Auswahl der wissenschaftlichen Literatur zum Thema „Ruthenium Isotopes“

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Zeitschriftenartikel zum Thema "Ruthenium Isotopes":

1

Journal, Baghdad Science. „Study of the properties of Ru-isotopes using the proton-neutron interacting boson model (IBM-2)“. Baghdad Science Journal 7, Nr. 1 (07.03.2010): 76–89. http://dx.doi.org/10.21123/bsj.7.1.76-89.

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The proton-neutron interacting boson model (IBM-2) has been used to make a schematic study of the Ruthenium ( ) isotopes of mass region around with and . For each isotope of the values of the IBM-2 Hamiltonian parameters, which yield an acceptable results for excitation energies in comparison with those of experimental data, have been determined. Fixed values of the effective charges ( ) and of the proton and neutron g factors ( and ) have been chosen for all isotopes under study. The calculated electric quadrupole moments of state, transitions, the magnetic dipole moments transitions and mixing ratios are in reasonable agreement with the experimental data.
2

Arora, B. K., D. Mehta, Rakesh Rani, T. S. Cheema und P. N. Trehan. „Coulomb excitation of ruthenium isotopes“. Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms 24-25 (April 1987): 460–63. http://dx.doi.org/10.1016/0168-583x(87)90683-5.

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3

Kim, Seonho, Kwang Hyun Sung und Kyujin Kwak. „Isotopic Compositions of Ruthenium Predicted from the NuGrid Project“. Astrophysical Journal 924, Nr. 2 (01.01.2022): 88. http://dx.doi.org/10.3847/1538-4357/ac35e1.

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Abstract The isotopic compositions of ruthenium (Ru) are measured from presolar silicon carbide (SiC) grains. In a popular scenario, the presolar SiC grains formed in the outskirt of an asymptotic giant branch (AGB) star, left the star as a stellar wind, and joined the presolar molecular cloud from which the solar system formed. The Ru isotopes formed inside the star, moved to the stellar surface during the AGB phase, and were locked into the SiC grains. Following this scenario, we analyze the Nucleosynthesis Grid (NuGrid) data, which provide the abundances of the Ru isotopes in the stellar wind for a set of stars in a wide range of initial masses and metallicities. We apply the C > O (carbon abundance larger than the oxygen abundance) condition, which is commonly adopted for the condition of the SiC formation in the stellar wind. The NuGrid data confirm that SiC grains do not form in the winds of massive stars. The isotopic compositions of Ru in the winds of low-mass stars can explain the measurements. We find that lower-mass stars (1.65 M ☉ and 2 M ☉) with low metallicity (Z = 0.0001) can explain most of the measured isotopic compositions of Ru. We confirm that the abundance of 99 Ru inside the presolar grain includes the contribution from the in situ decay of 99 Tc. We also verify our conclusion by comparing the isotopic compositions of Ru integrated over all the pulses with those calculated at individual pulses.
4

Arblaster, John W. „The Discoverers of the Ruthenium Isotopes“. Platinum Metals Review 55, Nr. 4 (01.10.2011): 251–62. http://dx.doi.org/10.1595/147106711x592448.

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5

Bork, J., H. Schatz, F. Käppeler und T. Rauscher. „Proton capture cross sections of the ruthenium isotopes“. Physical Review C 58, Nr. 1 (01.07.1998): 524–35. http://dx.doi.org/10.1103/physrevc.58.524.

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6

Shibata, Keiichi. „Evaluation of neutron nuclear data on ruthenium isotopes“. Journal of Nuclear Science and Technology 50, Nr. 12 (Dezember 2013): 1177–87. http://dx.doi.org/10.1080/00223131.2013.838912.

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7

Marti, Kurt, Mario Fischer-Gödde und Carina Proksche. „Meteoritic Molybdenum and Ruthenium Isotopic Abundances Document Nucleosynthetic p-process Components“. Astrophysical Journal 956, Nr. 1 (29.09.2023): 7. http://dx.doi.org/10.3847/1538-4357/acee81.

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Abstract Anomalies in isotopic abundances of Mo and Ru in solar system matter were found to document variable contributions of the nucleosynthetic s-process component. We report isotopic relations of ϵ 92Mo versus ϵ 100Ru in meteorites from chondritic parent bodies, iron meteorites, and achondrites that reveal deviations from expected s-process abundance variations. We show that two p-process isotopes 92Mo and 94Mo require the presence of distinct p-process components in meteoritic materials. The nucleosynthetic origin of abundant magic (N = 50) p-process nuclides, covering the mass range of Zr, Mo, and Ru, has long been an enigma, but contributions by several recognized pathways, including alpha and νp-antineutrino reactions on protons, may account for the observed relatively large solar system abundances. Specific core-collapse supernovae explosive regions may carry proton-rich matter. Since Mo and Ru isotopic records in solar system matter reveal the presence of more than one nucleosynthetic p-process component, these records are expected to be helpful in documenting different explosive synthesis pathways and the implied galactic evolution of p-nuclides.
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Hanson, Susan K., Matthew E. Sanborn, Holly R. Trellue und William S. Kinman. „Nuclear Sample Provenance and Age Determination Using Ruthenium Isotopes“. Analytical Chemistry 94, Nr. 8 (14.02.2022): 3645–51. http://dx.doi.org/10.1021/acs.analchem.1c05218.

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9

Forest, D. H., R. A. Powis, E. C. A. Cochrane, J. A. R. Griffith und G. Tungate. „High resolution laser spectroscopy of naturally occurring ruthenium isotopes“. Journal of Physics G: Nuclear and Particle Physics 41, Nr. 2 (20.01.2014): 025106. http://dx.doi.org/10.1088/0954-3899/41/2/025106.

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10

Nystrom, A., und M. Thoennessen. „Discovery of yttrium, zirconium, niobium, technetium, and ruthenium isotopes“. Atomic Data and Nuclear Data Tables 98, Nr. 2 (März 2012): 95–119. http://dx.doi.org/10.1016/j.adt.2011.12.002.

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Dissertationen zum Thema "Ruthenium Isotopes":

1

Takam, Rungdham. „Determination of dose distribution of Ruthenium-106 Ophthalmic applicators“. Title page, contents and abstract only, 2003. http://web4.library.adelaide.edu.au/theses/09SM/09smt1363.pdf.

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"August 2003" Bibliography: leaves 108-117. 1. Ruthenium-106 ophthalmic applicators -- 2. General principle of thermoluminescent dosimeter -- 3. Study of basic characteristics of CaSO4:Dy TLD -- 4. Measurements of COB and CCA type ruthenium-106 ophthalmic applicator dose distributions -- 5. Determination of the dose rate distribution using a MOSFET detector -- 6. Summary and conclusion. In this project, small CaSO4:Dy TLDs and a semiconductor MOSFET dosimeter were used for the determination of on-axis depth dose-rate distributions of 15-mm and 20-mm ruthenium-106 applicators in acrylic eye phantoms. The TLDs were also used to determine off-axis dose distributions.
2

Miradji, Faoulat. „Quantum modelling of Ruthenium chemistry in the field of nuclear power plant safety“. Thesis, Lille 1, 2016. http://www.theses.fr/2016LIL10192/document.

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Lors d’un Accident Grave (AG) survenant à un réacteur nucléaire à eau pressurisée, sous atmosphère fortement oxydante, des relâchements importants de ruthénium, depuis le combustible dégradé, sont attendus du fait de la formation d’oxydes gazeux. Les composés de Ru représentent un risque sanitaire lié aux isotopes 103Ru et 106Ru, radio-contaminants à court et moyen terme. En outre l’oxyde RuO4, volatil à température ambiante, est susceptible d’être relâché à l’environnement via les fuites de l’enceinte de confinement. L’évaluation de ce rejet à l’environnement présente des incertitudes importantes, liées entre autres aux données thermochimiques des composés de ruthénium gazeux avec des disparités entre les valeurs de la littérature pour les oxydes. Concernant les oxyhydroxydes, les données sont très parcellaires et celles disponibles sont sujettes à caution. Une première étape de ces travaux de thèse a consisté au développement d’une méthodologie de calcul pour obtenir les données thermochimiques des oxydes de ruthénium gazeux en fonction de la température, via des outils de chimie quantique, avec la fonctionnelle TPSSh-5%HF pour l’optimisation de géométrie, suivi de la méthode CCSD(T) pour le calcul des énergies électroniques. Cette méthodologie fut ensuite étendue aux oxyhydroxydes. Des calculs de spéciation chimique ont été effectués afin de prédire les espèces gazeuses les plus stables lors d’un AG. A l’aide des propriétés thermochimiques des espèces d’intérêts et des méthodologies développées, une étude cinétique a été conduite afin de déterminer les chemins réactionnels conduisant à la formation d’oxydes de Ru, espèces gazeuses les plus stables en conditions AG
During a severe accident (SA) occurring to a pressurized water reactor (PWR), fission products (FPs) are released from the nuclear fuel and may reach the nuclear containment building. Among the FPs, ruthenium (Ru) is of particular interest due to its ability to form volatile oxide compounds in highly oxidizing conditions combined with its high radiotoxicity (103Ru and 106Ru isotopes) at middle term after the accident. Uncertainties concerning evaluation releases of Ru are important and some R&D efforts are led to get a better understanding of ruthenium chemistry in such conditions. The thermodynamic database on ruthenium species used to estimate these releases shows some discrepancies for most ruthenium oxides and for other species such as oxyhydroxides, data are scarce and not reliable, calling for quantum chemical calculations. The most suitable approach corresponds to TPSSh-5%HF for geometry optimization, followed by CCSD(T) for the calculation of the total electronic energies. The energetics are combined with statistical physics to obtain the thermochemical properties of ruthenium oxides and ruthenium oxyhydroxide species as the latter may play an important role on the transport of ruthenium in the primary circuit due to high steam content. The revised thermodynamic database is then used to predict which species are most stable in representative severe accident conditions. Next, kinetic calculations are also performed to obtain pathways of formations for ruthenium trioxide and tetraoxide gaseous compounds, which are the most stable Ru volatile species in steam/air atmospheres
3

Leloire, Maëva. „Utilisation de matériaux poreux de type Metal-Organic Framework (MOF) pour l’adsorption de molécules gazeuses (I2, RuO4) dans le contexte d’un accident de réacteur nucléaire“. Electronic Thesis or Diss., Université de Lille (2018-2021), 2021. http://www.theses.fr/2021LILUR009.

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Les isotopes radiotoxiques de l'iode et du ruthénium, tels que 129I, 131I, 103Ru et 106Ru, sont produits en quantité significative durant la fission nucléaire. Après un accident de réacteur nucléaire, ces éléments peuvent être rapidement disséminés dans l’environnement, sous la forme d’espèces gazeuses très volatiles comme l'iode moléculaire (I2) ou le tétraoxyde de ruthénium (RuO4). Afin de limiter la dispersion de ces produits de fission en cas d’accident, des filtres composés de matériaux poreux (zéolites ou charbon actifs) peuvent être employés. Cependant, de tels solides poreux présentent des limitations dans le contexte d'accident nucléaire. En effet, la présence d'espèces empoisonnantes (par exemple NOx, H2O, COx) peut inhiber la capture d’espèces radiotoxiques. De plus, leur relative faible porosité n’est souvent pas adaptée au bon piégeage d’espèces volumineuses comme RuO4. Sur la base de ces limites, une classe récente de matériaux poreux appelés Metal-Organic Frameworks (MOFs) pourrait s’avérer être un substitut efficace. En effet, les composés MOFs sont des matériaux hybrides cristallisés, constitués de clusters inorganiques liés les uns aux autres par des ligands organiques. Cette organisation peu dense offre une porosité importante et des surfaces spécifiques élevées (jusqu'à 7000 m2.g-1), nettement supérieurs à celles des solides poreux habituels. Bien que ces solides aient déjà montré de bonnes capacités pour la capture d’espèces radioactives, très peu de données rapportent leur efficacité pour le piégeage d’espèces gazeuses (notamment RuO4) en conditions accidentelles.Afin de renforcer nos connaissances sur les composés MOFs pour une potentielle utilisation en sureté nucléaire, ce travail de thèse s’est intéressé à leur efficacité pour la capture de I2 et RuO4 volatils dans certaines matrices poreuses modèles (type UiO-66). Nous avons mis en évidence l'importance de la fonctionnalisation du ligand espaceur et du confinement de l’iode au sein du réseau poreux. Ainsi, l’iode créé une interaction forte avec la charpente des MOFs pour former d’autres espèces iodées de type Ix-. Cette transformation a notamment été analysée par spectroscopie RAMAN.Suite à cette première étude, nous avons sélectionné le solide UiO-66_NH2 comme matériau de filtration de référence pour réaliser un essai dans l’installation EPICUR de l’IRSN. Celle-ci permet la manipulation d’iode radioactif (131I) et l’étude de son confinement au sein de la charpente poreuse en conditions accidentelles (radiation, température, vapeur d’eau). Ce travail a nécessité, en amont, d’élaborer un protocole de mise en forme, afin de produire un matériau MOF avec une granulométrie sphérique millimétrique. En parallèle, un travail sur la résistance de ce matériau sous irradiation gamma a également été entrepris, dans l’installation IRMA de l’IRSN. Cette étude a confirmé l’excellente efficacité du UiO-66_NH2 dans le contexte choisi. Enfin, le matériau UiO-66_NH2 a également été le candidat choisi pour la capture de RuO4 gazeux. Les différentes analyses (MET, RMN) ont permis de quantifier le RuO4 au sein des pores et de proposer des mécanismes réactionnels expliquant sa très bonne adsorption
The radiotoxic isotopes of iodine and ruthenium, such as 129I, 131I, 103Ru and 106Ru, are produced in significant quantities during nuclear fission. After a nuclear accident, these elements can be rapidly disseminated in the environment, in the form of highly volatile species such as molecular iodine (I2) or ruthenium tetroxide (RuO4). In order to limit the dispersion of these fission products, in case of a nuclear accident, filters composed by porous materials (zeolites or activated carbon) can be used. However, such porous solids have limitations during a nuclear accident. Indeed, the presence of poisonous species (for example NOx, H2O, COx) can ihhibit the capture of radiotoxic species. In addition, their relatively low porosity is often not suitable for the good trapping of large species such as RuO4. Based on these limitations, a recent class of porous materials called Metal-Organic Frameworks (MOFs) could be an effective substitute. Indeed, MOFs are hybrid materials, composed of inorganic clusters linked to each other by organic ligands. This low-density organization allows high porosity and high specific surface areas (up to 7000 m2.g-1), significantly higher than those of the usual porous solids. Although MOFs have already shown good capacities for capturing radioactive species, very little data exist on their effectiveness for trapping gaseous species (especially RuO4) and under accident conditions.In order to strengthen our knowledge of MOFs for potential use in nuclear safety, this thesis work focused on the effectiveness of some model MOFs for the capture of volatile I2 and RuO4 under accident conditions. We have highlighted the importance of the organic linker functionalization and confinement of iodine in the porous matrix. Thus, iodine creates a strong interaction with the framework of MOFs to form other iodine species of type Ix-. This transformation was notably analyzed by RAMAN spectroscopy.Following this first study, we selected the compound UiO-66_NH2 as reference filtration material to be tested in an IRSN facility called EPICUR. This one allows the manipulation of radioactive iodine (isotope-131) and the study of the confinement of iodine in within the porous framework in accidental conditions (radiation, temperature, steam). This work needs, upstream, to develop a shaping process in order to produce a MOF material with a spherical millimeter particle size. In parallel, an investigation on the resistance of this material under gamma irradiation was also undertaken in IRMA facility at IRSN. This study confirmed the excellent capacity of the solid UiO-66_NH2 in the present context. Finally, UiO-66_NH2 was also the candidate of choice for the capture of gaseous RuO4. The various analyzes (TEM, NMR) made it possible to quantify the RuO4 within the pores and to propose reaction mechanisms explaining its very good capture in UiO-66_NH2
4

Cummins, Veronica Clare. „New and improved hydrogen isotope exchange reactions“. Thesis, University of Surrey, 1998. http://epubs.surrey.ac.uk/843371/.

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Compounds labelled with deuterium and tritium are widely used in the life sciences. Consequently there is always a need for improved methods - better incorporation, higher specificity, reduced reaction time etc. and in the case of tritium, less radioactive waste. This thesis is concerned with such aspects. Chapter 1 is a review of the background to tritium and current methods of labelling and analysis of hydrogen isotopes. In chapter 2 the possible use of an organometallic compound - the ruthenium dihydro complex, RuH2CO(PPh3)3, which is known to catalyse the insertion of olefins into the ortho position of aromatic ketones, is explored. Solid deuterated formates e.g. 2-naphthy methyl-d-formate and d-formanilide were prepared and these were used to make the deuterated complex, RuD2CO(PPh3)3 which was used to exchange deuterium into the ortho position of aromatic ketones. Aromatic compounds with other functionalities, however were not so amenable to labelling, aromatic amides were the only other compounds successfully labelled. The method is therefore more restrictive than was hoped. A method to prepare tritiated formates by ozonolysis of 2-[T]-5-phenyloxazole to a mixed anhydride followed by nucleophillic attack was discovered. [T]-formanilide was prepared in this way but only at low levels of radioactivity (0.1 Ci/mmol, 3.67 GBq/mmol) which prevented the tritiated complex being prepared. In chapter 3 the use of zeolites as strong acid catalysts for hydrogen isotope exchange reactions was explored. Isotope exchange was carried out on simple organic molecules using hydrogen, platinum and palladium exchanged zeolite-Y with D2O and HTO as isotope source. Some studies were also carried out using solid deuterium sources with the metal exchanged zeolites. Exchange occurred using 2-naphthgyl methyl-d-formate, tetrabutyl ammonium-d-formate and potassium-d-formate. In addition, microwave activation was used in order to reduce reaction times and improve isotopic incorporation.
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Pfister, Christian Ulrich. „Radioaktive Markierung eines tumorspezifischen monoklonalen Antikörpers mit Isotopen des Rutheniums /“. [S.l.] : [s.n.], 1987. http://e-collection.ethbib.ethz.ch/show?type=diss&nr=8244.

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6

Bechtoldt, Alexander. „Aerobic Ruthenium-Catalyzed C–H Activations“. Doctoral thesis, Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2018. http://hdl.handle.net/11858/00-1735-0000-002E-E492-A.

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7

Gao, Longhui. „C-H bond activation catalyzed by Ruthenium nanoparticles“. Thesis, Université Paris-Saclay (ComUE), 2017. http://www.theses.fr/2017SACLS348/document.

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Les molécules marquées par des isotopes de l’hydrogène possèdent de nombreuses applications dans divers domaines tels que la chimie, la biologie ou en science des matériaux. Dans le domaine de la recherche de nouveaux médicaments, les études liées à la pharmacocinétique nécessitent un accès rapide à des molécules marquées afin de ne pas impacter les coûts et les délais de développement. Le développement de la métabolomique a aussi entrainé une augmentation du besoin en molécules marquées isotopiquement. En effet, les molécules deuterées peuvent être utilisées en tant qu’étalons internes pour la quantification rapide des métabolites présents dans des tissus ou des fluides biologiques. La première partie de cette thèse concerne le développement d’une méthode générale de marquage de motifs de type thioéther dans des molécules complexes à l’aide d’une nouvelle réaction d’échange isotopique (catalysée par des nanoparticules de Ruthénium). D’un point de vue fondamental cette transformation représente le premier exemple de (Csp³)-H activation dirigée par un atome de soufre. En termes d’application, cette nouvelle réaction permet la synthèse rapide d’étalons internes pour la quantification LC-MS/MS et le marquage tritium de molécules complexes. La seconde partie de cette thèse relate le développement d’une nouvelle méthode d’homocouplage de phénylpyridines catalysée par Ru/C. Différents substrats comportant des substituants riches et pauvres en électron ont été couplés avec de bons rendements. Ces dimères ont ensuite été utilisés pour synthétiser de nouveaux complexes de bore dont les propriétés photophysiques ont été étudiées. Dans une troisième partie, la mise au point d’une réaction palladocatalysée permettant d’obtenir des molécules polycycliques contenant un motif de type pyridine est développée
Deuterated and tritiated compounds are widely used in numerous applications in chemistry, biology and material science. In the drug discovery and development process, ADME studies require quick access to labelled molecules, otherwise the drug development costs and timeline are significantly impacted. The rapid development of metabolomics has also increased the need for isotopically labelled compounds. In particular, deuterated molecules are used as internal standards for quantitative LC-MS/MS analysis of metabolites in biological fluids and tissues. In this context, a general method allowing the deuterium and tritium labelling of bioactive thioethers using a HIE reaction is described in the first chapter. From a fundamental point of view, this transformation is the first example of (Csp³)-H activation directed by a sulfur atom. In terms of application, this new reaction has been proved to be useful for the preparation of deuterated LC-MS/MS reference materials and tritiated pharmaceuticals owning high specific activity.In the second chapter of this manuscript, the development of a method allowing the cross-dehydrogenative homocoupling of 2-arylpyridines catalyzed by Ru/C is developed. Various substrates with different substituents were efficiently coupled to give the desired dimers in good yield. In terms of application, a series of pyridine-boron complexes derived from the phenyl pyridine dimers were also synthesized and their photophysical properties were studied.In the third chapter, a regioselective palladium catalyzed intramolecular arylation reaction allowing the synthesis of pyridine containing polycyclic compounds is described
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Kennel, Sybille. „Synthèse de traceurs bimodaux utilisables en imagerie médicale TEP/IRM“. Thesis, Bordeaux, 2015. http://www.theses.fr/2015BORD0190/document.

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Aujourd’hui les médecins disposent de nombreuses techniques d’imagerie médicale afin d’établir des diagnostics précis et précoces. Cependant, chacune de ces techniques possède ses propres avantages et inconvénients. C’est pourquoi, l’utilisation de méthodes bi- ou multi-modales paraît intéressante. Parmi celles-ci, la combinaison TEP/IRM permet d’apporter des informations complémentaires. Il est alors nécessaire d’injecter aux patients un traceur adapté à chacune de ces modalités. Ce travail de thèse a donc consisté à synthétiser des plateformes moléculaires « universelles » utilisables pour l’imagerie IRM et TEP selon deux stratégies. La première a consisté en la synthèse d’une molécule composée d’un macrocycle de type DO3A permettant à la fois la chélation d’un atome de gadolinium pour l’IRM mais aussi d’un atome de gallium 68 pour la TEP. L’idée étant, afin d’avoir une sonde bimodale, de réaliser un mélange des deux composés. La seconde stratégie a été de synthétiser une unique molécule pouvant être marquée à la fois par du gadolinium pour l’IRM et par un atome de fluor 18 pour la TEP. Afin de pouvoir cibler un phénomène physiopathologique donné, l’idée de ces plateformes est de pouvoir introduire de manière simple et versatile une biomolécule. La chimie « click » semble être une méthode particulièrement attractive pour pouvoir réaliser cet objectif. Cependant, cette réaction, habituellement catalysée au cuivre est difficilement applicable sur ce genre de plateforme du fait de l’affinité du cuivre pour le macrocycle DO3A. Ce problème a donc été contourné par utilisation de la réaction de chimie « click » catalysée par des complexes de ruthénium afin d’avoir accès aux deux plateformes macrocycliques
Today physicians can use a wide variety of medical imaging techniques to establish early and accurate diagnosis. Nevertheless, each modality has its own advantages and drawbacks. This is why bi- or multimodality approach seems interesting. Among them, PET/MRI combination seems very promising because it can bring complementary informations. It is therefore necessary to inject to patients tracers specific to each imaging modality. This work described the synthesis of molecular platforms for MRI and PET imaging, according to 2 different strategies. The first one consisted in the synthesis of a DO3A macrocycle allowing the chelation of both gadolinium for MRI and gallium 68 for PET. The aim here is to have a bimodal probe, with a mixture of each compound. The second strategy was the preparation of a single molecule that can be simultaneously labeled by both gadolinium for MRI and fluorine 18 for PET. The final goal is to introduce onto these platforms a biomolecule in a versatile and easy way, to be able to target a specific pathophysiological process. ‘‘Click’’ chemistry seems to be an attractive methodology to achieve this goal. However, this reaction, usually catalyzed with copper is not suitable to DO3A macrocyles due to the copper affinity with those azamacrocycles. This issue has been circumvent by the use of ruthenium catalyzed ‘‘click’’ chemistry. We were then able to access to both macrocycles platforms
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Ryberg, Per. „Concerted or Stepwise? : β-Elimination, Nucleophilic Substitution, Copper Catalysed Aziridination and Ruthenium Catalysed Transfer Hydrogenation Studied by Kinetic Isotope Effects and Linear Free-Energy Relationships“. Doctoral thesis, Uppsala universitet, Avdelningen för organisk kemi, 2002. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-2008.

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This thesis describes the use of kinetic isotope effects, linear free energy relationships and stereochamical studies to distinguish between different mechanistic alternatives and to obtain information about transition state structure. In the first part fluorine and deuterium kinetic isotope effects were determined for the base promoted HF elimination from 4-fluoro-4-(4’-nitrophenyl)butane-2-on. During this work a new method for the determination of fluorine kinetic isotope effects was developed. The results from the study demonstrates that the reaction proceeds via an E1cBip mechanism. In the second part the transition state structure for the SN2 reaction between ethyl chloride and cyanide ion in DMSO was studied. Kinetic isotope effects for six different positions in the reacting system, both in cyanide and ethyl chloride, were determined. The experimental isotope effects were then compared with the theoretically predicted isotope effects. The third part describes the use of Hammett type free-energy relationships and stereochemical evidence to study the mechanism of the copper catalysed alkene aziridination. The results from the study support a model that involves the simultaneous presence of two different copper nitrene intermediates. One which reacts non-stereospecifically via a radical intermediate and one which reacts stereospecifically via a concerted mechanism. In the fourth part a mechanistic study of the Ru(aminoalcohol) catalysed transfer hydrogenation of acetophenone in isopropanol is described. Kinetic isotope effects were determined for both proton and hydride transfer. The observation of significant primary deuterium kinetic isotope effects for both proton and hydride transfer support a mechanism where the proton and hydride are transferred simultaneously in a concerted mechanism.
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Hajar, Yasmine. „Effect of Electrochemical Promotion and Metal-Support Interaction on Catalytic Performance of Nano-catalysts“. Thesis, Université d'Ottawa / University of Ottawa, 2019. http://hdl.handle.net/10393/39701.

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In heterogeneous catalysis, promoting the activity of the catalytic metals is long known as an important method to make a process more efficient and viable. Noble metals have been promoted classically by a chemical coverage of an ionic solution on the surface of the catalyst or using inert support, e.g., silica or alumina, allowing an increase of the dispersion of the catalyst. Therefore, new methods of promotion needed to be better explored to improve the efficiency of metal and metal oxide catalysts. One way of enhancing the catalyst’s activity is to disperse the noble metal at the nanoscale using an active type of support that is ion-conducting. Not only lattice ions can be exchanged with the surface of the nanoparticles but it can also engage in the oxidation reaction on the surface, resulting in what is known as metal-support interaction (MSI). Another method of improving the catalytic activity is to polarize the catalyst, allowing ions to migrate from a solid electrolyte to the gas-exposed surface, in a phenomenon known as electrochemical promotion of catalysis (EPOC). The change in the ions concentration on the surface would change the adsorption energy of the gaseous reactants and enhance or supress the catalytic rate. In this thesis, the effect of supporting nanoparticles of noble and non-noble metal (oxides) (Pt, Ru, Ir, Ni) was studied for the case of ionic and ionic-electronic conducting supports (CeO2, TiO2, YSZ). The enhancement in their catalytic rate was found and correlated to an electrochemical property, the exchange current density. Then, using isotopically-labeled oxygen, the oxygen exchange ability of the conductive oxides was evaluated when supporting Ir and Ru nanoparticles and correlated with the results from C3H8 isotopic oxidation reaction, which showed the extent of involvement of oxygen from the support as carried by the isotopically-labeled CO2 produced. Following this, electrochemical promotion of catalysis experiments were performed for different reactant/catalyst systems (C2H4 - Pt, Ru; C3H8 - Pt; CH4 - Pd, Ni9Pd). In the first system, the main outcome was the functional equivalence found for the MSI and EPOC effect in promoting the catalysts as experiments were performed at different temperatures, reactants partial pressures and polarization values. In the case of C3H8/Pt, the novel dispersion of Pt on an intermediate supporting layer (LSM/GDC) was found as a feasible method to obtain long stability of the catalyst while electrochemically promoting the rate of reaction. For CH4 oxidation, the polarization of the Pd nanoparticles showed continuous oxidation of the bulk of the catalyst resulting in a continuous increase of the catalytic rate. The Ni9Pd synthesized in a way to form a core/double-shell layer of Ni/Pd resulted in an enhanced catalytic rate and enhanced stability compared to stand-alone Pd. And lastly, to comprehend the ions’ effect in the electrochemical promotion and the non-Faradaic nature of the phenomena, density-functional theory (DFT) modeling was used to demonstrate the increase of the heat of adsorption of reactants depending on their electronegative/positive nature.

Buchteile zum Thema "Ruthenium Isotopes":

1

Annett, James F. „The BCS theory of superconductivity“. In Superconductivity, Superfluids, and Condensates, 127–46. Oxford University PressOxford, 2004. http://dx.doi.org/10.1093/oso/9780198507550.003.0006.

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Abstract In 1957 Bardeen Cooper and Schrieffer (BCS) published the first truly microscopic theory of superconductivity. The theory was soon recognized to be correct in all the essential aspects, and to explain a number of important experimental phenomena. For example, the theory correctly explained the isotope effect: in which the transition temperature changes with the mass of the crystal lattice ions, M. The original BCS theory predicts that the isotope exponent α is 1/2. Most common superconductors agree very well with this prediction, as one can see in Table 6.1. However, it is also clear that there are exceptions to this prediction. Transition metals such as Molybdenum and Osmium (Mo, Os) show a reduced effect, and others such as Ruthenium, Ru, have essentially zero isotope effect.

Konferenzberichte zum Thema "Ruthenium Isotopes":

1

Pokhitonov, Yu, V. Romanovski und P. Rance. „Distribution of Palladium During Spent Fuel Reprocessing“. In ASME 2003 9th International Conference on Radioactive Waste Management and Environmental Remediation. ASMEDC, 2003. http://dx.doi.org/10.1115/icem2003-4766.

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The principal purpose of spent fuel reprocessing consists in the recovery of the uranium and plutonium and the separation of fission products so as to allow re-use of fissile and fertile isotopes and facilitate disposal of waste elements. Amongst the fission products present in spent nuclear fuel of Nuclear Power Plants (NPPs,) there are considerable quantities of platinum group metals (PGMs): ruthenium, rhodium and palladium. Given current predictions for nuclear power generation, it is predicted that the quantities of palladium to be accumulated by the middle of this century will be comparable with those of the natural sources, and the quantities of rhodium in spent nuclear fuel may even exceed those in natural sources. These facts allow one to consider spent nuclear fuel generated by NPPs as a potential source for creation of a strategic stock of platinum group metals. Despite of a rather strong prediction of growth of palladium consumption, demand for “reactor” palladium in industry should not be expected because it contains a long-lived radioactive isotope 107Pd (half-life 6,5·105 years) and will thus be radioactive for a very considerable period, which, naturally, restricts its possible applications. It is presently difficult to predict all the areas for potential use of “reactor” palladium in the future, but one can envisage that the use of palladium in radwaste reprocessing technology (e.g. immobilization of iodine-129 and trans-plutonium elements) and in the hydrogen energy cycle may play a decisive role in developing the demand for this metal. Realization of platinum metals recovery operation before HLW vitrification will also have one further benefit, namely to simplify the vitrification process, because platinum group metals may in certain circumstances have adverse effects on the vitrification process. The paper will report data on platinum metals (PGM) distribution in spent fuel reprocessing products and the different alternatives of palladium separation flowsheets from HLW are presented. It is shown, that spent fuel dissolution conditions can affect the palladium distribution between solution and insoluble precipitates. The most important factors, which determine the composition and the yield of residues resulting from fuel dissolution, are the temperature and acid concentration. Apparently, a careful selection of fuel dissolution process parameters would make it possible to direct the main part of palladium to the 1st cycle raffinate together with the other fission products. In the authors’ opinion, the development of an efficient technology for palladium recovery requires the conception of a suitable flow-sheet and the choice of optimal regimes of “reactor” palladium recovery concurrently with the resolution of the problem of HLW partitioning when using the same facilities.
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Fischer-Gödde, Mario, Carsten Münker, Harry Becker, Wolfgang Maier, Kristoffer Szilas, Carina Gerritzen, Martin Van Kranendonk und Hugh Smithies. „Ruthenium isotope constraints on the nature of Earth’s late-stage building blocks“. In Goldschmidt2021. France: European Association of Geochemistry, 2021. http://dx.doi.org/10.7185/gold2021.4362.

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3

Fischer-Gödde, Mario, Bo-Magnus Elfers, Alessandro Bragagni, Christian Koeberl, Steven Goderis, Philippe Claeys, François Tissot et al. „Ruthenium isotope composition of the K-Pg impactor and terrestrial impact structures“. In Goldschmidt2023. France: European Association of Geochemistry, 2023. http://dx.doi.org/10.7185/gold2023.18281.

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4

Fischer-Gödde, Mario, Carsten Münker, Harry Becker, Maier Wolfgang, Martin J. Van Kranendonk und Hugh Smithies. „Ruthenium Isotopic Evidence for a Missing Late Accretion Component in the Mantle Source of Pilbara Craton“. In Goldschmidt2020. Geochemical Society, 2020. http://dx.doi.org/10.46427/gold2020.719.

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