laboratory, U.S. Department of Energy, Ames, Iowa 50010, United States; Department of Chemistry, Iowa State University, 2416 Pammel Drive, Ames, Iowa 50011, United States; Stair, Peter C. [Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 S Cass Avenue, Lemont, Illinois 60439, United States; Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States; Delferro, Massimiliano [Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 S Cass Avenue, Lemont, Illinois 60439, United States

2018-02-22

Well-defined organoplatinum(IV) sites were grafted on a Zn(II)-modified SiO2 support via surface organometallic chemistry in toluene at room temperature. Solid-state spectroscopies including XAS, DRIFTS, DRUV-Vis, and solid-state (SS)NMR enhanced by dynamic nuclear polarization (DNP), as well as TPR-H2 and TEM techniques revealed highly dispersed (methylcyclopentadi-enyl)methylplatinum(IV) sites on the surface ((MeCp)PtMe/Zn/SiO2, 1). In addition, computational modelling suggests that the surface reaction of (MeCp)PtMe3 with Zn(II)-modified SiO2 support is thermodynamically favorable (ΔG = -12.4 kcal/mol), likely due to the increased acidity of the hydroxyl group, as confirmed by NH3-TPD and DNP-enhanced 17O{1H} SSNMR. In situ DRIFTS and XAS hydrogenation experiments reveal the formation of a surface Pt(IV)-H upon hydrogenolysis of Pt-Me groups. The heterogenized organoplatinum(IV)-H sites catalyze the selective partial hydrogenation of 1,3-butadiene to butenes (up to 95%) and the reduction of nitrobenzene derivatives to anilines (up to 100%) with excellent tolerance of reduction-sensitive func-tional groups (olefin, carbonyl, nitrile, halogens) under mild reaction conditions.

Me against we: in-group transgression, collective shame, and in-group-directed hostility.

Science.gov (United States)

Piff, Paul K; Martinez, Andres G; Keltner, Dacher

2012-01-01

People can experience great distress when a group to which they belong (in-group) is perceived to have committed an immoral act. We hypothesised that people would direct hostility toward a transgressing in-group whose actions threaten their self-image and evoke collective shame. Consistent with this theorising, three studies found that reminders of in-group transgression provoked several expressions of in-group-directed hostility, including in-group-directed hostile emotion (Studies 1 and 2), in-group-directed derogation (Study 2), and in-group-directed punishment (Study 3). Across studies, collective shame-but not the related group-based emotion collective guilt-mediated the relationship between in-group transgression and in-group-directed hostility. Implications for group-based emotion, social identity, and group behaviour are discussed.

Crystalline self-assembly of organic molecules with metal ions at the air-aqueous solution interface. A grazing incidence X-ray scattering study

DEFF Research Database (Denmark)

Weissbuch, I.; Buller, R.; Kjær, K.

2002-01-01

The advent of intense X-rays from synchrotron sources made possible to probe, at the molecular level, the structural aspects of self-assemblies generated at interfaces. Here we present the two-dimensional (2-D) packing arrangements of two-, three- and multi-component organo-metallic self......-assemblies formed via interfacial reaction at the air-aqueous solution interface, as determined by grazing incidence X-ray diffraction (GIRD) and X-ray specular reflectivity techniques. GIXD yields structural information on the crystalline part of the Langmuir film, including the ions and counterions lateral order...... of metal ions bound to the polar head groups of amphipilic molecules; use of bolaamphiphiles to generate oriented thin films with metal ions arranged in periodic layers; delineation of differences in the lateral organization of metal ions at interfaces as induced by racemates and enantiomerically pure...

On some homological functors of a Bieberbach group with symmetric point group

Science.gov (United States)

Ting, Tan Yee; Idrus, Nor'ashiqin Mohd; Masri, Rohaidah; Ladi, Nor Fadzilah Abdul

2017-05-01

Bieberbach groups with symmetric point group are polycyclic. The properties of the groups can be explored by computing their homological functors. In this paper, some homological functors of a Bieberbach group with symmetric point group, such as the Schur multiplier and the G-trivial subgroup of the nonabelian tensor square, are generalized up to finite dimension and are represented in the form of direct product of cyclic groups.

Group purchasing: an overview.

Science.gov (United States)

Wetrich, J G

1987-07-01

The various types and operational methods of purchasing groups are described, and evaluation of groups is discussed. Since group purchasing is increasing in popularity as a method of controlling drug costs, community and hospital pharmacy managers may need to evaluate various groups to determine the appropriateness of their services. Groups are categorized as independent, system based, or alliance or association based. Instead of "purchasing," some groups develop contracts for hospitals, which then purchase directly from the vendor. Aside from this basic difference between groups that purchase and groups that contract, comparisons among groups are difficult because of the wide variation in sizes and services. Competition developing from diversification among groups has led to "super groups," formed from local and regional groups. In evaluating groups, advantages and disadvantages germane to accomplishing the member's objectives must be considered. To ensure a group's success, members must be committed and support the group's philosophies; hospital pharmacists must help to establish a strong formulary system. To select vendors, groups should develop formal qualification and selection criteria and should not base a decision solely on price. The method of solicitation (bidding or negotiating), as well as the role of the prime vendor, should be studied. Legal implications of group purchasing, especially in the areas of administrative fees and drug diversion, must also be considered. The most advantageous group for each organization will include members with common missions and will be able to implement strategies for future success.

Perceived legitimacy follows in-group interests: Evidence from intermediate-status groups.

Science.gov (United States)

Caricati, Luca; Sollami, Alfonso

2017-03-01

In two experiments, the effect of (in)stability of status differences on the perception of perspective legitimacy and in-group threat among intermediate-status group members (i.e., nurses students or nurses) was analysed. Both studies indicated that in downwardly unstable condition, legitimacy was lower and in-group threat was higher than in stable condition. In upwardly unstable condition, perceived legitimacy was higher and in-group threat was lower than in stable condition. The indirect effects of (in)stability via in-group threat on perceived legitimacy were significant. © 2016 The British Psychological Society.

Group Play Therapy with Sexually Abused Preschool Children: Group Behaviors and Interventions

Science.gov (United States)

Jones, Karyn Dayle

2002-01-01

Group play therapy is a common treatment modality for children who have been sexually abused. Sexually abused preschoolers exhibit different group play therapy behaviors than do nonabused children. Group workers need to be aware of these differences and know the appropriate group interventions. This article describes group play therapy with…

Tuning spin transport across two-dimensional organometallic junctions

Science.gov (United States)

Liu, Shuanglong; Wang, Yun-Peng; Li, Xiangguo; Fry, James N.; Cheng, Hai-Ping

2018-01-01

We study via first-principles modeling and simulation two-dimensional spintronic junctions made of metal-organic frameworks consisting of two Mn-phthalocyanine ferromagnetic metal leads and semiconducting Ni-phthalocyanine channels of various lengths. These systems exhibit a large tunneling magnetoresistance ratio; the transmission functions of such junctions can be tuned using gate voltage by three orders of magnitude. We find that the origin of this drastic change lies in the orbital alignment and hybridization between the leads and the center electronic states. With physical insight into the observed on-off phenomenon, we predict a gate-controlled spin current switch based on two-dimensional crystallines and offer general guidelines for designing spin junctions using 2D materials.

Organometallic complex chemistry of plutonium and selected lanthanides

International Nuclear Information System (INIS)

Seemann, U.

1987-01-01

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

Spin-Crossing in an Organometallic Pt-Benzene Complex

Czech Academy of Sciences Publication Activity Database

Granatier, Jaroslav; Dubecký, M.; Lazar, P.; Otyepka, M.; Hobza, Pavel

2013-01-01

Roč. 9, č. 3 (2013), s. 1461-1468 ISSN 1549-9618 R&D Projects: GA ČR GBP208/12/G016 Grant - others:GA ČR(CZ) GAP208/10/1742 Program:GA Institutional support: RVO:61388963 Keywords : quantum Monte Carlo * 2nd-order perturbation-theory * density-functional theory * augmented-wave method Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.310, year: 2013

Ferrocenyl helquats: unusual chiral organometallic nonlinear optical chromophores

Czech Academy of Sciences Publication Activity Database

Buckley, L. E. R.; Coe, B. J.; Rusanova, D.; Sánchez, S.; Jirásek, Michael; Joshi, Vishwas; Vávra, Jan; Khobragade, Dushant; Pospíšil, Lubomír; Ramešová, Šárka; Císařová, I.; Šaman, David; Pohl, Radek; Clays, K.; Van Steerteghem, N.; Brunschwig, B. S.; Teplý, Filip

2017-01-01

Roč. 46, č. 4 (2017), s. 1052-1064 ISSN 1477-9226 R&D Projects: GA ČR GA13-19213S; GA ČR(CZ) GA16-03085S Grant - others:AV ČR(CZ) M200551208 Institutional support: RVO:61388963 ; RVO:61388955 Keywords : hyper-Rayleigh scattering * structure-property relationship * transition metal complexes Subject RIV: CC - Organic Chemistry; CC - Organic Chemistry (UFCH-W) OBOR OECD: Organic chemistry; Organic chemistry (UFCH-W) Impact factor: 4.029, year: 2016

Mass spectrometry of rhenium complexes: a comparative study by using LDI-MS, MALDI-MS, PESI-MS and ESI-MS.

Science.gov (United States)

Petroselli, Gabriela; Mandal, Mridul Kanti; Chen, Lee Chuin; Ruiz, Gustavo T; Wolcan, Ezequiel; Hiraoka, Kenzo; Nonami, Hiroshi; Erra-Balsells, Rosa

2012-03-01

A group of rhenium (I) complexes including in their structure ligands such as CF(3)SO(3)-, CH(3)CO(2)-, CO, 2,2'-bipyridine, dipyridil[3,2-a:2'3'-c]phenazine, naphthalene-2-carboxylate, anthracene-9-carboxylate, pyrene-1-carboxylate and 1,10-phenanthroline have been studied for the first time by mass spectrometry. The probe electrospray ionization (PESI) is a technique based on electrospray ionization (ESI) that generates electrospray from the tip of a solid metal needle. In this work, mass spectra for organometallic complexes obtained by PESI were compared with those obtained by classical ESI and high flow rate electrospray ionization assisted by corona discharge (HF-ESI-CD), an ideal method to avoid decomposition of the complexes and to induce their oxidation to yield intact molecular cation radicals in gas state [M](+·) and to produce their reduction yielding the gas species [M](-·). It was found that both techniques showed in general the intact molecular ions of the organometallics studied and provided additional structure characteristic diagnostic fragments. As the rhenium complexes studied in the present work showed strong absorption in the UV-visible region, particularly at 355 nm, laser desorption ionization (LDI) mass spectrometry experiments could be conducted. Although intact molecular ions could be detected in a few cases, LDI mass spectra showed diagnostic fragments for characterization of the complexes structure. Furthermore, matrix-assisted laser desorption ionization (MALDI) mass spectra were obtained. Nor-harmane, a compound with basic character, was used as matrix, and the intact molecular ions were detected in two examples, in negative ion mode as the [M](-·) species. Results obtained with 2-[(2E)-3-(4-tert-buthylphenyl)-2-methylprop-2-enylidene] malononitrile (DCTB) as matrix are also described. LDI experiments provided more information about the rhenium complex structures than did the MALDI ones. Copyright © 2012 John Wiley & Sons, Ltd.

Energy Innovation. IVO Group`s Research and Development Report

Energy Technology Data Exchange (ETDEWEB)

Salminen, P.; Laiho, Y.; Kaikkonen, H.; Leisio, C.; Hinkkanen, S. [eds.

1996-11-01

This annual booklet of the IVO Group`s research and development activities presents a number of articles, written by experts from IVO. The products described are examples of the environmentally-oriented selection made available by the IVO Group. In fact, the entire energy technology developed in Finland is environmentally oriented, if seen from the international perspective. The new business potential of environmental technology is great, and it is believed that in the year 2000, exportation of Finnish know-how in the field of energy-saving and efficiency will exceed the value of out energy imports

Energy Innovation. IVO group`s research and development report

Energy Technology Data Exchange (ETDEWEB)

Salminen, P.; Laiho, Y.; Kaikkonen, H.; Leisio, C.; Hinkkanen, S.; Fletcher, R. [eds.

1997-11-01

This annual booklet of the IVO Group`s research and development activities presents a number of articles, written by experts from IVO. The products described are examples of the environmentally-oriented selection made available by the IVO Group. In fact, the entire energy technology developed in Finland is environmentally oriented, if seen from the international perspective. The new business potential of environmental technology is great, and it is believed that in the year 2000, exportation of Finnish know-how in the field of energy-saving and efficiency will exceed the value of out energy imports