A ruthenium anticancer compound interacts with histones and impacts differently on epigenetic and death pathways compared to cisplatin.

Science.gov (United States)

Licona, Cynthia; Spaety, Marie-Elodie; Capuozzo, Antonelle; Ali, Moussa; Santamaria, Rita; Armant, Olivier; Delalande, Francois; Van Dorsselaer, Alain; Cianferani, Sarah; Spencer, John; Pfeffer, Michel; Mellitzer, Georg; Gaiddon, Christian

2017-01-10

Ruthenium complexes are considered as potential replacements for platinum compounds in oncotherapy. Their clinical development is handicapped by a lack of consensus on their mode of action. In this study, we identify three histones (H3.1, H2A, H2B) as possible targets for an anticancer redox organoruthenium compound (RDC11). Using purified histones, we confirmed an interaction between the ruthenium complex and histones that impacted on histone complex formation. A comparative study of the ruthenium complex versus cisplatin showed differential epigenetic modifications on histone H3 that correlated with differential expression of histone deacetylase (HDAC) genes. We then characterized the impact of these epigenetic modifications on signaling pathways employing a transcriptomic approach. Clustering analyses showed gene expression signatures specific for cisplatin (42%) and for the ruthenium complex (30%). Signaling pathway analyses pointed to specificities distinguishing the ruthenium complex from cisplatin. For instance, cisplatin triggered preferentially p53 and folate biosynthesis while the ruthenium complex induced endoplasmic reticulum stress and trans-sulfuration pathways. To further understand the role of HDACs in these regulations, we used suberanilohydroxamic acid (SAHA) and showed that it synergized with cisplatin cytotoxicity while antagonizing the ruthenium complex activity. This study provides critical information for the characterization of signaling pathways differentiating both compounds, in particular, by the identification of a non-DNA direct target for an organoruthenium complex.

Utilization of ruthenium volatilization at heating of residue containing phosphates and nitrates for ruthenium separation and for its qualitative proof

International Nuclear Information System (INIS)

Holgye, Z.

1979-01-01

The volatility of ruthenium during the heating of a residue after evaporation of a solution containing ruthenium, phosphates and nitrates may be utilized for the separation of ruthenium from various substances. Sup(103,106) Ru may be rapidly, selectively, and quantitatively separated from fission products mixture. Ruthenium may be also separated in this way from various inorganic salts or from biological material. The volatility of ruthenium may be used also for its qualitative proof. (author)

Light-Induced Activation of a Molybdenum Oxotransferase Model within a Ru(II)-Mo(VI) Dyad.

Science.gov (United States)

Ducrot, Aurélien B; Coulson, Ben A; Perutz, Robin N; Duhme-Klair, Anne-Kathrin

2016-12-19

Nature uses molybdenum-containing enzymes to catalyze oxygen atom transfer (OAT) from water to organic substrates. In these enzymes, the two electrons that are released during the reaction are rapidly removed, one at a time, by spatially separated electron transfer units. Inspired by this design, a Ru(II)-Mo(VI) dyad was synthesized and characterized, with the aim of accelerating the rate-determining step in the cis-dioxo molybdenum-catalyzed OAT cycle, the transfer of an oxo ligand to triphenyl phosphine, via a photo-oxidation process. The dyad consists of a photoactive bis(bipyridyl)-phenanthroline ruthenium moiety that is covalently linked to a bioinspired cis-dioxo molybdenum thiosemicarbazone complex. The quantum yield and luminescence lifetimes of the dyad [Ru(bpy) 2 (L 2 )MoO 2 (solv)] 2+ were determined. The major component of the luminescence decay in MeCN solution (τ = 1149 ± 2 ns, 67%) corresponds closely to the lifetime of excited [Ru(bpy) 2 (phen-NH 2 )] 2+ , while the minor component (τ = 320 ± 1 ns, 31%) matches that of [Ru(bpy) 2 (H 2 -L 2 )] 2+ . In addition, the (spectro)electrochemical properties of the system were investigated. Catalytic tests showed that the dyad-catalyzed OAT from dimethyl sulfoxide to triphenyl phosphine proceeds significantly faster upon irradiation with visible light than in the dark. Methylviologen acts as a mediator in the photoredox cycle, but it is regenerated and hence only required in stoichiometric amounts with respect to the catalyst rather than sacrificial amounts. It is proposed that oxidative quenching of the photoexcited Ru unit, followed by intramolecular electron transfer, leads to the production of a reactive one-electron oxidized catalyst, which is not accessible by electrochemical methods. A significant, but less pronounced, rate enhancement was observed when an analogous bimolecular system was tested, indicating that intramolecular electron transfer between the photosensitizer and the catalytic center

Analysis of radioactive ruthenium

International Nuclear Information System (INIS)

1977-01-01

This manual explains the procedures of analysis of radioactive ruthenium in the drain water from atomic energy plants. The most important radioactive ruthenium is 106 Ru, and the method of measurement described in this manual is to measure the beta ray of the daughter nuclide 106 Rh. The samples to be measured are collected from seawater, marine living things, and sediment of sea bottom near atomic energy plants. In case of sea water, the ruthenium is separated by the co-precipitation with magnesium hydroxide and distillation or the extraction with carbon tetrachloride, reduction and precipitation. The beta ray of the obtained sample is measured by a gas-flow type low background β counting system. Alkali dissolution-distillation or nitric acid extraction-distillation, reduction and precipitation are applied for marine living things. The sediment of sea bottom is treated with nitric acid or strong phosphoric acid, and distilled then the ruthenium is reduced and precipitated, and the beta-counting of the precipitation is made. The method to fix radioactive ruthenium on polyethylene films after the co-precipitation is also described for reference. The detectable levels by the present methods are 0.05 pCi/l for sea water, 0.1 pCi/g for marine living things, and 20 pCi/kg for the sediment of sea bottom. (Kato, T.)

IR-doped ruthenium oxide catalyst for oxygen evolution

Science.gov (United States)

Valdez, Thomas I. (Inventor); Narayanan, Sekharipuram R. (Inventor)

2012-01-01

A method for preparing a metal-doped ruthenium oxide material by heating a mixture of a doping metal and a source of ruthenium under an inert atmosphere. In some embodiments, the doping metal is in the form of iridium black or lead powder, and the source of ruthenium is a powdered ruthenium oxide. An iridium-doped or lead-doped ruthenium oxide material can perform as an oxygen evolution catalyst and can be fabricated into electrodes for electrolysis cells.

Ruthenium transport experiments in air ingress accident conditions

Energy Technology Data Exchange (ETDEWEB)

Teemu, Karkele; Ulrika, Backman; Ari, Auvinen; Unto, Tapper; Jorma, Jokiniemi [VTT Technical Research Centre of Finland, Fine Particles (Finland); Riitta, Zilliacus; Maija, Lipponen; Tommi, Kekki [VTT Technical Research Centre of Finland, Accident Management (Finland); Jorma, Jokiniemi [Kuopio Univ., Dept. of Environmental Sciences, Fine Particle and Aerosol Technology Lab. (Finland)

2007-07-01

In this study the release, transport and speciation of ruthenium in conditions simulating an air ingress accident was studied. Ruthenium dioxide was exposed to oxidising environment at high temperature (1100-1700 K) in a tubular flow furnace. At these conditions volatile ruthenium species were formed. A large fraction of the released ruthenium was deposited in the tube as RuO{sub 2}. Depending on the experimental conditions 1-26 wt% of the released ruthenium was trapped in the outlet filter as RuO{sub 2} particles. In stainless steel tube 0-8.8 wt% of the released ruthenium reached the trapping bottle as gaseous RuO{sub 4}. A few experiments were carried out, in which revaporization of ruthenium deposited on the tube walls was studied. In these experiments, oxidation of RuO{sub 2} took place at a lower temperature. During revaporization experiments 35-65 % of ruthenium was transported as gaseous RuO{sub 4}. In order to close mass balance and achieve better time resolution 4 experiments were carried out using a radioactive tracer. In these experiments ruthenium profiles were measured. These experiments showed that the most important retention mechanism was decomposition of gaseous RuO{sub 3} into RuO{sub 2} as the temperature of the furnace was decreasing. In these experiments the transport rate of gaseous ruthenium was decreasing while the release rate was constant.

Cyclotron production of ruthenium-97 for radiopharmaceutical applications

International Nuclear Information System (INIS)

Music, S.; Gessner, M.

1980-01-01

Ruthenium-97 is of interest for clinical practice in nuclear medicine. The combination of the excellent physical and chemical properties of Ruthenium-97 make this isotope worth evaluating. Ruthenium-97 has been prepared by irradiation of a sheet of molybdenum with the internal alpha-beam of the Ruthenium-97 as a function of the alpha particle energy has been measured. The radiochemical separation and its possible clinical applications have been discussed. (author)

Method of dissolving metal ruthenium

International Nuclear Information System (INIS)

Tsuno, Masao; Soda, Yasuhiko; Kuroda, Sadaomi; Koga, Tadaaki.

1988-01-01

Purpose: To dissolve and clean metal ruthenium deposited to the inner surface of a dissolving vessel for spent fuel rods. Method: Metal ruthenium is dissolved in a solution of an alkali metal hydroxide to which potassium permanganate is added. As the alkali metal hydroxide used herein there can be mentioned potassium hydroxide, sodium hydroxide and lithium hydroxide can be mentioned, which is used as an aqueous solution from 5 to 20 % concentration in view of the solubility of metal ruthenium and economical merit. Further, potassium permanganate is used by adding to the solution of alkali metal hydroxide at a concentration of 1 to 5 %. (Yoshihara, H.)

The biokinetics of ruthenium in the human body

International Nuclear Information System (INIS)

Leggett, Richard Wayne

2011-01-01

The biokinetics of ruthenium (Ru) in the human body is of interest due mainly to the potential for occupational or environmental exposure to 106Ru (T1/2 = 373.6 d) and 103Ru (T1/2 = 39.3 d), which typically represent a significant portion of the fission products in a reactor inventory. During reactor operations or nuclear fuel reprocessing these ruthenium isotopes may be present as ruthenium tetroxide (RuO4) vapor, a highly mobile form of ruthenium that has been involved in a number of cases of accidental exposure to 106Ru or 103Ru. This paper summarizes the biokinetic database for ruthenium and proposes a new respiratory model for inhaled RuO4 vapor, a new biokinetic for systemic (absorbed) ruthenium, and material-specific gastrointestinal absorption fractions for ruthenium. The proposed respiratory model for RuO4 differs from the current ICRP model mainly in that it depicts slower clearance of deposited activity from the respiratory tract and lower absorption to blood than depicted in the current ICRP model. The proposed systemic biokinetic model depicts more realistic paths of movement of absorbed ruthenium in the body than the current ICRP model and, in contrast to the present model, a less uniform distribution of systemic activity. Implications of the proposed models with regard to inhalation and ingestion dose coefficients for 106Ru are examined.

Reactions of dihydridotetrakis(triphenylphosphine)ruthenium(II) with olefins and isolation of new ruthenium-olefin complexes

International Nuclear Information System (INIS)

Komiya, Sanshiro; Yamamoto, Akio

1976-01-01

Dihydridotetrakis(triphenylphosphine)ruthenium (II), RuH 2 (PPh 3 ) 4 , reacts with olefins (ethylene, propylene, stylene and butadiene) to give olefin-coordinated complexes of the type, Ru(olefin)(PPh 3 ) 3 and equimolar amounts of their hydrogenation products per mol of the dihydride complex. The olefin coordinated with ruthenium can be exchanged with other olefins. Olefin-coordinated complexes easily react with molecular hydrogen to afford tetrahydridotris(triphenylphosphine)ruthenium, RuH 4 (PPh 3 ) 3 , releasing alkane at room temperature, Under hydrogen atmosphere catalytic hydrogenation of the olefins smoothly takes place with RuH 2 (PPh 3 ) 4 . (Ethylene)tris(triphenylphosphine)ruthenium(0) reacts with methyl iodide to give propylene and a trace of butadiene along with methane, ethylene, and small amounts of ethane and butenes. The formation of propylene suggests that oxidative addition involving cleavage of the C-H bond of ethylene to ruthenium giving a hydridovinyl complex may be taking place. Reactions of Ru(C 2 H 4 )(PPh 3 ) 3 with methyl-d 3 iodide and ethyl iodide, and of Ru(C 3 H 6 )(PPh 3 ) 3 with methyl iodide were examined to test the generality of this type of reaction. The reaction of Ru(C 2 H 4 )(PPh 3 ) 3 with CD 3 I released CD 4 and CD 2 H 2 together with CD 3 H suggesting the involvement of α-hydrogen abstraction. (auth.)

Volatilization and trapping of ruthenium in high temperature processes

International Nuclear Information System (INIS)

Klein, M.; Weyers, C.; Goossens, W.R.A.

1983-01-01

This experimental study has indicated the importance of moisture and NO/sub x/ vapors on the volatility and trapping conditions of ruthenium in high temperature processes. Also the process operating conditions have a great influence on the ruthenium behavior in the off-gas purification units. Of particular interest is the observation that the ruthenium release during direct vitrification of simulated high-level liquid waste is a factor of about 5 smaller than the ruthenium release during calcination of this type of waste. Moreover, in the direct vitrification case the ruthenium escapes mostly in the form of an aerosol whereas in the calcination case a volatile ruthenium compound is dominating. Consequently, a specific ruthenium filter is not needed in the off-gas line of a direct vitrifier simplifying in this way the number of units in this off-gas line and avoiding the handling and controlling problems of such a ruthenium filter. In the future, a similar program will be started on the volatility of cesium and antimony in a liquid fed melter and on the technical reliability of the liquid fed melter and its associated gas purification units on a semi-pilote scale under simulated conditions

Ruthenium Dioxide Catalysts for the Selective Oxidation of Benzylamine to Benzonitrile: Investigating the Effect of Ruthenium Loading on Physical and Catalytic Properties

DEFF Research Database (Denmark)

Nordvang, Emily Catherine; Schill, Leonhard; Riisager, Anders

2017-01-01

The oxidative dehydrogenation of benzylamine to benzonitrile was studied in batch and continuous flow processes using ruthenium dioxide catalysts with varying ruthenium loadings. Increased conversions were observed in the continuous flow process compared with the batch process (up to 100% in the ......The oxidative dehydrogenation of benzylamine to benzonitrile was studied in batch and continuous flow processes using ruthenium dioxide catalysts with varying ruthenium loadings. Increased conversions were observed in the continuous flow process compared with the batch process (up to 100......% in the flow process compared with up to 92% in the batch process), with increased selectivity to benzonitrile (82 and 65%, respectively) and benzonitrile yields (84 and 58%, respectively). The major by-product was N-benzylidenebenzylamine. The ruthenium loading in the catalyst was successfully optimised...... and the most active catalyst had a ruthenium loading of 2.5-3.5 wt%....

PATTERNS OF EMOTIONAL AVAILABILITY IN MOTHER-INFANT DYADS: ASSOCIATIONS WITH MULTIPLE LEVELS OF CONTEXT.

Science.gov (United States)

Mingo, M Verónica; Easterbrooks, M Ann

2015-01-01

This study explored emotional availability (EA)- an individual's emotional responsiveness and attunement to another's needs and goals (R.N. Emde, 1980)- among a high social risk group of 226 adolescent mothers and their infants (average = 12 months old). The aim was to identify dyadic patterns of EA and to examine their association with multiple indicators of the ecological context. Maternal sensitivity, maternal nonhostility, and child responsiveness were assessed with the Emotional Availability Scales, Third Edition (Z. Biringen, J. Robinson, & R.N. Emde, 1998) during free play and teaching observations at home. Four EA patterns were identified using k-means cluster analysis: (a) "low functioning," (b) "high functioning," (c) "low functioning dyads with nonhostile mothers," and (d) "inconsistently sensitive mother and responsive child." These patterns had distinct associations with (a) mothers' parenting attitudes regarding children's power and independence and parent-child role reversal, (b) mothers' strategies in conflict resolution with their partners and their children, and (c) the dyads' living arrangements. This study makes a contribution to the understanding of the mother-child relationship from a systemic and relational perspective and explores the association of EA patterns with the dyads' relational context. Implications for programs and treatment approaches aimed at supporting dyads at social risk are discussed. © 2015 Michigan Association for Infant Mental Health.

Photophysical properties of novel Porphyrin-Flavin Dyads

International Nuclear Information System (INIS)

Stark, S.

2001-10-01

Photosynthesis belongs to the fundamentals of life on earth, therefore it is an important matter in natural sciences. The basic principle of photosynthesis is the transformation of solar light into chemical energy. The starting steps of photosynthesis are light-induced energy- and electron-transfer-steps with singular efficiency. One attempt to enlighten the molecular processes involved is to synthesize simpler model systems with similar properties. Important research goals are the dependencies of light-induced processes on distance and orientation of donor and acceptor. A second aim next to the clarification of the molecular conditions of photosynthesis is to create molecular light-driven machines. The most simple so-called biomimetic model system consists of an electron-donor connected to an electron-acceptor via a spacer-group. This simplest form is also referred to as dyad. Beyond dyads far more complicated compounds have been introduced consisting of several donors and/or acceptors, so-called triads, tetrads, pentads etc. Usually porphyrin serves as electron-donor. Next to chinones several other electron-acceptors are used, e.g. anthracene, pyromellitimide and fullerene. Artificial photosynthetic centers are often more stable and/or the excited states are easier to detect compared to the natural photosynthetic center. The photophysical characteristics of four dyads are reported in this work. The dyads consist of porphyrin (either free-base or zinc-metallated) and flavin, connected by different spacers. These dyads reveal photo-induced electron transfer from porphyrin to flavin and energy-transfer in the reversed direction with different efficiencies. The object of the study is the dependency of these processes on the structural features. The spacer of the dyads 1a-1c is an aromatic bridge which leads to well defined donor-acceptor distances. Because of this structure conjugation through the spacer is increased, whereas the absorption in the visible and near UV

Electro-volatilization of ruthenium in nitric medium: influences of ruthenium species nature and models solutions composition

International Nuclear Information System (INIS)

Mousset, F.

2004-12-01

Ruthenium is one of the fission products in the reprocessing of irradiated fuels that requires a specific processing management. Its elimination, upstream by the PUREX process, has been considered. A process, called electro-volatilization, which take advantage of the RuO 4 volatility, has been optimised in the present study. It consists in a continuous electrolysis of ruthenium solutions in order to generate RuO 4 species that is volatilized and easily trapped. This process goes to satisfying ruthenium elimination yields with RuNO(NO 3 ) 3 (H 2 O) 2 synthetic solutions but not with fuel dissolution solutions. Consequently, this work consisted in the speciation studies of dissolved ruthenium species were carried out by simulating fuel solutions produced by hot acid attack of several ruthenium compounds (Ru(0), RuO 2 ,xH 2 O, polymetallic alloy). In parallel with dissolution kinetic studies, the determination of dissolved species was performed using voltammetry, spectrometry and spectro-electrochemistry. The results showed the co-existence of Ru(IV) and RuNO(NO 2 ) 2 (H 2 O) 3 . Although these species are different from synthetic RuNO(NO 3 ) 3 (H 2 O) 2 , their electro-oxidation behaviour are similar. The electro-volatilization tests of these dissolution solutions yielded to comparable results as the synthetic RuNO(NO 3 ) 3 (H 2 O) 2 solutions. Then, complexity increase of models solutions was performed by in-situ generation of nitrous acid during ruthenium dissolution. Nitrous acid showed a catalytic effect on ruthenium dissolution. Its presence goes to quasi exclusively RuNO(NO 2 ) 2 (H 2 O) 3 species. It is also responsible of the strong n-bond formation between Ru 2+ and NO + . In addition, it has been shown that its reducing action on RuO 4 hinders the electro-volatilization process. Mn 2+ and Ce 3+ cations also reveal, but to a lesser extent, an electro-eater behaviour as well as Pu 4+ and Cr 3+ according to the thermodynamics data. These results allow one to

Application of the chemical properties of ruthenium to decontamination processes; L'application des proprietes chimiques du ruthenium a des procedes de decontamination

Energy Technology Data Exchange (ETDEWEB)

Fontaine, A; Berger, D [Commissariat a l' Energie Atomique, Centre de Production de Plutonium, Marcoule (France). Centre d' Etudes Nucleaires

1965-07-01

The chemical properties of ruthenium in the form of an aqueous solution of the nitrate and of organic tributylphosphate solution are reviewed. From this data, some known examples are given: they demonstrate the processes of separation or of elimination of ruthenium from radioactive waste. (authors) [French] Les proprietes chimiques du ruthenium en solutions aqueuses nitriques et en solutions organiques de tributylphosphate, sont passees en revue. A partir de ces donnees, quelques exemples connus sont cites: ils exposent des procedes de separation ou d'elimination du ruthenium de dechets radioactifs. (auteurs)

Medical students' perception of dyad practice

DEFF Research Database (Denmark)

Tolsgaard, Martin G; Rasmussen, Maria Birkvad; Bjørck, Sebastian

2014-01-01

Training in pairs (dyad practice) has been shown to improve efficiency of clinical skills training compared with single practice but little is known about students' perception of dyad practice. The aim of this study was to explore the reactions and attitudes of medical students who were instructed....... The students felt dyad practice improved their self-efficacy through social interaction with peers, provided useful insight through observation, and contributed with shared memory of what to do, when they forgot essential steps of the physical examination of the patient. However, some students were concerned...

Ruthenium Sensitizers and Their Applications in Dye-Sensitized Solar Cells

Directory of Open Access Journals (Sweden)

Yuancheng Qin

2012-01-01

Full Text Available Dye-sensitized solar cells (DSSCs have attracted considerable attention in recent years due to the possibility of low-cost conversion of photovoltaic energy. The DSSCs-based ruthenium complexes as sensitizers show high efficiency and excellent stability, implying potential practical applications. This review focuses on recent advances in design and preparation of efficient ruthenium sensitizers and their applications in DSSCs, including thiocyanate ruthenium sensitizers and thiocyanate-free ruthenium sensitizers.

Development of a method for analyzing traces of ruthenium in plant materials and determination of the transfer factors soil/plant for ruthenium compounds from reprocessing plants

International Nuclear Information System (INIS)

Blasius, E.; Huth, R.; Neumann, W.

1988-01-01

In an artificial humous and sandy soil spiked with 106 Ru as RuO 2 and RuCl 3 , pasture grass was grown under artificial illumination in our laboratory. The amounts of ruthenium taken up by the plants were determined by γ-spectrometry. For open-air investigations with pasture grass, wheat and potatoes inactive ruthenium(III) chloride and ruthenium nitrosylchloride were used. Ruthenium was determined by electrothermal atomic absorption spectrometry (ETAAS) after destroying the organic material and concentrating the solution. The concentration and chemical form of the ruthenium exert an unimportant influence on the transfer factor. For the pasture-grass, the stems of wheat and the weed of potatoes it amounts to 0.00005 to 0.0015, for the ear of wheat to about 0.00005. In peeled potatoes there was no ruthenium detectable, therefore the limit of detection leads to a transfer factor ≤ 0.00001. So it is evident that ruthenium is little available for the roots of the plants. In the event of an accident in a nuclear plant the uptake of radioactive ruthenium by roots has only negligible radioecological consequences. This applies even if 50 years of ruthenium enrichment in the soil are assumed. (orig./RB)

Application of the chemical properties of ruthenium to decontamination processes; L'application des proprietes chimiques du ruthenium a des procedes de decontamination

Energy Technology Data Exchange (ETDEWEB)

Fontaine, A.; Berger, D. [Commissariat a l' Energie Atomique, Centre de Production de Plutonium, Marcoule (France). Centre d' Etudes Nucleaires

1965-07-01

The chemical properties of ruthenium in the form of an aqueous solution of the nitrate and of organic tributylphosphate solution are reviewed. From this data, some known examples are given: they demonstrate the processes of separation or of elimination of ruthenium from radioactive waste. (authors) [French] Les proprietes chimiques du ruthenium en solutions aqueuses nitriques et en solutions organiques de tributylphosphate, sont passees en revue. A partir de ces donnees, quelques exemples connus sont cites: ils exposent des procedes de separation ou d'elimination du ruthenium de dechets radioactifs. (auteurs)

Analysis of uranium and its compounds. Ruthenium spectrographic determination

International Nuclear Information System (INIS)

Anon.

Ruthenium determination in uranium and its compounds, suitable for content greater than 0.1 ppm with respect to uranium, by dissolution in sulfuric acid and addition of palladium as an internal standard, separation of the precipitated ruthenium, in the presence of gold, by reduction with zinc, the precipitate is calcined and ruthenium is determined by spectrography [fr

Relational demography in coach-athlete dyads | Zhang | African ...

African Journals Online (AJOL)

This study used an adapted version of Zhang's (2004) trust questionnaire to examine perceived characteristic and trust differences between coach and athlete dyads that differ in gender or ethnicity as well as in dyads that were similar. The four different gender dyad groups were male athlete with male coach (MAMC), ...

Scaling-resistance of ruthenium- and ruthenium phosphides powders in argon and air

International Nuclear Information System (INIS)

Chernogorebko, V.B.; Semenov-Kobzar', A.A.; Kulik, L.Ya.

1976-01-01

The thermal stability of ruthenium phosphides in air diminishes as the content of phosphorus in the compound increases. The temperatures at which active oxidation of the powders starts are as follows: Ru-600, Ru 2 P-590, RuP-390, and RuP 2 -270 0 C. The oxidation of phosphorus in the phosphides proceeds in steps. The atoms of phosphorus which are most accessible to oxygen are first oxidated. Phosphorus atoms in the octahedral spaces are oxidated less easily, simultaneously with the oxidation of the ruthenium atoms. When heated in argon, Ru 2 P and RuP fuse congruently at 1,500 and 1,555 0 C respectively, while RuP 2 dissociates at 950 0 C. (author)

Quantum chemical studies on electronic structure and photodynamics of ruthenium complexes

International Nuclear Information System (INIS)

Freitag, L.

2015-01-01

Ruthenium complexes have found their way into many applications in the last decades. Among those, ruthenium polypyridyl compounds have been employed as light harvesting devices and photosensitisers in artificial photosynthesis and molecular photocatalysis. Ruthenium nitrosyl complexes are rapidly emerging as NO delivery agents to biological tissues with promising applications in anticancer photodynamic therapy, thanks to their ability to photorelease nitric oxide (NO). This thesis encompasses computational studies on reactivity, electronic structure, excited states and photodynamics of several ruthenium nitrosyl and polypyridyl complexes. The first part of the thesis deals with ruthenium nitrosyls. The cis-trans isomerisation mechanism of RuHIndNO, a ruthenium nitrosyl derivate of the prominent anti-cancer drug candidate KP1019, is investigated with density functional theory calculations. Next, the electronic structure of the ground and the first excited triplet state of RuHIndNO is studied with multiconfigurational methods including the density-matrix renormalisation group (DMRG). The obtained multiconfigurational wavefunctions and DMRG-based orbital entanglement analysis provides theoretical insight into the non-innocence of the NO ligand in nitrosyl complexes by describing the electron correlation in the Ru--NO bond and assigning oxidation states to the metal and the NO ligand. Another study is performed on excited states of ruthenium nitrosyl complexes with quantum chemical calculations and surface-hopping dynamics to obtain insights into the photodissociation mechanism of NO. The second part of this thesis is devoted to the excited states and photophysics of ruthenium polypyridyl complexes. Accurate excitation energies of tris(2,2-bipyridine)ruthenium (II), the prototype ruthenium polypyridyl are obtained with multiconfigurational calculations assisted by an orbital entanglement analysis. Subsequently, the effect of the ligand substitution on the photophysics

Electro-volatilization of ruthenium in nitric medium: influences of ruthenium species nature and models solutions composition; Electro-volatilisation du ruthenium en milieu nitrique: influence de la nature des formes chimiques du ruthenium et de la composition des solutions modeles de dissolution

Energy Technology Data Exchange (ETDEWEB)

Mousset, F

2004-12-15

Ruthenium is one of the fission products in the reprocessing of irradiated fuels that requires a specific processing management. Its elimination, upstream by the PUREX process, has been considered. A process, called electro-volatilization, which take advantage of the RuO{sub 4} volatility, has been optimised in the present study. It consists in a continuous electrolysis of ruthenium solutions in order to generate RuO{sub 4} species that is volatilized and easily trapped. This process goes to satisfying ruthenium elimination yields with RuNO(NO{sub 3}){sub 3}(H{sub 2}O){sub 2} synthetic solutions but not with fuel dissolution solutions. Consequently, this work consisted in the speciation studies of dissolved ruthenium species were carried out by simulating fuel solutions produced by hot acid attack of several ruthenium compounds (Ru(0), RuO{sub 2},xH{sub 2}O, polymetallic alloy). In parallel with dissolution kinetic studies, the determination of dissolved species was performed using voltammetry, spectrometry and spectro-electrochemistry. The results showed the co-existence of Ru(IV) and RuNO(NO{sub 2}){sub 2}(H{sub 2}O){sub 3}. Although these species are different from synthetic RuNO(NO{sub 3}){sub 3}(H{sub 2}O){sub 2}, their electro-oxidation behaviour are similar. The electro-volatilization tests of these dissolution solutions yielded to comparable results as the synthetic RuNO(NO{sub 3}){sub 3}(H{sub 2}O){sub 2} solutions. Then, complexity increase of models solutions was performed by in-situ generation of nitrous acid during ruthenium dissolution. Nitrous acid showed a catalytic effect on ruthenium dissolution. Its presence goes to quasi exclusively RuNO(NO{sub 2}){sub 2}(H{sub 2}O){sub 3} species. It is also responsible of the strong n-bond formation between Ru{sup 2+} and NO{sup +}. In addition, it has been shown that its reducing action on RuO{sub 4} hinders the electro-volatilization process. Mn{sup 2+} and Ce{sup 3+} cations also reveal, but to a lesser

Experiments on the behaviour of ruthenium in air ingress accidents

International Nuclear Information System (INIS)

Kaerkelae, T.; Backman, Ul; Auvinen, A.; Zilliacus, R.; Lipponen, M.; Kekki, T.; Tapper, U.; Jokiniemi, J.

2007-03-01

During routine nuclear reactor operation, ruthenium will accumulate in the fuel in relatively high concentrations. In a severe accident in a nuclear power plant it is possible that air gets into contact with the reactor core. In this case ruthenium may oxidise and form volatile ruthenium species, RuO3 and RuO4, which can be transported into the containment. In order to estimate the amount of gaseous ruthenium species, it is of interest to know, how they are formed and how they behave. In our experiments the formation and transport of volatile ruthenium oxides was studied by exposing RuO2 powder to diverse oxidising atmospheres at a relatively high temperature. Transport of gaseous RuO4 was further investigated by injecting it into the facility in similar conditions. Upon cooling of the gas flow RuO2 aerosol particles were formed in the system. They were removed from the gas stream with plane filters. Gaseous ruthenium species were trapped in 1M NaOH-water solution, which is capable of trapping RuO4 totally. Ruthenium in the solution was filtered for analysis. The determination of ruthenium both in aerosol and in liquid filters was made using instrumental neutron activation analysis (INAA). In order to close the mass balance and to achieve better time resolution seven experiment were carried out using radioactive tracer. In this report, the facility for the ruthenium behaviour study and results from experiments are presented. Preliminary conclusions from the experiments are reported as well. Final conclusions will be made after modelling of the facility is completed in a continuation work of this study. (au)

Experiments on the behaviour of ruthenium in air ingress accidents

Energy Technology Data Exchange (ETDEWEB)

Kaerkelae, T.; Backman, Ul; Auvinen, A.; Zilliacus, R.; Lipponen, M.; Kekki, T.; Tapper, U.; Jokiniemi, J. [Technical Research Centre of Finland VTT (Finland)

2007-03-15

During routine nuclear reactor operation, ruthenium will accumulate in the fuel in relatively high concentrations. In a severe accident in a nuclear power plant it is possible that air gets into contact with the reactor core. In this case ruthenium may oxidise and form volatile ruthenium species, RuO3 and RuO4, which can be transported into the containment. In order to estimate the amount of gaseous ruthenium species, it is of interest to know, how they are formed and how they behave. In our experiments the formation and transport of volatile ruthenium oxides was studied by exposing RuO2 powder to diverse oxidising atmospheres at a relatively high temperature. Transport of gaseous RuO4 was further investigated by injecting it into the facility in similar conditions. Upon cooling of the gas flow RuO2 aerosol particles were formed in the system. They were removed from the gas stream with plane filters. Gaseous ruthenium species were trapped in 1M NaOH-water solution, which is capable of trapping RuO4 totally. Ruthenium in the solution was filtered for analysis. The determination of ruthenium both in aerosol and in liquid filters was made using instrumental neutron activation analysis (INAA). In order to close the mass balance and to achieve better time resolution seven experiment were carried out using radioactive tracer. In this report, the facility for the ruthenium behaviour study and results from experiments are presented. Preliminary conclusions from the experiments are reported as well. Final conclusions will be made after modelling of the facility is completed in a continuation work of this study. (au)

In situ formed catalytically active ruthenium nanocatalyst in room temperature dehydrogenation/dehydrocoupling of ammonia-borane from Ru(cod)(cot) precatalyst.

Science.gov (United States)

Zahmakiran, Mehmet; Ayvalı, Tuğçe; Philippot, Karine

2012-03-20

The development of simply prepared and effective catalytic materials for dehydrocoupling/dehydrogenation of ammonia-borane (AB; NH(3)BH(3)) under mild conditions remains a challenge in the field of hydrogen economy and material science. Reported herein is the discovery of in situ generated ruthenium nanocatalyst as a new catalytic system for this important reaction. They are formed in situ during the dehydrogenation of AB in THF at 25 °C in the absence of any stabilizing agent starting with homogeneous Ru(cod)(cot) precatalyst (cod = 1,5-η(2)-cyclooctadiene; cot = 1,3,5-η(3)-cyclooctatriene). The preliminary characterization of the reaction solutions and the products was done by using ICP-OES, ATR-IR, TEM, XPS, ZC-TEM, GC, EA, and (11)B, (15)N, and (1)H NMR, which reveal that ruthenium nanocatalyst is generated in situ during the dehydrogenation of AB from homogeneous Ru(cod)(cot) precatalyst and B-N polymers formed at the initial stage of the catalytic reaction take part in the stabilization of this ruthenium nanocatalyst. Moreover, following the recently updated approach (Bayram, E.; et al. J. Am. Chem. Soc.2011, 133, 18889) by performing Hg(0), CS(2) poisoning experiments, nanofiltration, time-dependent TEM analyses, and kinetic investigation of active catalyst formation to distinguish single metal or in the present case subnanometer Ru(n) cluster-based catalysis from polymetallic Ru(0)(n) nanoparticle catalysis reveals that in situ formed Ru(n) clusters (not Ru(0)(n) nanoparticles) are kinetically dominant catalytically active species in our catalytic system. The resulting ruthenium catalyst provides 120 total turnovers over 5 h with an initial turnover frequency (TOF) value of 35 h(-1) at room temperature with the generation of more than 1.0 equiv H(2) at the complete conversion of AB to polyaminoborane (PAB; [NH(2)BH(2)](n)) and polyborazylene (PB; [NHBH](n)) units.

Method of suppressing evaporation loss of ruthenium

International Nuclear Information System (INIS)

Muromura, Tadazumi; Sato, Tadashi.

1987-01-01

Purpose: To prevent evaporation loss of ruthenium from liquid wastes by adding an aluminum compound upon applying evaporating and drying to solid treatment to reprocessing liquid wastes for spent fuels. Method: An aluminum compound such as aluminum nitrate or aluminum hydroxide to reprocessing liquid wastes of spent fuels such that aluminum/ruthenium mixing ratio corresponds to 1.3 - 70.0 by g/atom ratio (0.34 - 187 by weight ratio), and the liquid mixture is heated to a temperature of about 130 deg C to be evaporated and dried to solidness. This enables to recover ruthenium without settling and depositing insoluble matters in the liquid wastes and without decomposing nitric acid. (Yoshino, Y.)

Titrimetric determination of ruthenium

International Nuclear Information System (INIS)

Velichko, V.V.; Belyaeva, T.I.; Kudinova, V.K.; Usatenko, Yu.I.

1978-01-01

Titration of ruthenium(4) hydrochloric-acid solutions with Mohr's salt, hydroquinone, and thiourea has been studied with the use of biampero- and potentiometric indication of the titration end point (t.e.p.) Potentiometric and amperometric indication of the t.e.p. is applicable when Ru(4) concentration is from 20 to 6000 mkg in 20 ml of the titrated solution; biamperometric indication can be used at a concentration of 5-1000 mkg in the same volume. It has been established that titration of Ru(4) (in the form of the Na 2 RuCl 6 solution) with Mohr's salt is not hindered by the presence of 1000-fold excess of alkaline and alkali-earth metals, Al, Ti(4), Mn(2), Cr(3), Fe(3), Co, Ni, Cu, Zn, Ga, Ge(4), As, Se, Mo(6), Cd, In, and Te; 100-fold excess of Rh, Pd, W, Bi, and Sn; 10-fold excess of Ag, Au, Pt, Hg, Os. Along with Ru(4) titrated are Ir(4), Te(3), V(5), and Ce(4). Selectivity of hydroquinone and thiourea is lower. Titrimetric procedure of determining ruthenium has been tested for ruthenium alloy containing cobalt tungsten. It cannot be recommended for analysis of the samples which dissolve in aqua regia

The Effectiveness of Healthy Start Home Visit Program: Cluster Randomized Controlled Trial

Science.gov (United States)

Leung, Cynthia; Tsang, Sandra; Heung, Kitty

2015-01-01

Purpose: The study reported the effectiveness of a home visit program for disadvantaged Chinese parents with preschool children, using cluster randomized controlled trial design. Method: Participants included 191 parents and their children from 24 preschools, with 84 dyads (12 preschools) in the intervention group and 107 dyads (12 preschools) in…

Experiments on the behaviour of ruthenium in air ingress accidents - Progress report

International Nuclear Information System (INIS)

Kaerkelae, T.; Backman, U.; Auvinen, A.; Ziliacus, R.; Lipponen, M.; Kekki, T.; Tapper, U.; Jokiniemi, J.

2006-02-01

During routine nuclear reactor operation, ruthenium will accumulate in the fuel in relatively high concentrations. In an accident in a nuclear power plant it is possible that air gets into contact with the reactor core. In this case ruthenium can oxidise and form volatile ruthenium species, RuO3 and RuO4, which can be transported into the containment. In order to estimate the amount of gaseous ruthenium species it is of interest to know, how it is formed and how it behaves. In our experiments RuO2 is exposed to diverse oxidising atmospheres at a relatively high temperature. In this report, the experimental system for the ruthenium behaviour study is presented. Also preliminary results from experiments carried out during year 2005 are reported. In the experiments gaseous ruthenium oxides were produced in a furnace. Upon cooling RuO2 aerosol particles were formed in the system. They were removed with plane filters from the gas stream. Gaseous ruthenium species were trapped in 1M NaOH-water solution, which is capable of trapping RuO4 totally. Ruthenium in the solution was filtered for analysis. The determination of ruthenium both in aerosol and in liquid filters was made using instrumental neutron activation analysis (INAA). In order to close mass balance and achieve better time resolution three experiment using radioactive tracer were carried out. (au)

Experiments on the behaviour of ruthenium in air ingress accidents - Progress report

Energy Technology Data Exchange (ETDEWEB)

Kaerkelae, T.; Backman, U.; Auvinen, A.; Ziliacus, R.; Lipponen, M.; Kekki, T.; Tapper, U.; Jokiniemi, J. [VTT Technical Research Centre of Finland (Finland)

2006-02-15

During routine nuclear reactor operation, ruthenium will accumulate in the fuel in relatively high concentrations. In an accident in a nuclear power plant it is possible that air gets into contact with the reactor core. In this case ruthenium can oxidise and form volatile ruthenium species, RuO3 and RuO4, which can be transported into the containment. In order to estimate the amount of gaseous ruthenium species it is of interest to know, how it is formed and how it behaves. In our experiments RuO2 is exposed to diverse oxidising atmospheres at a relatively high temperature. In this report, the experimental system for the ruthenium behaviour study is presented. Also preliminary results from experiments carried out during year 2005 are reported. In the experiments gaseous ruthenium oxides were produced in a furnace. Upon cooling RuO2 aerosol particles were formed in the system. They were removed with plane filters from the gas stream. Gaseous ruthenium species were trapped in 1M NaOH-water solution, which is capable of trapping RuO4 totally. Ruthenium in the solution was filtered for analysis. The determination of ruthenium both in aerosol and in liquid filters was made using instrumental neutron activation analysis (INAA). In order to close mass balance and achieve better time resolution three experiment using radioactive tracer were carried out. (au)

Characterization of ultrasonic spray pyrolysed ruthenium oxide thin films

Energy Technology Data Exchange (ETDEWEB)

Patil, P.S.; Ennaoui, E.A.; Lokhande, C.D.; Mueller, M.; Giersig, M.; Diesner, K.; Tributsch, H. [Hahn-Meitner-Institut Berlin GmbH (Germany). Bereich Physikalische Chemie

1997-11-21

The ultrasonic spray pyrolysis (USP) technique was employed to deposit ruthenium oxide thin films. The films were prepared at 190 C substrate temperature and further annealed at 350 C for 30 min in air. The films were 0.22 {mu} thick and black grey in color. The structural, compositional and optical properties of ruthenium oxide thin films are reported. Contactless transient photoconductivity measurement was carried out to calculate the decay time of excess charge carriers in ruthenium oxide thin films. (orig.) 28 refs.

Surface and sub-surface thermal oxidation of thin ruthenium films

Energy Technology Data Exchange (ETDEWEB)

Coloma Ribera, R.; Kruijs, R. W. E. van de; Yakshin, A. E.; Bijkerk, F. [MESA+ Institute for Nanotechnology, University of Twente, P.O. Box 217, 7500 AE Enschede (Netherlands); Kokke, S.; Zoethout, E. [FOM Dutch Institute for Fundamental Energy Research (DIFFER), P.O. Box 1207, 3430 BE Nieuwegein (Netherlands)

2014-09-29

A mixed 2D (film) and 3D (nano-column) growth of ruthenium oxide has been experimentally observed for thermally oxidized polycrystalline ruthenium thin films. Furthermore, in situ x-ray reflectivity upon annealing allowed the detection of 2D film growth as two separate layers consisting of low density and high density oxides. Nano-columns grow at the surface of the low density oxide layer, with the growth rate being limited by diffusion of ruthenium through the formed oxide film. Simultaneously, with the growth of the columns, sub-surface high density oxide continues to grow limited by diffusion of oxygen or ruthenium through the oxide film.

Contribution to the study of ruthenium fluorides, oxyfluorides and oxides

International Nuclear Information System (INIS)

Corbin, Odile.

1982-08-01

Studies on the dry processing of spent fuels reveal a poor ruthenium decontamination of plutonium. For a better understanding of this result a study of ruthenium fluorides, oxyfluorides and oxides is carried out here as follows: - bibliographical review; - thermochromatographic identification of the number and nature of compounds formed by fluorination of microquantities of ruthenium; - confirmation of the thermochromatographic results by two other analytical methods: thermogravimetry and infrared spectroscopy [fr

Adsorption of aliphatic alcohols on ruthenium

International Nuclear Information System (INIS)

Shapovalova, L.B.; Zakumbaeva, G.D.

1977-01-01

The adsorption is studied of allyl-, propyl- and propargyl alcohols on a ruthenium catalyst-electrode at 20, 30 and 40 deg C in H 2 SO 4 in helium. Above adsorption has been found to grow with increased concentration of the alcohols in the solution. In solutions with the same concentration, propargyl alcohol has been noted to show highest sorptive capacity, followed by that of allyl- and propyl alcohols. With variations in the ruthenium electrode potential, alcohol adsorption occurs via maximum at potential = 0.18

Characterization of self-assembled monolayers on a ruthenium surface

NARCIS (Netherlands)

Shaheen, Amrozia; Sturm, Jacobus Marinus; Ricciardi, R.; Huskens, Jurriaan; Lee, Christopher James; Bijkerk, Frederik

2017-01-01

We have modified and stabilized the ruthenium surface by depositing a self-assembled monolayer (SAM) of 1-hexadecanethiol on a polycrystalline ruthenium thin film. The growth mechanism, dynamics, and stability of these monolayers were studied. SAMs, deposited under ambient conditions, on

Optimization of screen-printed ruthenium dioxide electrodes for pH measurements

International Nuclear Information System (INIS)

Wyzkiewicz, I.

2002-01-01

Optimization of disposable, screen-printed pH-sensors based on ruthenium dioxide is described in this paper. The electrodes were prepared with the use of thick-film technology. The pH-sensitive layers were deposited onto polyester foil. Polymer graphite paste containing ruthenium dioxide from 0% to 90% has been investigated. The dependence of the pH-sensitive layers related to ruthenium dioxide content is presented. The investigation proved that the electrodes containing 40-60% ruthenium dioxide exhibit linear high sensitivity (∼ 50 mV/pH) in the wide range of pH (2 - 11) as well as very good reproducibility. (author)

An XPS study on ruthenium compounds and catalysts

International Nuclear Information System (INIS)

Bianchi, C.L.; Ragaini, V.; Cattania, M.G.

1991-01-01

The binding energy (BE) of the relevant peaks of several ruthenium compounds have been measured with a monochromatic small spot XPS. The BE of the 3d 5/2 level of ruthenium is in the range 279.91-282.88 eV. The variation of BE is due either to the variation of the oxidation state or to the different counter-ion. A series of catalysts with varying amounts of ruthenium supported on alumina and prepared using different precursors was also analyzed. The presence of more ruthenium species other than the metal was observed. On the basis of the values previously obtained on unsupported compounds, the species with higher BE were assigned to oxides. On all the samples prepared from RuCl 3 , an additional peak at a very high BE (283.79 eV) has been observed. This peak is related to the presence of chlorine on the surface: it is suggested that it is related to a charge transfer interaction. The influence of this species on the CO reactivity in the Fischer-Tropsch reaction is discussed. (orig.)

Oxidation of ruthenium thin films using atomic oxygen

Energy Technology Data Exchange (ETDEWEB)

McCoy, A.P.; Bogan, J.; Brady, A.; Hughes, G.

2015-12-31

In this study, the use of atomic oxygen to oxidise ruthenium thin films is assessed. Atomic layer deposited (ALD) ruthenium thin films (~ 3 nm) were exposed to varying amounts of atomic oxygen and the results were compared to the impact of exposures to molecular oxygen. X-ray photoelectron spectroscopy studies reveal substantial oxidation of metallic ruthenium films to RuO{sub 2} at exposures as low as ~ 10{sup 2} L at 575 K when atomic oxygen was used. Higher exposures of molecular oxygen resulted in no metal oxidation highlighting the benefits of using atomic oxygen to form RuO{sub 2}. Additionally, the partial oxidation of these ruthenium films occurred at temperatures as low as 293 K (room temperature) in an atomic oxygen environment. - Highlights: • X-ray photoelectron spectroscopy study of the oxidation of Ru thin films • Oxidation of Ru thin films using atomic oxygen • Comparison between atomic oxygen and molecular oxygen treatments on Ru thin films • Fully oxidised RuO{sub 2} thin films formed with low exposures to atomic oxygen.

Thermodynamic properties of gaseous ruthenium species.

Science.gov (United States)

Miradji, Faoulat; Souvi, Sidi; Cantrel, Laurent; Louis, Florent; Vallet, Valérie

2015-05-21

The review of thermodynamic data of ruthenium oxides reveals large uncertainties in some of the standard enthalpies of formation, motivating the use of high-level relativistic correlated quantum chemical methods to reduce the level of discrepancies. The reaction energies leading to the formation of ruthenium oxides RuO, RuO2, RuO3, and RuO4 have been calculated for a series of reactions. The combination of different quantum chemical methods has been investigated [DFT, CASSCF, MRCI, CASPT2, CCSD(T)] in order to predict the geometrical parameters, the energetics including electronic correlation and spin-orbit coupling. The most suitable method for ruthenium compounds is the use of TPSSh-5%HF for geometry optimization, followed by CCSD(T) with complete basis set (CBS) extrapolations for the calculation of the total electronic energies. SO-CASSCF seems to be accurate enough to estimate spin-orbit coupling contributions to the ground-state electronic energies. This methodology yields very accurate standard enthalpies of formations of all species, which are either in excellent agreement with the most reliable experimental data or provide an improved estimate for the others. These new data will be implemented in the thermodynamical databases that are used by the ASTEC code (accident source term evaluation code) to build models of ruthenium chemistry behavior in severe nuclear accident conditions. The paper also discusses the nature of the chemical bonds both from molecular orbital and topological view points.

Exciplex mediated photoinduced electron transfer reactions of phthalocyanine-fullerene dyads

NARCIS (Netherlands)

Niemi, Marja; Tkachenko, Nikolai V.; Efimov, Alexander; Lehtivuori, Heli; Ohkubo, Kei; Fukuzumi, Shunichi; Lemmetyinen, Helge

2008-01-01

Evidences of an intramolecular exciplex intermediate in a photoinduced electron transfer (ET) reaction of double-linked free-base and zinc phthalocyanine-C-60 dyads were found. This was the first time for a dyad with phthalocyanine donor. Excitation of the phthalocyanine moiety of the dyads results

Synthesis of PVP-stabilized ruthenium colloids with low boiling point alcohols.

Science.gov (United States)

Zhang, Yuqing; Yu, Jiulong; Niu, Haijun; Liu, Hanfan

2007-09-15

A route to the preparation of poly(N-vinyl-2-pyrrolidone) (PVP)-stabilized ruthenium colloids by refluxing ruthenium(III) chloride in low boiling point alcohols was developed. Deep purple colloids with shuttle-like ruthenium particles were also synthesized. XPS measurement verified the nanoparticles were in the metallic state. The morphology of metal nanoparticles was characterized by UV-visible absorption spectrophotometry, TEM and XRD.

Similarity in Depressive Symptoms in Adolescents’ Friendship Dyads: Selection or Socialization?

Science.gov (United States)

Giletta, Matteo; Scholte, Ron H. J.; Burk, William J.; Engels, Rutger C. M. E.; Larsen, Junilla K.; Prinstein, Mitchell J.; Ciairano, Silvia

2012-01-01

This study examined friendship selection and socialization as mechanisms explaining similarity in depressive symptoms in adolescent same-gender best friend dyads. The sample consisted of 1,752 adolescents (51% male) ages 12–16 years (M = 13.77, SD = 0.73) forming 487 friend dyads and 389 nonfriend dyads (the nonfriend dyads served as a comparison group). To test our hypothesis, we applied a multigroup actor–partner interdependence model to 3 friendship types that started and ended at different time points during the 2 waves of data collection. Results showed that adolescents reported levels of depressive symptoms at follow-up that were similar to those of their best friends. Socialization processes explained the increase in similarity exclusively in female dyads, whereas no evidence for friendship selection emerged for either male or female dyads. Additional analyses revealed that similarity between friends was particularly evident in the actual best friend dyads (i.e., true best friends), in which evidence for socialization processes emerged for both female and male friend dyads. Findings highlight the importance of examining friendship relations as a potential context for the development of depressive symptoms. PMID:21639621

Method of removing clogging materials due to ruthenium precipitates and sealing them in device

International Nuclear Information System (INIS)

Hoshikawa, Tadahiro; Sasahira, Akira.

1994-01-01

In a facility, such as a reprocessing facility, for processing a solution containing a great amount of ruthenium, precipitates due to evaporated ruthenium and cooled NO x are brought into contact with each other to decompose the precipitates due to the evaporated ruthenium. Precipitates due to ruthenium evaporated from the solution are reacted with cooled NO x , and the precipitates of ruthenium are decomposed and returned to the solution in the form of extremely fine particles together with recycling flow from the inner wall of the device. Since the precipitates of ruthenium returned to the solution are stable, they are no more evaporated and precipitated on the inner wall of the device. In the solution processing device having a possibility of clogging, clogging can be prevented and the precipitates of ruthenium can be sealed by decomposing them. (T.M.)

A thermodynamic/mass-transport model for the release of ruthenium from irradiated fuel

International Nuclear Information System (INIS)

Garisto, F.; Iglesias, F.C.; Hunt, C.E.L.

1990-01-01

Some postulated nuclear reactor accidents lead to fuel failures and hence release of fission products into the primary heat transport system (PHTS). To determine the consequences of such accidents, it is important to understand the behavior of fission products both in the PHTS and in the reactor containment building. Ruthenium metal has a high boiling point and is nonvolatile under reducing conditions. However, under oxidizing conditions ruthenium can form volatile oxides at relatively low temperatures and, hence, could escape from failed fuel and enter the containment building. The ruthenium radioisotope Ru-106 presents a potentially significant health risk if it is released outside the reactor containment building. Consequently, it is important to understand the behavior of ruthenium during a nuclear reactor accident. The authors review the thermodynamic behavior of ruthenium at high temperatures. The qualitative behavior of ruthenium, predicted using thermodynamic calculations, is then compared with experimental results from the Chalk River Nuclear Laboratories (CRNL). Finally, a simple thermodynamic/mass-transport model is proposed to explain the release behavior of ruthenium in a steam atmosphere

Ruthenium based redox flow battery for solar energy storage

International Nuclear Information System (INIS)

Chakrabarti, Mohammed Harun; Roberts, Edward Pelham Lindfield; Bae, Chulheung; Saleem, Muhammad

2011-01-01

Research highlights: → Undivided redox flow battery employing porous graphite felt electrodes was used. → Ruthenium acetylacetonate dissolved in acetonitrile was the electrolyte. → Charge/discharge conditions were determined for both 0.02 M and 0.1 M electrolytes. → Optimum power output of 0.180 W was also determined for 0.1 M electrolyte. → 55% voltage efficiency was obtained when battery was full of electrolytes. -- Abstract: The technical performance for the operation of a stand alone redox flow battery system for solar energy storage is presented. An undivided reactor configuration has been employed along with porous graphite felt electrodes and ruthenium acetylacetonate as electrolyte in acetonitrile solvent. Limiting current densities are determined for concentrations of 0.02 M and 0.1 M ruthenium acetylacetonate. Based on these, operating conditions for 0.02 M ruthenium acetylacetonate are determined as charging current density of 7 mA/cm 2 , charge electrolyte superficial velocity of 0.0072 cm/s (through the porous electrodes), discharge current density of 2 mA/cm 2 and discharge electrolyte superficial velocity of 0.0045 cm/s. An optimum power output of 35 mW is also obtained upon discharge at 2.1 mA/cm 2 . With an increase in the concentration of ruthenium species from 0.02 M to 0.1 M, the current densities and power output are higher by a factor of five approximately (at same superficial velocities) due to higher mass transport phenomenon. Moreover at 0.02 M concentration the voltage efficiency is better for battery full of electrolytes prior to charging (52.1%) in comparison to an empty battery (40.5%) due to better mass transport phenomenon. Voltage efficiencies are higher as expected at concentrations of 0.1 M ruthenium acetylacetonate (55% when battery is full of electrolytes and 48% when empty) showing that the all-ruthenium redox flow battery has some promise for future applications in solar energy storage. Some improvements for the

Solventless synthesis of ruthenium nanoparticles

Energy Technology Data Exchange (ETDEWEB)

García-Peña, Nidia G. [Departmento de Tecnociencias, Universidad Nacional Autónoma de México, Centro de Ciencias Aplicadas y Desarrollo Tecnológico, Universidad Nacional Autónoma de México, Cd. Universitaria A.P. 70-186, C.P. 04510 Coyoacán, México D.F. (Mexico); Redón, Rocío, E-mail: rredon@unam.mx [Departmento de Tecnociencias, Universidad Nacional Autónoma de México, Centro de Ciencias Aplicadas y Desarrollo Tecnológico, Universidad Nacional Autónoma de México, Cd. Universitaria A.P. 70-186, C.P. 04510 Coyoacán, México D.F. (Mexico); Herrera-Gomez, Alberto [Estudios Avanzados del Instituto Politécnico Nacional, Campus Juriquilla, Querétaro (Mexico); Fernández-Osorio, Ana Leticia [FES-Cuautitlán, Universidad Nacional Autónoma de México, Edo. de Mexico (Mexico); Bravo-Sanchez, Mariela; Gomez-Sosa, Gustavo [Estudios Avanzados del Instituto Politécnico Nacional, Campus Juriquilla, Querétaro (Mexico)

2015-06-15

Graphical abstract: - Highlights: • Successful synthesis of Ru nanoparticles by a cheap, fast and solventless approach was achieved. • The zero-valent state as well as the by-product/impurity free of the mechanochemical obtained Ru nanoparticles was proven by XPS, TEM and XRD. • Compared to two other synthesis strategies, the above-mentioned synthesis was more suitable to obtain smaller particles with fewer impurities in shorter time. - Abstract: This paper presents a novel solventless method for the synthesis of zero-valent ruthenium nanoparticles Ru(0). The proposed method, although not entirely new in the nanomaterials world, was used for the first time to synthesize zero-valent ruthenium nanoparticles. This new approach has proved to be an environmentally friendly, clean, cheap, fast, and reproducible technique which employs low amounts of solvent. It was optimized through varying amounts of reducing salt on a determined quantity of precursor and measuring the effect of this variation on the average particle size obtained. The resulting products were fully characterized by powder XRD, TEM, HR-TEM, and XPS studies, all of which corroborated the purity of the nanoparticles achieved. In order to verify the advantages of our method over other techniques, we compared our nanoparticles with two common colloidal-synthesized ruthenium nanoparticles.

Electrochemical studies of ruthenium compounds

International Nuclear Information System (INIS)

Kumar Ghosh, B.; Chakravorty, A.

1989-01-01

In many ways the chemistry of transition metals is the chemistry of multiple oxidation states and the associated redox phenomena. If a particular element were to be singeld out to illustrate this viewpoint, a model choice would be ruthenium - an element that is directly or indirectly the active centre of a plethora of redox phenomena encompassing ten different oxidation states and a breathtaking diversity of structure and bonding. In the present review the authors are primarily concerned with the oxidation states of certain ligands coordinated to ruthenium. This choice is deliberate since this is one area where the unique power of electrochemical methods is splendidly revealed. Without these methods, development in this area would have been greatly hampered. A brief summary of metal oxidation states is also included as a prelude to the main subject of this review. The authors have generally emphasize the information derived which is of chemical interest leaving the details of formal electrochemical arguments in the background. The authors have reviewed the pattern and systematics of ligand redox in ruthenium complexes. The synergistic combination of electrochemical and spectroscopic methods have vastly increased our understanding of ligand phenomena during the last 15 years or so. This in turn has led to better understanding and new developments in other fields. Photophysics and photochemistry could be cited as examples. (author). 176 refs.; 10 figs.; 10 tabs

Humor style similarity and difference in friendship dyads.

Science.gov (United States)

Hunter, Simon C; Fox, Claire L; Jones, Siân E

2016-01-01

This study assessed the concurrent and prospective (fall to spring) associations between four different humor styles to assess the degree to which stable friendships are characterized by similarity, and to assess whether best friends' humor styles influence each other's later use of humor. Participants were aged 11-13 years, with 87 stable, reciprocal best friend dyads. Self-report assessments of humor styles were completed on both occasions. Results indicated that there was no initial similarity in dyads' levels of humor. However, dyads' use of humor that enhances interpersonal relationships (Affiliative humor) became positively correlated by spring. Additionally, young people's use of this humor style was positively associated with their best friend's later use of the same. No such effects were present for humor which was aggressive, denigrating toward the self, or used to enhance the self. These results have clear implications for theories of humor style development, highlighting an important role for Affiliative humor within stable friendship dyads. Copyright © 2015 The Authors. Published by Elsevier Ltd.. All rights reserved.

Wechsler Adult Intelligence Scale-IV Dyads for Estimating Global Intelligence.

Science.gov (United States)

Girard, Todd A; Axelrod, Bradley N; Patel, Ronak; Crawford, John R

2015-08-01

All possible two-subtest combinations of the core Wechsler Adult Intelligence Scale-IV (WAIS-IV) subtests were evaluated as possible viable short forms for estimating full-scale IQ (FSIQ). Validity of the dyads was evaluated relative to FSIQ in a large clinical sample (N = 482) referred for neuropsychological assessment. Sample validity measures included correlations, mean discrepancies, and levels of agreement between dyad estimates and FSIQ scores. In addition, reliability and validity coefficients were derived from WAIS-IV standardization data. The Coding + Information dyad had the strongest combination of reliability and validity data. However, several other dyads yielded comparable psychometric performance, albeit with some variability in their particular strengths. We also observed heterogeneity between validity coefficients from the clinical and standardization-based estimates for several dyads. Thus, readers are encouraged to also consider the individual psychometric attributes, their clinical or research goals, and client or sample characteristics when selecting among the dyadic short forms. © The Author(s) 2014.

Photoinduced electron transfer within a novel synthesized short-chain dyad

International Nuclear Information System (INIS)

Bhattacharya, Sudeshna; Bardhan, Munmun; Kumar De, Avijit; De, Asish; Ganguly, Tapan

2010-01-01

The investigations were made by using electrochemical, steady state and time resolved spectroscopic (time correlated single photon counting and laser flash photolysis) techniques on a novel synthesized dyad, 1-(4-chloro-phenyl)-3-(4-methoxy-naphthalen-1-yl)-propenone (MNCA) where the donor 1-methoxy-naphthalene (MNT) is connected with the acceptor p-chloroacetophenone (PCA) by an unsaturated olefinic bond. This dyad possesses mainly extended (E-type) conformation both in the ground and excited state. The unchanged conformational geometry of this dyad even after photoexcitation makes it different from the previously studied benzothiophene-p-chloroacetophenone dyads, though both the donors present are isosteric molecules. In the cases of the latter dyads though E-type isomeric structure dominates in the ground state, considerable amount of Z-type (folded) species are produced in the excited state. It is hinted that the proximity effect of methoxy functionality in donor moiety, may be the reason for the formation of mostly E-isomeric species in the case of the present dyad MNCA system. The observed unchanged values of charge recombination and ion-pair lifetime, estimated from the analysis of transient absorption spectra of the dyad in presence of βCD and without it, confirm the proposition about the maintenance of the extended conformation even upon photoexcitation. From the transient absorption measurements it appears that due to increase of delay times between the exciting and probe pulses, higher triplet T n of the donor being generated gets involved in PET reactions with the surrounding medium ACN. From the present findings, MNCA in aqueous medium seems to be better candidate to build light energy conversion devices than the previously studied benzothiophene dyads where artificial devices like βCD were used to make elongated geometry. This geometry would help to prevent charge recombination processes within the redox components due to minimal overlapping between

Photoinduced electron transfer within a novel synthesized short-chain dyad

Energy Technology Data Exchange (ETDEWEB)

Bhattacharya, Sudeshna; Bardhan, Munmun; Kumar De, Avijit [Department of Spectroscopy, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700032, West Bengal (India); De, Asish [Department of Physics, Belda College, Midnapore, West Bengal (India); Ganguly, Tapan, E-mail: sptg@mahendra.iacs.res.i [Department of Spectroscopy, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700032, West Bengal (India)

2010-07-15

The investigations were made by using electrochemical, steady state and time resolved spectroscopic (time correlated single photon counting and laser flash photolysis) techniques on a novel synthesized dyad, 1-(4-chloro-phenyl)-3-(4-methoxy-naphthalen-1-yl)-propenone (MNCA) where the donor 1-methoxy-naphthalene (MNT) is connected with the acceptor p-chloroacetophenone (PCA) by an unsaturated olefinic bond. This dyad possesses mainly extended (E-type) conformation both in the ground and excited state. The unchanged conformational geometry of this dyad even after photoexcitation makes it different from the previously studied benzothiophene-p-chloroacetophenone dyads, though both the donors present are isosteric molecules. In the cases of the latter dyads though E-type isomeric structure dominates in the ground state, considerable amount of Z-type (folded) species are produced in the excited state. It is hinted that the proximity effect of methoxy functionality in donor moiety, may be the reason for the formation of mostly E-isomeric species in the case of the present dyad MNCA system. The observed unchanged values of charge recombination and ion-pair lifetime, estimated from the analysis of transient absorption spectra of the dyad in presence of betaCD and without it, confirm the proposition about the maintenance of the extended conformation even upon photoexcitation. From the transient absorption measurements it appears that due to increase of delay times between the exciting and probe pulses, higher triplet T{sub n} of the donor being generated gets involved in PET reactions with the surrounding medium ACN. From the present findings, MNCA in aqueous medium seems to be better candidate to build light energy conversion devices than the previously studied benzothiophene dyads where artificial devices like betaCD were used to make elongated geometry. This geometry would help to prevent charge recombination processes within the redox components due to minimal

Dansyl-anthracene dyads for ratiometric fluorescence recognition of Cu2+.

Science.gov (United States)

Kaur, Kuljit; Kumar, Subodh

2011-03-21

Dansyl-anthracene dyads 1 and 2 in CH(3)CN-H(2)O (7:3) selectively recognize Cu(2+) ions amongst alkali, alkaline earth and other heavy metal ions using both absorbance and fluorescence spectroscopy. In absorbance, the addition of Cu(2+) to the solution of dyads 1 or 2 results in appearance of broad absorption band from 200 nm to 725 nm for dyad 1 and from 200 nm to 520 nm for dyad 2. This is associated with color change from colorless to blue (for 1) and fluorescent green (for 2). This bathochromic shift of the spectrum could be assigned to internal charge transfer from sulfonamide nitrogen to anthracene moiety. In fluorescence, under similar conditions dyads 1 and 2 on addition of Cu(2+) selectively quench fluorescence due to dansyl moiety between 520-570 nm (for 1)/555-650 nm (for 2) with simultaneous fluorescence enhancement at 470 nm and 505 nm for dyads 1 and 2, respectively. Hence these dyads provide opportunity for ratiometric analysis of 1-50 μM Cu(2+). The other metal ions viz. Fe(3+), Co(2+), Ni(2+), Cd(2+), Zn(2+), Hg(2+), Ag(+), Pb(2+), Li(+), Na(+), K(+), Mg(2+), Ca(2+), Ba(2+) do not interfere in the estimation of Cu(2+) except Cr(3+) in case of dyad 1. The coordination of dimethylamino group of dansyl unit with Cu(2+) causes quenching of fluorescence due to dansyl moiety between 520-600 nm and also restricts the photoinduced electron transfer from dimethylamino to anthracene moiety to release fluorescence between 450-510 nm. This simultaneous quenching and release of fluorescence respectively due to dansyl and anthracene moieties emulates into Cu(2+) induced ratiometric change.

Ruthenium determination in new composite materials by coulometric titration with generated iron(2)

International Nuclear Information System (INIS)

Butakova, N.A.; Oganesyan, L.B.

1983-01-01

A coulometric technique is developed for ruthenium (4) titration with generated iron (2) in a mixture of hydrochloric-, sulfuric- and phosphoric acids with potentiometric and biammetric indication of the final titration point. Bi (3), Pd (2), Nb (5), Pt (4) Pb (2), Rh (3) do not interfere with the titration. Together with Ru (4) titrated are Ir (4), V (5), Au (3). The method is applied to analyze commercial samples of ruthenium dioxides, lead- and bismuth ruthenites, ruthenium pentafluorides containing 30-80% of ruthenium. The Ssub(r) values do not exceed 0.002

A preliminary conceptual framework for cancer couple dyads: live with love.

Science.gov (United States)

Li, Qiuping; Loke, Alice Y

2015-01-01

With the research focus on family caregiving shifting from the individual to the dyadic level, there is a need to develop a conceptual framework that focused on caregiver-patient dyads. The aim of this study was to develop a preliminary conceptual framework for cancer couple dyads, to "Live With Love." A literature search was conducted among 4 electronic databases to identify couple-based intervention studies related to couples coping with cancer. This report differs from a traditional literature review in that we synthesized the models or frameworks used in these studies rather than the outcomes of the studies. A preliminary Live With Love Conceptual Framework (P-LLCF) for cancer couple dyads was developed based on the conceptual frameworks adopted in related literature on spousal caregiving for patients with cancer. This P-LLCF contains 3 domains: event situation, dyadic mediators, and caregiver-patient dyads (appraisal, coping, and adjustment/outcomes). The various components in this P-LLCF will work together to benefit the positive dyadic adjustment/outcomes of the spousal caregiver-patient dyads in the cancer dyads' journey of coping with cancer. This P-LLCF sheds new light on the study of cancer couple dyads. It will be potentially valuable for guiding the related research and development of interventions on cancer couple dyads. Future research is needed to assess the outcome of interventions that focus on different components. It is also needed to develop measurements to assess dyadic adjustment/outcomes in nursing practice.

Removal of fission product ruthenium from purex process solutions: thiourea as complexing agent

International Nuclear Information System (INIS)

Floh, B.; Abrao, A.

1980-01-01

A new method for the treatment of spent uranium fuel is presented. It is based on the Purex Process using thiourea to increase the ruthenium decontamination factor. Thiourea exhibits a strong tendency for the formation of coordination compounds in acidic media. This tendency serves as a basis to transform nitrosyl-ruthenium species into Ru /SC(NH)(NH 2 )/ 2+ and Ru /SC(NH)(NH 2 )/ 3 complexes which are unextractable by TBP-varsol. The best conditions for the ruthenium-thiourea complex formation were found to be: thiourea-ruthenium ratio (mass/mass) close to 42, at 75 0 C, 30 minutes reaction time and aging period of 60 minutes. The ruthenium decontamination factor for a single uranium extraction are ca. 80-100, not interfering with extraction of actinides. These values are rather high in comparison to those obtained using the conventional Purex Process (e.g. F.D. sub(Ru)=10). By this reason the method developed here is suitable for the treatment of spent uranium fuels. Thiourea (100g/l) scrubbing experiments of ruthenium, partially co-extracted with actinides, confirmed the possibility of its removal from the extract. A decontamination greater than 83,5% for ruthenium as fission product is obtained in two stages with this procedure. (Author) [pt

Consonance perception of complex-tone dyads and chords

DEFF Research Database (Denmark)

Rasmussen, Marc; Santurette, Sébastien; MacDonald, Ewen

2014-01-01

Sensory consonance and dissonance are perceptual attributes of musical intervals conveying pleasant- ness, tension, and harmony in musical phrases. For complex-tone dyads, corresponding to two musical notes played simultaneously, consonance is known to vary with the ratio in fundamental frequency...... for a potential role of frequency selectivity for consonance perception of dyads, might not hold for chords...

Dendrimer-Encapsulated Ruthenium Nanoparticles as Catalysts for Lithium-O2 Batteries

Energy Technology Data Exchange (ETDEWEB)

Bhattacharya, Priyanka; Nasybulin, Eduard N.; Engelhard, Mark H.; Kovarik, Libor; Bowden, Mark E.; Li, Shari; Gaspar, Daniel J.; Xu, Wu; Zhang, Jiguang

2014-12-01

Dendrimer-encapsulated ruthenium nanoparticles (DEN-Ru) have been used as catalysts in lithium-O2 batteries for the first time. Results obtained from UV-vis spectroscopy, electron microscopy and X-ray photoelectron spectroscopy show that the nanoparticles synthesized by the dendrimer template method are ruthenium oxide instead of metallic ruthenium reported earlier by other groups. The DEN-Ru significantly improve the cycling stability of lithium (Li)-O2 batteries with carbon black electrodes and decrease the charging potential even at low catalyst loading. The monodispersity, porosity and large number of surface functionalities of the dendrimer template prevent the aggregation of the ruthenium nanoparticles making their entire surface area available for catalysis. The potential of using DEN-Ru as stand-alone cathode materials for Li-O2 batteries is also explored.

Application of the chemical properties of ruthenium to decontamination processes

International Nuclear Information System (INIS)

Fontaine, A.; Berger, D.

1965-01-01

The chemical properties of ruthenium in the form of an aqueous solution of the nitrate and of organic tributylphosphate solution are reviewed. From this data, some known examples are given: they demonstrate the processes of separation or of elimination of ruthenium from radioactive waste. (authors) [fr

Graphene/Ruthenium Active Species Aerogel as Electrode for Supercapacitor Applications.

Science.gov (United States)

Gigot, Arnaud; Fontana, Marco; Pirri, Candido Fabrizio; Rivolo, Paola

2017-12-30

Ruthenium active species containing Ruthenium Sulphide (RuS₂) is synthesized together with a self-assembled reduced graphene oxide (RGO) aerogel by a one-pot hydrothermal synthesis. Ruthenium Chloride and L-Cysteine are used as reactants. The hydrothermal synthesis of the innovative hybrid material occurs at 180 °C for 12 h, by using water as solvent. The structure and morphology of the hybrid material are fully characterized by Raman, XRD, XPS, FESEM and TEM. The XRD and diffraction pattern obtained by TEM display an amorphous nanostructure of RuS₂ on RGO crystallized flakes. The specific capacitance measured in planar configuration in 1 M NaCl electrolyte at 5 mV s -1 is 238 F g -1 . This supercapacitor electrode also exhibits perfect cyclic stability without loss of the specific capacitance after 15,000 cycles. In summary, the RGO/Ruthenium active species hybrid material demonstrates remarkable properties for use as active material for supercapacitor applications.

Activity and selectivity regulation of synthesis gas reaction over supported ruthenium catalysts

Energy Technology Data Exchange (ETDEWEB)

Fujimoto, K; Nobusawa, T; Fukushima, T; Tominaga, H

1985-01-01

The catalytic activities of supported ruthenium for synthesis-gas conversion to hydrocarbons was found to be in the following order: TiOS > Nb2O3 > ZrO2 > SiO2 > Ta2O5 > Al2O3 > V2O5 > MoO3 > WO3 > MnO2 > ZnO. Turnover frequencies of the supported ruthenium increased with decrease in dispersion of the metal particles for every carrier material. Even the activities per unit weight of metals were higher for low-dispersion ruthenium of Al2O3, TiO2, and ZrO2. The chain-growth probability of a hydrocarbon product, which is characterized by the Schulz-Flory distribution, increased markedly with decrease in the metal dispersion irrespective of the carrier material. The catalytic activity of ruthenium particles with a dispersed ruthenium increased almost linearly with an increase in reaction pressure (up to at least 2.0 MPa). 23 references, 10 figures, 3 tables.

Extraction of ruthenium thiocyanate and its separation from rhodium by polyurethane foam

International Nuclear Information System (INIS)

Al-Bazi, S.J.; Chow, A.

1984-01-01

Conditions for the formation and extraction of the thiocyanate complex of ruthenium are reported. Distribution coefficients of more than 10 4 and a capacity of about 0.24 mole per kg of foam were obtained. The effect of the chloride salts of various univalent cations on the extraction of Ru(SCN) 6 3- indicated that the efficiency of ruthenium extraction depends on how well the cation fits into the polyether segment of the polyurethane foam, which agrees with the 'cation-chelation' mechanism. The separation of ruthenium and rhodium indicated that more than 95% of the rhodium remained in the aqueous phase and about 95% of the ruthenium was retained by the polyurethane foam and could be easily recovered. (author)

Hydrothermal synthesis and physicochemical properties of ruthenium(0) nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Dikhtiarenko, A., E-mail: dikhtiarenkoalla@uniovi.es [Departamento de Quimica Organica e Inorganica, Universidad de Oviedo - CINN, 33006 Oviedo (Spain); Khainakov, S.A.; Garcia, J.R.; Gimeno, J. [Departamento de Quimica Organica e Inorganica, Universidad de Oviedo - CINN, 33006 Oviedo (Spain); Pedro, I. de; Fernandez, J. Rodriguez [CITIMAC, Facultad de Ciencias, Universidad de Cantabria, 39005 Santander (Spain); Blanco, J.A. [Departamento de Fisica, Universidad de Oviedo, 33007 Oviedo (Spain)

2012-09-25

Highlights: Black-Right-Pointing-Pointer Ruthenium nanoparticles were synthesized by hydrothermal technique. Black-Right-Pointing-Pointer The average size of the nanoparticles are depend on the reducing agent used. Black-Right-Pointing-Pointer The magnetic response seems to be dominated by a paramagnetic contribution characteristic of the band electronic magnetism of the ruthenium(0) nanoparticles. - Abstract: The synthesis of ruthenium nanoparticles in hydrothermal conditions using mild reducing agents (succinic acid, ascorbic acid and sodium citrate) is reported. The shape of the nanoparticles depends on the type of the reducing agent, while the size is more influenced by the pH of the medium. The magnetic response seems to be dominated by a paramagnetic contribution characteristic of the band electronic magnetism of the nanoparticles.

Surface and sub-surface thermal oxidation of thin ruthenium films

NARCIS (Netherlands)

Coloma Ribera, R.; van de Kruijs, Robbert Wilhelmus Elisabeth; Kokke, S.; Zoethout, E.; Yakshin, Andrey; Bijkerk, Frederik

2014-01-01

A mixed 2D (film) and 3D (nano-column) growth of ruthenium oxide has been experimentally observed for thermally oxidized polycrystalline ruthenium thin films. Furthermore, in situ x-ray reflectivity upon annealing allowed the detection of 2D film growth as two separate layers consisting of low

Thermodynamic data bases for multivalent elements: An example for ruthenium

International Nuclear Information System (INIS)

Rard, J.A.

1987-11-01

A careful consideration and understanding of fundamental chemistry, thermodynamics, and kinetics is absolutely essential when modeling predominance regions and solubility behavior of elements that exhibit a wide range of valence states. Examples of this are given using the ruthenium-water system at 298.15 K, for which a critically assessed thermochemical data base is available. Ruthenium exhibits the widest range of known aqueous solution valence states. Known solid anhydrous binary oxides of ruthenium are crystalline RuO 2 , RuO 4 , and possibly RuO 3 (thin film), and known hydroxides/hydrated oxides (all amorphous) are Ru(OH) 3 . H 2 O, RuO 2 . 2H 2 O, RuO 2 . H 2 O, and a poorly characterized Ru(V) hydrous oxide. Although the other oxides, hydroxides, and hydrous oxides are generally obtained as precipitates from aqueous solutions, they are thermodynamically unstable with regard to RuO 2 (cr) formation. Characterized aqueous species of ruthenium include RuO 4 (which slowly oxidizes water and which dissociates as a weak acid), RuO 4 - and RuO 4 2- (which probably contain lesser amounts of RuO 3 (OH) 2 - and RuO 3 (OH) 2 2- , respectively, and other species), Ru(OH) 2 2+ , Ru 4 (OH) 12 4+ , Ru(OH) 4 , Ru 3+ , Ru(OH) 2+ , Ru(OH) 2 + , Ru 2+ , and some hydroxytetramers with formal ruthenium valences of 3.75 ≥ Z ≥ 2.0. Potential pH diagrams of the predominance regions change significantly with concentration due to polymerization/depolymerization reactions. Failure to consider the known chemistry of ruthenium can yield large differences in predicted solubilities

Hazards and control of ruthenium in the nuclear fuel cycle

International Nuclear Information System (INIS)

Eichholz, G.G.

1978-01-01

A review is presented of present information on the possible hazards of radioruthenium in the nuclear fuel cycle and its behaviour in nuclear operations and in the environment. The subject is dealt with under the following headings: basic chemical and nuclear properties of ruthenium; chemistry (including the ruthenium-nitric acid system, electrochemistry, extraction processes); ruthenium toxicity; generation of radioruthenium (fallout sources, reactor sources, fuel reprocessing operations); waste treatment (cementation and bitumenization, calcining processes, vitrification); movement in the environment (movement of airborne effluents, liquid effluents and the freshwater environment, marine environment, bottom sediments, marine organisms, terrestrial environments, uptake in vegetation and animals); conclusion. (U.K.)

Ruthenium determination by the method of inversion voltammetry on graphite electrode

Energy Technology Data Exchange (ETDEWEB)

Dominova, I G; Kolpakova, N A; Stromberg, A G [Tomskij Politekhnicheskij Inst. (USSR)

1978-12-01

Optimal conditions for determining ruthenium by inversion voltammetry on a graphite electrode are 0.1 M KCl or KNO/sub 3/, pH 2-3, electrolysis potential - 1.0 V. A linear dependence of ruthenium electrodissolution current on its concentration in the solution makes it possible to use inversion voltammetry for determining 5x10/sup -7/ - 1x10/sup -4/ g-ion Ru/l. Ruthenium can be determined in the presence of a large excess of nickel and copper but commensurable amounts of mercury adn platinum metals interfere.

Ruthenium nitrosyl complexes in radioactive waste solutions in reprocessing plants. Pt. 3

International Nuclear Information System (INIS)

Blasius, E.; Mueller, K.

1984-01-01

With capillary isotachophoresis and free-flow isotachophoresis it is possible to separate and isolate preparatively the mononuclear cationic ruthenium nitrosyl nitrato complexes. The behaviour of these complexes during storage, concentration and calcination is studied: The conversion of six ruthenium nitrosyl nitrato complexes as a function of time is studied at -36 0 C, 0 0 C, +3 0 C and 100 0 C. The percentage of ruthenium nitrosyl complexes with NO 3 - as ligand increased markedly during concentration experiments. Above 250 0 C NOsub(x) is liberated and the colour of the residue changes from brown to brownish-grey. At 400 0 C ruthenium complexes are no longer detected and the inner walls of the apparatus are covered with RuO 2 . (orig.)

Processing of radioactive ruthenium with aluminosilicate gels

International Nuclear Information System (INIS)

Kanno, Takuji; Ichinose, Yasuhiro; Ito, Katsuo

1979-01-01

Coprecipitation of radioactive Ru with hydroxides has been studied for the purpose of the management of the high level waste from the nuclear fuel reprocessing. Aluminosilicate gel used as coprecipitant was prepared by addition of aqueous sodium hydroxide to sodium aluminate-sodium silicate solution containing ruthenium nitrate. Ruthenium quantitatively precipitates under the conditions, aluminate > 4 x 10 -2 M, Al/Si 0 C. However, volatilization rate of Ru is suppressed by coating with mullite phase into which aluminosilicate gel transformes above 900 0 C. The amount of Ru volatilized in Ar-flow was reduced to about 10% of that in air-flow. (author)

Electrochemistry of ruthenium acetate trigonal cluster with dimethylsulfoxide and pyridine

International Nuclear Information System (INIS)

Alexiou, A.D.P.; Toma, H.E.

1990-01-01

The electrochemical behaviour of asymetric cluster with two ligands, pyridine and dimethyl-sulfoxide is studied for determining the changes from cluster oxidation influence on DMSO-Ru ligand and for verifying the ligand isomers which were detected in two systems; [Ru(NHsub(3))dmso] sup(3+/2+) [9] and [Ru(edta)dmso] sup(1-/2-)[10]. (author)

Ruthenium release from thermally overheated nitric acid solution containing ruthenium nitrosyl nitrate and sodium nitrate to solidify

Energy Technology Data Exchange (ETDEWEB)

Sawada, Kayo; Ueda, Yasuyuki; Enokida, Youichi [Nuclear Chemical Engineering Laboratory, Nagoya University, Nagoya 4648603 (Japan)

2016-07-01

Radioactive ruthenium (Ru) is one of the dominant elemental species released into the environment from a fuel reprocessing plant in a hypothetical design accident due to its relatively higher fission yield and longer half-life. After the hypothetical accident assuming the loss of all electric power and cooling functions, high-level liquid waste (HLLW) may be overheated by the energetic decays of many fission products in it, and Ru may be oxidized to the volatile tetroxide, RuO{sub 4}, which is released through the off-gas pathway. At a reprocessing plant in Japan, alkaline solution from the solvent scrubbing stream is sometimes mixed with the HLLW followed by vitrification, which can be influenced by the addition of sodium nitrate to a simulated HLLW containing ruthenium nitrosyl nitrate that was experimentally evaluated on a small scale using the overheated nitric acid solution of 2 mol/dm{sup 3}, which was kept at 180 Celsius degrees in a glass evaporator placed in a thermostatic bath. The release fraction of Ru increased by approximately 30% by the addition of sodium nitrate. This may be partially explained by the existence of relatively highly concentrated nitrate ions in the liquid phase that oxidize the ruthenium species to RuO{sub 4} during the drying process. (authors)

Method of improving the decontaminating efficiency of ruthenium in evaporating treatment of nitric acid

International Nuclear Information System (INIS)

Kubota, Kanya; Yamana, Hajime; Takeda, Seiichiro.

1984-01-01

Purpose: To significantly improve the ruthenium removing efficiency in a nitric acid solution in an acid recovery system for the recovery of nitric acid from nitric acid liquid wastes through evaporating condensation. Method: Upon evaporating treatment of nitric acid solution containing ruthenium by supplying and heating the solution to a nitric acid evaporating device, hydrazine is previously added to the nitric acid solution. Hydrazine and intermediate reaction product of hydrazine such as azide causes a reduction reaction with intermediate reaction product of ruthenium tetraoxide to suppress the oxidation of ruthenium and thereby improve the decontaminating efficiency of ruthenium. The amount of hydrazine to be added is preferably between 20 - 500 mg/l and most suitably between 200 - 2000 mg/l per one liter of the liquid in the evaporating device. (Seki, T.)

Catalytic Ammonia Decomposition Over Ruthenium Nanoparticles Supported on Nano-Titanates

DEFF Research Database (Denmark)

Klerke, Asbjørn; Klitgaard, Søren Kegnæs; Fehrmann, Rasmus

2009-01-01

Nanosized Na2Ti3O7, K2Ti6O13 and Cs2Ti6O13 materials were prepared and used as supports of ruthenium nanoparticles for catalytic ammonia decomposition. It is shown that these catalysts exhibit higher catalytic activity than ruthenium supported on TiO2 nanoparticles promoted with cesium. The diffe...

Ruthenium-Catalyzed Aerobic Oxidation of Amines.

Science.gov (United States)

Ray, Ritwika; Hazari, Arijit Singha; Lahiri, Goutam Kumar; Maiti, Debabrata

2018-01-18

Amine oxidation is one of the fundamental reactions in organic synthesis as it leads to a variety of value-added products such as oximes, nitriles, imines, and amides among many others. These products comprise the key N-containing building blocks in the modern chemical industry, and such transformations, when achieved in the presence of molecular oxygen without using stoichiometric oxidants, are much preferred as they circumvent the production of unwanted wastes. In parallel, the versatility of ruthenium catalysts in various oxidative transformations is well-documented. Herein, this review focuses on aerobic oxidation of amines specifically by using ruthenium catalysts and highlights the major achievements in this direction and challenges that still need to be addressed. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Recommendation of ruthenium source for sludge batch flowsheet studies

Energy Technology Data Exchange (ETDEWEB)

Woodham, W. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

2017-09-13

Included herein is a preliminary analysis of previously-generated data from sludge batches 7a, 7b, 8, and 9 sludge simulant and real-waste testing, performed to recommend a form of ruthenium for future sludge batch simulant testing under the nitric-formic flowsheet. Focus is given to reactions present in the Sludge Receipt and Adjustment Tank cycle, given that this cycle historically produces the most changes in chemical composition during Chemical Process Cell processing. Data is presented and analyzed for several runs performed under the nitric-formic flowsheet, with consideration given to effects on the production of hydrogen gas, nitrous oxide gas, consumption of formate, conversion of nitrite to nitrate, and the removal and recovery of mercury during processing. Additionally, a brief discussion is given to the effect of ruthenium source selection under the nitric-glycolic flowsheet. An analysis of data generated from scaled demonstration testing, sludge batch 9 qualification testing, and antifoam degradation testing under the nitric-glycolic flowsheet is presented. Experimental parameters of interest under the nitric-glycolic flowsheet include N2O production, glycolate destruction, conversion of glycolate to formate and oxalate, and the conversion of nitrite to nitrate. To date, the number of real-waste experiments that have been performed under the nitric-glycolic flowsheet is insufficient to provide a complete understanding of the effects of ruthenium source selection in simulant experiments with regard to fidelity to real-waste testing. Therefore, a determination of comparability between the two ruthenium sources as employed under the nitric-glycolic flowsheet is made based on available data in order to inform ruthenium source selection for future testing under the nitric-glycolic flowsheet.

C-N bond cleavage of anilines by a (salen)ruthenium(VI) nitrido complex.

Science.gov (United States)

Man, Wai-Lun; Xie, Jianhui; Pan, Yi; Lam, William W Y; Kwong, Hoi-Ki; Ip, Kwok-Wa; Yiu, Shek-Man; Lau, Kai-Chung; Lau, Tai-Chu

2013-04-17

We report experimental and computational studies of the facile oxidative C-N bond cleavage of anilines by a (salen)ruthenium(VI) nitrido complex. We provide evidence that the initial step involves nucleophilic attack of aniline at the nitrido ligand of the ruthenium complex, which is followed by proton and electron transfer to afford a (salen)ruthenium(II) diazonium intermediate. This intermediate then undergoes unimolecular decomposition to generate benzene and N2.

Monodispersed Zinc Oxide Nanoparticle-Dye Dyads and Triads

Energy Technology Data Exchange (ETDEWEB)

Gladfelter, Wayne L. [Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry; Blank, David A. [Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry; Mann, Kent R. [Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry

2017-06-22

The overall energy conversion efficiency of photovoltaic cells depends on the combined efficiencies of light absorption, charge separation and charge transport. Dye-sensitized solar cells are photovoltaic devices in which a molecular dye absorbs light and uses this energy to initiate charge separation. The most efficient dye-sensitized solar cells (DSSCs) use nanocrystal titanium dioxide films to which are attached ruthenium complexes. Numerous studies have provided valuable insight into the dynamics of these and analogous photosystems, but the lack of site homogeneity in binding dye molecules to metal oxide films and nanocrystals (NCs) is a significant impediment to extracting fundamental details about the electron transfer across the interface. Although zinc oxide is emerging as a potential semiconducting component in DSSCs, there is less known about the factors controlling charge separation across the dye/ZnO interface. Zinc oxide crystallizes in the wurtzite lattice and has a band gap of 3.37 eV. One of the features that makes ZnO especially attractive is the remarkable ability to control the morphology of the films. Using solution deposition processes, one can prepare NCs, nanorods and nanowires having a variety of shapes and dimensions. This project solved problems associated with film heterogeneity through the use of dispersible sensitizer/ZnO NC ensembles. The overarching goal of this research was to study the relationship between structure, energetics and dynamics in a set of synthetically controlled donor-acceptor dyads and triads. These studies provided access to unprecedented understanding of the light absorption and charge transfer steps that lie at the heart of DSSCs, thus enabling significant future advances in cell efficiencies. The approach began with the construction of well-defined dye-NC dyads that were sufficiently dispersible to allow the use of state of the art pulsed laser spectroscopic and kinetic methods to understand the charge transfer

Device for separating ruthenium ion from spent fuel material

International Nuclear Information System (INIS)

Izumida, Tatsuo; Sasahira, Akira; Ozawa, Yoshihiro; Kawamura, Fumio.

1988-01-01

Purpose: To separate plutonium ions efficiently and selectively from organic solvent containing tributyl phosphate used in the main step of reprocessing process. Constitution: The device comprises, as the main constituent factor, a liquid-liquid contact device for bringing not water soluble organic solvent into contact with a nitric acid solution of spent fuel substances and a liquid-liquid contact-separation device for bringing an organic solvent solution containing spent fuel substances separated with nitric acid into contact again with nitric acid. Then, a device is disposed between two liquid-liquid contact devices for staying ruthenium ions and organic solvent for a sufficient time. In this way, ruthenium ions in the organic solvent containing butyl phosphate are gradually converted into complex compounds combined with tributyl phosphate thereby enabling to separate ruthenium ions efficiently and remarkably reduce the corrosion of equipments. (Horiuchi, T.)

Design and development of novel MRI compatible zirconium- ruthenium alloys with ultralow magnetic susceptibility.

Science.gov (United States)

Li, H F; Zhou, F Y; Li, L; Zheng, Y F

2016-04-19

In the present study, novel MRI compatible zirconium-ruthenium alloys with ultralow magnetic susceptibility were developed for biomedical and therapeutic devices under MRI diagnostics environments. The results demonstrated that alloying with ruthenium into pure zirconium would significantly increase the strength and hardness properties. The corrosion resistance of zirconium-ruthenium alloys increased significantly. High cell viability could be found and healthy cell morphology observed when culturing MG 63 osteoblast-like cells and L-929 fibroblast cells with zirconium-ruthenium alloys, whereas the hemolysis rates of zirconium-ruthenium alloys are zirconium-ruthenium alloys (1.25 × 10(-6) cm(3)·g(-1)-1.29 × 10(-6) cm(3)·g(-1) for zirconium-ruthenium alloys) are ultralow, about one-third that of Ti-based alloys (Ti-6Al-4V, ~3.5 × 10(-6) cm(3)·g(-1), CP Ti and Ti-6Al-7Nb, ~3.0 × 10(-6) cm(3)·g(-1)), and one-sixth that of Co-Cr alloys (Co-Cr-Mo, ~7.7 × 10(-6) cm(3)·g(-1)). Among the Zr-Ru alloy series, Zr-1Ru demonstrates enhanced mechanical properties, excellent corrosion resistance and cell viability with lowest magnetic susceptibility, and thus is the optimal Zr-Ru alloy system as therapeutic devices under MRI diagnostics environments.

Some thermophysical properties of ruthenium in the neighbourhood of the melting point

International Nuclear Information System (INIS)

Sheindlin, A.E.; Kats, S.A.; Berezin, B.Ya.; Chekhovskoy, V.Ya.; Kenisarin, M.M.

1975-01-01

The technique of levitation calorimetry has been used to study for the first time thermophysical properties of ruthenium in the neighbourhood of the melting point. To measure enthalpy a copper block calorimeter with an istohermal jacket has been used. Basing on the values measured the equations for enthalpy of solid and liquid ruthenium within the temperature ranges of 2,270-2,607 K and 2,607-2,760 K respectively have been obtained by the least squares method. In addition the melting temperature of ruthenium and its brightness temperature at the melting point, the wavelength being 0.65 micron, have been measured. The results of the measurements have been used to calculate the heat and entropy of fusion, the specific heat of solid and that of liquid ruthenium and its normal spectral emissivity at the melting point

Anchoring selenido-carbonyl ruthenium clusters to functionalized silica xerogels

International Nuclear Information System (INIS)

Cauzzi, Daniele; Graiff, Claudia; Pattacini, Roberto; Predieri, Giovanni; Tiripicchio, Antonio

2003-01-01

Silica Xerogels containing carbonyl Ru 3 Se 2 nido clusters were prepared in three different ways. The simple dispersion of [Ru 3 (μ 3 -Se) 2 (CO) 7 (PPh 3 ) 2 ] via sol gel process produces an inhomogeneous material; by contrast, homogeneous xerogels were obtained by reaction of [Ru 3 (μ 3 -Se) 2 (CO) 8 (PPh 3 )] with functionalized xerogels containing grafted diphenylphosphine moieties and by reaction of [Ru 3 (CO) 12 ] with a xerogel containing grafted phosphine-selenide groups. The reaction between [Ru 3 (CO) 12 ] and dodecyl diphenylphosphine selenide led to the formation of four selenido carbonyl clusters, which are soluble in hydrocarbon solvents and can be deposited as thin films from their solution by slow evaporation. (author)

Verbal and nonverbal behavior of ability-grouped dyads

Science.gov (United States)

Jones, M. Gail; Carter, Glenda

In this study we describe the social interactions of ability-grouped dyads as they constructed knowledge of balance concepts to elucidate the relationship between interactions and conceptual growth. The verbal and nonverbal behaviors of 30 fifth-grade students were recorded as they completed three activities related to balance. These student interactions were examined within a framework of social cognition. For each dyad, characteristics of ability-grouped dyads were identified. Results revealed that high-achieving students effectively used prior experiences, maintained focus on the learning task, and were able to manipulate the equipment effectively to construct knowledge. Low-achieving students exhibited off-task behavior, lacked a metacognitive framework for organizing the learning tasks, centered on irrelevant features of the equipment, and were unable to use language effectively to mediate learning. Within low-high student dyads, high-achieving students typically modeled thinking processes and strategies for manipulating equipment. In addition, they focused the low-achieving students on the components of the tasks while verbally monitoring their progress, thus enabling low students to identify the critical features necessary for concept construction. These results highlighted the differences that students have in the use of language and tools. Low students' inefficient use of tools has implications for the ways science teachers structure lessons and group students for laboratory work.Received: 8 March 1993; Revised: 6 January 1994;

Kinetics and Photochemistry of Ruthenium Bisbipyridine Diacetonitrile Complexes: An Interdisciplinary Inorganic and Physical Chemistry Laboratory Exercise

Science.gov (United States)

Rapp, Teresa L.; Phillips, Susan R.; Dmochowski, Ivan J.

2016-01-01

The study of ruthenium polypyridyl complexes can be widely applied across disciplines in the undergraduate curriculum. Ruthenium photochemistry has advanced many fields including dye-sensitized solar cells, photoredox catalysis, lightdriven water oxidation, and biological electron transfer. Equally promising are ruthenium polypyridyl complexes…

Design and development of novel MRI compatible zirconium- ruthenium alloys with ultralow magnetic susceptibility

Science.gov (United States)

Li, H.F.; Zhou, F.Y.; Li, L.; Zheng, Y.F.

2016-01-01

In the present study, novel MRI compatible zirconium-ruthenium alloys with ultralow magnetic susceptibility were developed for biomedical and therapeutic devices under MRI diagnostics environments. The results demonstrated that alloying with ruthenium into pure zirconium would significantly increase the strength and hardness properties. The corrosion resistance of zirconium-ruthenium alloys increased significantly. High cell viability could be found and healthy cell morphology observed when culturing MG 63 osteoblast-like cells and L-929 fibroblast cells with zirconium-ruthenium alloys, whereas the hemolysis rates of zirconium-ruthenium alloys are alloys and Ti-based alloys, the magnetic susceptibilities of the zirconium-ruthenium alloys (1.25 × 10−6 cm3·g−1–1.29 × 10−6 cm3·g−1 for zirconium-ruthenium alloys) are ultralow, about one-third that of Ti-based alloys (Ti–6Al–4V, ~3.5 × 10−6 cm3·g−1, CP Ti and Ti–6Al–7Nb, ~3.0 × 10−6 cm3·g−1), and one-sixth that of Co–Cr alloys (Co–Cr–Mo, ~7.7 × 10−6 cm3·g−1). Among the Zr–Ru alloy series, Zr–1Ru demonstrates enhanced mechanical properties, excellent corrosion resistance and cell viability with lowest magnetic susceptibility, and thus is the optimal Zr–Ru alloy system as therapeutic devices under MRI diagnostics environments. PMID:27090955

Confinement of ruthenium oxides volatilized during nuclear fuels reprocessing

International Nuclear Information System (INIS)

Maas, E.T. Jr.; Longo, J.M.

1980-01-01

While many materials have been suggested and employed as trapping agents for gaseous oxides of fission product ruthenium volatilized during nuclear fuels reprocessing, none that is known to form thermodynamically stable compounds with rutheniunm has been utilized. We have employed alkaline earth metal compounds for this purpose because of their ability to form stable mixed metal oxide phases with ruthenium. Results of experiments in which RuO 4 was volatilized from either a solid source (RuO 2 .xH 2 O) or from solution [Ru(NO)(NO 3 ) 3 ] in HNO 3 and passed through beds of alkaline earth metal carbonates and calcium oxide held at 600 to 750 0 C have demonstrated that compounds of formulation MRuO 3 (M = calcium, strontium, barium) are formed. Under oxidizing conditions, these materials exist as stable ceramic phases, whereas under reducing conditions, they are transformed into intimate mixtures of the alkaline earth metal oxide and nonvolatile ruthenium metal

A trident dithienylethene-perylenemonoimide dyad with super fluorescence switching speed and ratio

Science.gov (United States)

Li, Chong; Yan, Hui; Zhao, Ling-Xi; Zhang, Guo-Feng; Hu, Zhe; Huang, Zhen-Li; Zhu, Ming-Qiang

2014-12-01

Photoswitchable fluorescent diarylethenes are promising in molecular optical memory and photonic devices. However, the performance of current diarylethenes is far from satisfactory because of the scarcity of high-speed switching capability and large fluorescence on-off ratio. Here we report a trident perylenemonoimide dyad modified by triple dithienylethenes whose photochromic fluorescence quenching ratio at the photostationary state exceeds 10,000 and the fluorescence quenching efficiency is close to 100% within seconds of ultraviolet irradiation. The highly sensitive fluorescence on/off switching of the trident dyad enables recyclable fluorescence patterning and all-optical transistors. The prototype optical device based on the trident dyad enables the optical switching of incident light and conversion from incident light wavelength to transmitted light wavelength, which is all-optically controlled, reversible and wavelength-convertible. In addition, the trident dyad-staining block copolymer vesicles are observed via optical nanoimaging with a sub-100 nm resolution, portending a potential prospect of the dithienylethene dyad in super-resolution imaging.

How Not to Let Secrets Out When Conducting Qualitative Research With Dyads.

Science.gov (United States)

Ummel, Deborah; Achille, Marie

2016-05-01

Confidentiality is one of the cornerstones of research involving human participants. Researchers are the frontline gatekeepers of their participants' right to confidentiality, and situations can arise that challenge this responsibility. This is the case when individuals who have shared a common experience (i.e., dyads) are interviewed separately, but interview results are disseminated within the context of dyads. Based on our experience of conducting research with dyads and given how little literature is available to serve as guide, we set out to write this article to share the knowledge we acquired and the solutions we found. We will describe both the ethical challenges and the methodological decisions involved in conducting qualitative research with dyads. The article also describes different modalities of dyadic analysis, their benefits and drawbacks. This endeavor seems especially relevant as research with dyads is emerging in several domains involving couples, families, caregivers and health. © The Author(s) 2016.

Patient and caregiver congruence: the importance of dyads in heart failure care.

Science.gov (United States)

Retrum, Jessica H; Nowels, Carolyn T; Bekelman, David B

2013-01-01

Informal (family) caregivers are integrally involved in chronic heart failure (HF) care. Few studies have examined HF patients and their informal caregiver as a unit in a relationship, or a dyad. Dyad congruence, or consistency in perspective, is relevant to numerous aspects of living with HF and HF care. Incongruence or lack of communication could impair disease management and advance care planning. The purpose of this qualitative study was to examine for congruence and incongruence between HF patients and their informal (family) caregivers. Secondary analyses examined the relationship of congruence to emotional distress and whether dyad relationship characteristics (eg, parent-child vs spouse) were associated with congruence. Thirty-four interviews consisting of HF patients and their current informal caregiver (N = 17 dyads) were conducted. Each dyad member was asked similar questions about managing HF symptoms, psychosocial care, and planning for the future. Interviews were transcribed and analyzed using the general inductive approach. Congruence, incongruence, and lack of communication between patients and caregivers were identified in areas such as managing illness, perceived care needs, perspectives about the future of HF, and end-of-life issues. Seven dyads were generally congruent, 4 were incongruent, and 6 demonstrated a combination of congruence and incongruence. Much of the tension and distress among dyads related to conflicting views about how emotions should be dealt with or expressed. Dyad relationship (parent-child vs spouse) was not clearly associated with congruence, although the relationship did appear to be related to perceived caregiving roles. Several areas of HF clinical and research relevance, including self-care, advance care planning, and communication, were affected by congruence. Further research is needed to define how congruence is related to other relationship characteristics, such as relationship quality, how congruence can best be

Dyad conversations about self-stigma in two Scottish communities.

Science.gov (United States)

Mackay, Rob; Bradstreet, Simon; McArthur, Andy; Dunion, Linda

2015-06-01

This study explored self-stigma in 2 Scottish communities and strategies for challenging stigma and discrimination. A mixed-methods approach was used encompassing a survey including the Internalized Stigma of Mental Illness Inventory (ISMI) and facilitated dyad conversations with people with lived experience of mental illness. Self-reported experience of self-stigma across 2 communities was most closely associated with the ISMI Alienation cluster, accompanied by a high level of agreement with the Stigma Resistance cluster. Some 44% agreed that stereotypes about people with mental health problems applied to them, and almost 2/3 felt that having a mental health problem had spoiled their lives. Many participants reported reduced confidence, loss of hope, a sense of failure, and protecting oneself through social withdrawal. The findings also offer hope through narratives from people who have "pushed back" and are striving to reduce their own self-stigma by engaging with others and managing their own recovery journey. The journey through self-stigma and beyond has to be informed by what we know works with recovery from a mental health problem. At a policy and practice level, we recommend emphasis on 4 priorities: (a) refocusing antistigma and discrimination efforts more on the experiences of people who report stigma, (b) rights-based approaches, (c) identity-based work, and (d) information sharing and educational strategies. (c) 2015 APA, all rights reserved).

A new approach to synthesize supported ruthenium phosphides for hydrodesulfurization

International Nuclear Information System (INIS)

Wang, Qingfang; Wang, Zhiqiang; Yin, Xiaoqian; Zhou, Linxi; Zhang, Minghui

2016-01-01

Highlights: • We bring out a new method to synthesize noble metal phosphides at low temperature. • Both RuP and Ru_2P were synthesized using triphenylphosphine as phosphorus sources. • Ru_2P was the better active phase for HDS than RuP and metal Ru. • RuP/SiO_2 prepared by new method had better HDS activity to that by TPR method. - Abstract: Supported noble metal ruthenium phosphides were synthesized by one-step H_2-thermal treatment method using triphenylphosphine (TPP) as phosphorus sources at low temperatures. Two phosphides RuP and Ru_2P can be prepared by this method via varying the molar ratio of metal salt and TPP. The as-prepared phosphides were characterized by X-ray powder diffraction (XRD), low-temperature N_2 adsorption, CO chemisorption and transmission electronic microscopy (TEM). The supported ruthenium phosphides prepared by new method and conventional method together with contradistinctive metallic ruthenium were evaluated in hydrodesulfurization (HDS) of dibenzothiophene (DBT). The catalytic results showed that metal-rich Ru_2P was the better active phase for HDS than RuP and metal Ru. Besides this, ruthenium phosphide catalyst prepared by new method exhibited superior HDS activity to that prepared by conventional method.

A new approach to synthesize supported ruthenium phosphides for hydrodesulfurization

Energy Technology Data Exchange (ETDEWEB)

Wang, Qingfang [Tianjin Key Laboratory of Water Environment and Resources, Tianjin Normal University, Tianjin 300387 (China); Key Laboratory of Advanced Energy Materials Chemistry (MOE), Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), College of Chemistry, Nankai University, Tianjin 300071 (China); Wang, Zhiqiang [Tianjin Key Laboratory of Water Environment and Resources, Tianjin Normal University, Tianjin 300387 (China); Yin, Xiaoqian; Zhou, Linxi [Key Laboratory of Advanced Energy Materials Chemistry (MOE), Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), College of Chemistry, Nankai University, Tianjin 300071 (China); Zhang, Minghui, E-mail: zhangmh@nankai.edu.cn [Key Laboratory of Advanced Energy Materials Chemistry (MOE), Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), College of Chemistry, Nankai University, Tianjin 300071 (China); College of Chemistry and Environmental Science, Kashgar University, Kashgar 844006 (China)

2016-02-15

Highlights: • We bring out a new method to synthesize noble metal phosphides at low temperature. • Both RuP and Ru{sub 2}P were synthesized using triphenylphosphine as phosphorus sources. • Ru{sub 2}P was the better active phase for HDS than RuP and metal Ru. • RuP/SiO{sub 2} prepared by new method had better HDS activity to that by TPR method. - Abstract: Supported noble metal ruthenium phosphides were synthesized by one-step H{sub 2}-thermal treatment method using triphenylphosphine (TPP) as phosphorus sources at low temperatures. Two phosphides RuP and Ru{sub 2}P can be prepared by this method via varying the molar ratio of metal salt and TPP. The as-prepared phosphides were characterized by X-ray powder diffraction (XRD), low-temperature N{sub 2} adsorption, CO chemisorption and transmission electronic microscopy (TEM). The supported ruthenium phosphides prepared by new method and conventional method together with contradistinctive metallic ruthenium were evaluated in hydrodesulfurization (HDS) of dibenzothiophene (DBT). The catalytic results showed that metal-rich Ru{sub 2}P was the better active phase for HDS than RuP and metal Ru. Besides this, ruthenium phosphide catalyst prepared by new method exhibited superior HDS activity to that prepared by conventional method.

Atomic Layer Deposition of Ruthenium with TiN Interface for Sub-10 nm Advanced Interconnects beyond Copper

DEFF Research Database (Denmark)

Wen, Liang Gong; Roussel, Philippe; Pedreira, Olalla Varela

2016-01-01

. These extremely scaled ruthenium lines show excellent electromigration behavior. Time-dependent dielectric breakdown measurements reveal negligible ruthenium ion drift into low-kappa dielectrics up to 200 degrees C, demonstrating that ruthenium can be used as a barrierless metallization in interconnects...

Exciplex mediated photoinduced electron transfer reactions of phthalocyanine-fullerene dyads.

Science.gov (United States)

Niemi, Marja; Tkachenko, Nikolai V; Efimov, Alexander; Lehtivuori, Heli; Ohkubo, Kei; Fukuzumi, Shunichi; Lemmetyinen, Helge

2008-07-31

Evidences of an intramolecular exciplex intermediate in a photoinduced electron transfer (ET) reaction of double-linked free-base and zinc phthalocyanine-C60 dyads were found. This was the first time for a dyad with phthalocyanine donor. Excitation of the phthalocyanine moiety of the dyads results in rapid ET from phthalocyanine to fullerene via an exciplex state in both polar and nonpolar solvents. Relaxation of the charge-separated (CS) state Pc(*+)-C60(*-) in a polar solvent occurs directly to the ground state in 30-70 ps. In a nonpolar solvent, roughly 20% of the molecules undergo transition from the CS state to phthalocyanine triplet state (3)Pc*-C60 before relaxation to the ground state. Formation of the CS state was confirmed with electron spin resonance measurements at low temperature in both polar and nonpolar solvent. Reaction schemes for the photoinduced ET reactions of the dyads were completed with rate constants obtained from the time-resolved absorption and emission measurements and with state energies obtained from the fluorescence, phosphorescence, and voltammetric measurements.

Influences on Infant Feeding: Perceptions of Mother-Father Parent Dyads.

Science.gov (United States)

Majee, Wilson; Thullen, Matthew J; Davis, Alexandra N; Sethi, Tarunjot K

The purpose of this study was to examine interrelational-, organizational-, and community-level influences on how coparents collaborate about infant and toddler feeding. Using qualitative methods, we interviewed mother-father parent dyads to explore the potential influences on infant and toddler feeding. Participants were purposively recruited from two Midwest, rural, university-system pediatric clinics. Thematic analysis was used to code the data. Mother-father dyadic interviews were conducted using a semistructured interview schedule. Twenty-four mother-father dyads who had a child between the ages of 6 and 36 months were interviewed together. Major themes include interpersonal factors (peer behavior reinforcement, dyad and important others infant feeding conflict, conflict resolution proactiveness), organizational factors (healthcare provider infant-feeding support, workplace flexibility), and community factors (public perception on breastfeeding and social media influence). Community-based collaboration can be a platform for mother-father dyads, researchers, public health nurses, and other healthcare providers to proactively create interventions that include opportunity for building coparenting skills and infant-feeding knowledge that promote team management of common early childhood feeding challenges.

The use of ruthenium in various fields of industry

International Nuclear Information System (INIS)

Sinitsin, N.M.

1990-03-01

Metallic ruthenium, its alloys, and compounds with other metals have a number of valuable and specific properties which allow the usage of ruthenium in various fields of modern technology, which is described here. In the atomic technology, Ru can be used in the building of reactors as a material of construction since its isotopes don't possess a high neutron capture cross section. Ruthenium is used for the preparation of γ- and β-ray emission sources. Isotopes Ru-103 and Ru-106 are widely used as tracers. They are successfully used for the monitoring of production, for the development of new technological and analytical methods of the extraction of Ru, for the cleansing of other valuable metals from Ru, for the monitoring of the thickness of Ru microfilm on the substrate, and for the monitoring of Ru losses in various processes. In the nuclear reactor, during the process of uranium and plutonium decay, large amounts of stable Ru isotopes are formed together with radioactive isotopes. In such a manner, a nuclear reactor can supply Ru. Special attention must be paid to the usage of direct coordination Ru compounds. Ru and its compounds possess a large number of very valuable properties, many of the secrets of Ru must still be discovered. It can be presumed that the demand for ruthenium will grow in the forthcoming years and the range and volume of its applications will increase

Ruthenium oxide resistors as sensitive elements of composite bolometers

International Nuclear Information System (INIS)

Benassai, M.; Gallinaro, G.; Gatti, F.; Siri, S.; Vitale, S.

1988-01-01

Bolometers for particle detection made with Ruthenium oxide thermistors could be produced by means of a simple technique on a variety of different materials as substrata. Preliminary results on alpha particle detection with devices realized using commercial RuO 2 thick film resistor (Tfr) are considered positive for devices operating between. 3 and .1 k and determined us to pursue further the idea. Ruthenium oxide resistors on sapphire at the moment are being prepared. The behaviour of these devices st temperatures lower than .1 k has to be investigated in more detail

Effect of dyad training on medical students' cardiopulmonary resuscitation performance.

Science.gov (United States)

Wang, Candice; Huang, Chin-Chou; Lin, Shing-Jong; Chen, Jaw-Wen

2017-03-01

We investigated the effects of dyadic training on medical students' resuscitation performance during cardiopulmonary resuscitation (CPR) training.We provided students with a 2-hour training session on CPR for simulated cardiac arrest. Student teams were split into double groups (Dyad training groups: Groups A and B) or Single Groups. All groups received 2 CPR simulation rounds. CPR simulation training began with peer demonstration for Group A, and peer observation for Group B. Then the 2 groups switched roles. Single Groups completed CPR simulation without peer observation or demonstration. Teams were then evaluated based on leadership, teamwork, and team member skills.Group B had the highest first simulation round scores overall (P = 0.004) and in teamwork (P = 0.001) and team member skills (P = 0.031). Group B also had the highest second simulation round scores overall (P training groups with those of Single Groups in overall scores, leadership scores, teamwork scores, and team member scores. In the second simulation, Dyad training groups scored higher in overall scores (P = 0.002), leadership scores (P = 0.044), teamwork scores (P = 0.005), and team member scores (P = 0.008). Dyad training groups also displayed higher improvement in overall scores (P = 0.010) and team member scores (P = 0.022).Dyad training was effective for CPR training. Both peer observation and demonstration for peers in dyad training can improve student resuscitation performance.

Effect of dyad training on medical students’ cardiopulmonary resuscitation performance

Science.gov (United States)

Wang, Candice; Huang, Chin-Chou; Lin, Shing-Jong; Chen, Jaw-Wen

2017-01-01

Abstract We investigated the effects of dyadic training on medical students’ resuscitation performance during cardiopulmonary resuscitation (CPR) training. We provided students with a 2-hour training session on CPR for simulated cardiac arrest. Student teams were split into double groups (Dyad training groups: Groups A and B) or Single Groups. All groups received 2 CPR simulation rounds. CPR simulation training began with peer demonstration for Group A, and peer observation for Group B. Then the 2 groups switched roles. Single Groups completed CPR simulation without peer observation or demonstration. Teams were then evaluated based on leadership, teamwork, and team member skills. Group B had the highest first simulation round scores overall (P = 0.004) and in teamwork (P = 0.001) and team member skills (P = 0.031). Group B also had the highest second simulation round scores overall (P training groups with those of Single Groups in overall scores, leadership scores, teamwork scores, and team member scores. In the second simulation, Dyad training groups scored higher in overall scores (P = 0.002), leadership scores (P = 0.044), teamwork scores (P = 0.005), and team member scores (P = 0.008). Dyad training groups also displayed higher improvement in overall scores (P = 0.010) and team member scores (P = 0.022). Dyad training was effective for CPR training. Both peer observation and demonstration for peers in dyad training can improve student resuscitation performance. PMID:28353555

Dyads, a generalisation of monads

NARCIS (Netherlands)

Fokkinga, M.M.

The concept of dyad is defined as the least common generalisation of monads and co-monads. So, taking some of the ingredients to be the identity, the concept specialises to the concept of monad, and taking other ingredients to be the identity it specialises to co-monads. Except for one axiom, all

Depression impacts the physiological responsiveness of mother–daughter dyads during social interaction

Science.gov (United States)

Amole, Marlissa C.; Cyranowski, Jill M.; Wright, Aidan G. C.; Swartz, Holly A.

2017-01-01

Background Maternal depression is associated with increased risk of psychiatric illness in offspring. While risk may relate to depressed mothers' difficulties regulating emotions in the context of interacting with offspring, physiological indicators of emotion regulation have rarely been examined during mother–child interactions—and never among mother–adolescent dyads in which both mother and adolescent have histories of major depressive disorder (MDD). Methods We examined changes in high-frequency heart rate variability (HF-HRV), an indicator of parasympathetic (vagal) function that has been related to depression, stress, social engagement, and emotion regulation, in 46 mother–daughter dyads (23 in which both mother and daughter had an MDD history and 23 never-depressed controls). Hierarchical linear models evaluated changes in HF-HRV while mother–daughter dyads engaged in discussions about shared pleasant events and relationship conflicts. Results While control dyads displayed positive slopes (increases) in HF-HRV during both discussions, MDD dyads displayed minimal change in HF-HRV across discussions. Among controls, HF-HRV slopes were positively correlated between mothers and daughters during the pleasant events' discussion. In contrast, HF-HRV slopes were negatively correlated between MDD mothers and daughters during both discussions. Conclusions Vagal responses observed in control mother–daughter dyads suggest a pattern of physiological synchrony and reciprocal positive social engagement, which may play a role in adolescent development of secure social attachments and healthy emotion regulation. In contrast, MDD mothers and daughters displayed diminished and discordant patterns of vagal responsiveness. More research is needed to understand the development and consequences of these patterns of parasympathetic responses among depressed mother–daughter dyads. PMID:28060443

Depression impacts the physiological responsiveness of mother-daughter dyads during social interaction.

Science.gov (United States)

Amole, Marlissa C; Cyranowski, Jill M; Wright, Aidan G C; Swartz, Holly A

2017-02-01

Maternal depression is associated with increased risk of psychiatric illness in offspring. While risk may relate to depressed mothers' difficulties regulating emotions in the context of interacting with offspring, physiological indicators of emotion regulation have rarely been examined during mother-child interactions-and never among mother-adolescent dyads in which both mother and adolescent have histories of major depressive disorder (MDD). We examined changes in high-frequency heart rate variability (HF-HRV), an indicator of parasympathetic (vagal) function that has been related to depression, stress, social engagement, and emotion regulation, in 46 mother-daughter dyads (23 in which both mother and daughter had an MDD history and 23 never-depressed controls). Hierarchical linear models evaluated changes in HF-HRV while mother-daughter dyads engaged in discussions about shared pleasant events and relationship conflicts. While control dyads displayed positive slopes (increases) in HF-HRV during both discussions, MDD dyads displayed minimal change in HF-HRV across discussions. Among controls, HF-HRV slopes were positively correlated between mothers and daughters during the pleasant events' discussion. In contrast, HF-HRV slopes were negatively correlated between MDD mothers and daughters during both discussions. Vagal responses observed in control mother-daughter dyads suggest a pattern of physiological synchrony and reciprocal positive social engagement, which may play a role in adolescent development of secure social attachments and healthy emotion regulation. In contrast, MDD mothers and daughters displayed diminished and discordant patterns of vagal responsiveness. More research is needed to understand the development and consequences of these patterns of parasympathetic responses among depressed mother-daughter dyads. © 2016 Wiley Periodicals, Inc.

Autonomy and control in dyads: effects on interaction quality and joint creative performance.

Science.gov (United States)

Weinstein, Netta; Hodgins, Holley S; Ryan, Richard M

2010-12-01

Two studies examined interaction quality and joint performance on two creative tasks in unacquainted dyads primed for autonomy or control orientations. It was hypothesized that autonomy-primed dyads would interact more constructively, experience more positive mood, and engage the task more readily, and as a result these dyads would perform better. To test this, Study 1 primed orientation and explored verbal creative performance on the Remote Associates Task (RAT). In Study 2, dyads were primed with autonomy and control orientation and videotaped during two joint creative tasks, one verbal (RAT) and one nonverbal (charades). Videotapes were coded for behavioral indicators of closeness and task engagement. Results showed that autonomy-primed dyads felt closer, were more emotionally and cognitively attuned, provided empathy and encouragement to partners, and performed more effectively. The effects of primed autonomy on creative performance were mediated by interpersonal quality, mood, and joint engagement.

Effect of ruthenium cluster on the photoluminescence of chemically derivatized porous silicon

International Nuclear Information System (INIS)

Boukherroub, Rabah; Zargarian, Davit; Reber, Christian; Lockwood, David J.; Carty, Arthur J.; Wayner, Danial D.M.

2003-01-01

A green photoluminescent triruthenium cluster (I) has been chemisorbed on highly luminescent porous silicon (PSi) layers, either freshly prepared or chemically modified with 1-decene, ethyl undecylenate, or undecylenic acid, in order to study the influence of the cluster on the photoluminescence (PL) arising from the PSi. Immersing the hydrogen-terminated PSi in a hexane solution of (I) for several days at room temperature led to the quenching of PL arising from PSi; the only PL detected was due to the Ru cluster (I). A complete quenching of the PL due to PSi was also observed when derivatized PSi surfaces were exposed to the same solution of (I); in these cases, the PL of (I) also shifted to lower energies. Both the quenching of the PL arising from the PSi layers and the shift in the PL of the cluster (I) are likely due to the difference in the chemical interaction of the PO moiety and the CO groups of the Ru cluster with the terminal functional group of the organic monolayer

Effect of ruthenium cluster on the photoluminescence of chemically derivatized porous silicon

Energy Technology Data Exchange (ETDEWEB)

Boukherroub, Rabah; Zargarian, Davit; Reber, Christian; Lockwood, David J.; Carty, Arthur J.; Wayner, Danial D.M

2003-07-15

A green photoluminescent triruthenium cluster (I) has been chemisorbed on highly luminescent porous silicon (PSi) layers, either freshly prepared or chemically modified with 1-decene, ethyl undecylenate, or undecylenic acid, in order to study the influence of the cluster on the photoluminescence (PL) arising from the PSi. Immersing the hydrogen-terminated PSi in a hexane solution of (I) for several days at room temperature led to the quenching of PL arising from PSi; the only PL detected was due to the Ru cluster (I). A complete quenching of the PL due to PSi was also observed when derivatized PSi surfaces were exposed to the same solution of (I); in these cases, the PL of (I) also shifted to lower energies. Both the quenching of the PL arising from the PSi layers and the shift in the PL of the cluster (I) are likely due to the difference in the chemical interaction of the PO moiety and the CO groups of the Ru cluster with the terminal functional group of the organic monolayer.

Effect of ruthenium cluster on the photoluminescence of chemically derivatized porous silicon

Science.gov (United States)

Boukherroub, Rabah; Zargarian, Davit; Reber, Christian; Lockwood, David J.; Carty, Arthur J.; Wayner, Danial D. M.

2003-07-01

A green photoluminescent triruthenium cluster (I) has been chemisorbed on highly luminescent porous silicon (PSi) layers, either freshly prepared or chemically modified with 1-decene, ethyl undecylenate, or undecylenic acid, in order to study the influence of the cluster on the photoluminescence (PL) arising from the PSi. Immersing the hydrogen-terminated PSi in a hexane solution of (I) for several days at room temperature led to the quenching of PL arising from PSi; the only PL detected was due to the Ru cluster (I). A complete quenching of the PL due to PSi was also observed when derivatized PSi surfaces were exposed to the same solution of (I); in these cases, the PL of (I) also shifted to lower energies. Both the quenching of the PL arising from the PSi layers and the shift in the PL of the cluster (I) are likely due to the difference in the chemical interaction of the PO moiety and the CO groups of the Ru cluster with the terminal functional group of the organic monolayer.

Mitigation of strontium and ruthenium release in the CANDU primary heat transport system

International Nuclear Information System (INIS)

McFarlane, J.

1998-03-01

In certain severe accident scenarios, low-volatility fission products can appear to contribute significantly to dose, if treated with undue conservatism. Hence a survey was performed, to see if factors that may mitigate release of strontium and ruthenium could be incorporated into safety analyses, to cover parameters such as location in the fuel matrix under normal operating conditions, release from fuel, transport and deposition in the primary heat transport system and chemistry. In addition chemical equilibrium calculations were performed to investigate the volatility of strontium and ruthenium in the presence of uranium and important fission products. Strontium is very soluble in the U0 2 fuel, up to 12 atom %, and hence release is improbable, particularly under oxidizing conditions until volatilization of the fuel matrix itself occurs. Ruthenium, however, can be released at low temperatures, but only under oxidizing conditions. These may occur during a fuel-handling accident or as a result of an end-fitting failure. Under these conditions, the primary heat transport system cannot be credited for retention. The volatile form of ruthenium, RuO 4 (g), is thermally unstable above 381 K and decomposes to RuO 2 (s) and O 2 (g) upon contact with surfaces, a factor that is likely to minimize the release of ruthenium into the environment. (author)

Ruthenium(III Chloride Catalyzed Acylation of Alcohols, Phenols, and Thiols in Room Temperature Ionic Liquids

Directory of Open Access Journals (Sweden)

Mingzhong Cai

2009-09-01

Full Text Available Ruthenium(III chloride-catalyzed acylation of a variety of alcohols, phenols, and thiols was achieved in high yields under mild conditions (room temperature in the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]. The ionic liquid and ruthenium catalyst can be recycled at least 10 times. Our system not only solves the basic problem of ruthenium catalyst reuse, but also avoids the use of volatile acetonitrile as solvent.

Interface behaviour and electrical performance of ruthenium ...

Indian Academy of Sciences (India)

Rutherford backscattering spectrometry; Raman spectroscopy; oxidation; silicide; Schottky barrier diodes; ruthenium ... water and then dried with nitrogen gas before being loaded into the vacuum ... laser of wavelength 514.6 nm. Full I–V and ...

A Study of the Effect of Dyad Practice Versus That of Individual Practice on Simulation-Based Complex Skills Learning and of Students’ Perceptions of How and Why Dyad Practice Contributes to Learning

DEFF Research Database (Denmark)

Räder, Sune Bernd Emil Werner; Henriksen, Ann-Helen; Butrymovich, Vitalij

2014-01-01

PURPOSE: The aims of this study were (1) to explore the effectiveness of dyad practice compared with individual practice on a simulator for learning a complex clinical skill and (2) to explore medical students' perceptions of how and why dyad practice on a simulator contributes to learning...... a complex skill. METHOD: In 2011, the authors randomly assigned 84 medical students to either the dyad or the individual practice group to learn coronary angiography skills using instruction videos and a simulator. Two weeks later, participants each performed two video-recorded coronary angiographies...... of the two groups (mean±standard deviation, 68%±13% for individual versus 63%±16% for dyad practice; P=.18). Dyad practice participants noted that several key factors contributed to their learning: being equal-level novices, the quality of the cooperation between partners, observational learning and overt...

Autonomous Motivation and Fruit/Vegetable Intake in Parent–Adolescent Dyads

Science.gov (United States)

Dwyer, Laura A.; Bolger, Niall; Laurenceau, Jean-Philippe; Patrick, Heather; Oh, April Y.; Nebeling, Linda C.; Hennessy, Erin

2017-01-01

Introduction Autonomous motivation (motivation to engage in a behavior because of personal choice, interest, or value) is often associated with health behaviors. The present study contributes to research on motivation and eating behaviors by examining: (1) how autonomous motivation is correlated within parent–adolescent dyads; and (2) whether parent- and adolescent-reported autonomous motivation predicts the parent–adolescent correlation in fruit and vegetable (FV) intake frequency. Methods Data were drawn from the Family Life, Activity, Sun, Health, and Eating (FLASHE) Study, a cross-sectional U.S. survey of parent–adolescent dyads led by the National Cancer Institute and fielded between April and October 2014. In 2016, data were analyzed from dyads who had responses on a six-item self-report measure of daily frequency of FV consumption and a two-item self-report measure of autonomous motivation for consuming FVs. Results Parents' and adolescents' reports of autonomous motivation and FV intake frequency were positively correlated. Both parents' and adolescents' autonomous motivation predicted higher levels of their own FV intake frequency and that of their dyad partner (p-values ≤0.001). These effects of autonomous motivation explained 22.6% of the parent–adolescent correlation in FV intake frequency. Actor effects (one's motivation predicting their own FV intake frequency) were stronger than partner effects (one's motivation predicting their partner's FV intake frequency). Conclusions Parent–adolescent similarity in autonomous motivation for healthy eating may contribute to similarity in eating behaviors. Future research should further examine how individual-level health behavior correlates influence health behaviors within dyads. PMID:28526363

Autonomous Motivation and Fruit/Vegetable Intake in Parent-Adolescent Dyads.

Science.gov (United States)

Dwyer, Laura A; Bolger, Niall; Laurenceau, Jean-Philippe; Patrick, Heather; Oh, April Y; Nebeling, Linda C; Hennessy, Erin

2017-06-01

Autonomous motivation (motivation to engage in a behavior because of personal choice, interest, or value) is often associated with health behaviors. The present study contributes to research on motivation and eating behaviors by examining (1) how autonomous motivation is correlated within parent-adolescent dyads and (2) whether parent- and adolescent-reported autonomous motivation predicts the parent-adolescent correlation in fruit and vegetable (FV) intake frequency. Data were drawn from the Family Life, Activity, Sun, Health, and Eating (FLASHE) Study, a cross-sectional U.S. survey of parent-adolescent dyads led by the National Cancer Institute and fielded between April and October 2014. In 2016, data were analyzed from dyads who had responses on a six-item self-report measure of daily frequency of FV consumption and a two-item self-report measure of autonomous motivation for consuming FVs. Parents' and adolescents' reports of autonomous motivation and FV intake frequency were positively correlated. Both parents' and adolescents' autonomous motivation predicted higher levels of their own FV intake frequency and that of their dyad partner (p-values ≤0.001). These effects of autonomous motivation explained 22.6% of the parent-adolescent correlation in FV intake frequency. Actor effects (one's motivation predicting their own FV intake frequency) were stronger than partner effects (one's motivation predicting their partner's FV intake frequency). Parent-adolescent similarity in autonomous motivation for healthy eating may contribute to similarity in eating behaviors. Future research should further examine how individual-level health behavior correlates influence health behaviors within dyads. Published by Elsevier Inc.

Synthesis of the first dimetallacarborane ruthenium-iridium cluster

International Nuclear Information System (INIS)

Lobanova, I.A.; Chizhevskij, I.T.; Petrovskij, P.V.; Bregadze, V.I.

1996-01-01

New electron-deficient dimetallic cluster (η 4 -C 8 H 12 )IrRu(μ-H)(PPh 3 ) 2 (η 5 -C 2 B 9 H 11 ) (1), has been prepared by the reaction of exo-nido-5,6,10-[Cl(PPh 3 ) 2 Ru]-5,6.10-(μ-H) 3 -10-H-7,8-C 2 B 9 H 8 with dimeric or acetylacetonate complexes of Ir in the presence of KOH in ethanol at 22 deg C. 1 H, 13 C, 31 P, 11 B NMR and IR spectral data for 1 are presented. 8 refs., 1 scheme

Spectrophotometric determination of ruthenium(III) and rhodium(III) after extraction of their cyclohexylthioglycolate complexes into chloroform

International Nuclear Information System (INIS)

Rao, A.L.J.; Gupta, Usha; Puri, B.K.

1986-01-01

Cyclohexylthioglycolate has been used as a reagent for the spectrophotometric determination of ruthenium(III) and rhodium(III) after the extraction of their complexes into chloroform. Various parameters involved in the extraction have been studied and the composition of the extracted complex has been established in each instance. Ruthenium and rhodium complexes are extracted into chloroform in the pH ranges 5.0-9.0 and 9.0-12.5, respectively. The ruthenium complex absorbs strongly at 365 nm, whereas the rhodium complex shows a maximum absorption at 345 nm. Beer's law is obeyed over the concentration range 6-96 μg for ruthenium and 2-41 μg for rhodium in 10 ml of the chloroform solution. The molar absorptivities are 5.02 x 10 3 l mol -1 cm -1 for ruthenium and 1.60 x 10 4 l mol -1 cm -1 for rhodium. Ten replicate determinations on a sample solution containing 60.3 μg of ruthenium or 20.6 μg of rhodium gave mean absorbances of 0.300 and 0.320 with standard deviations of 0.0021 and 0.0025 and relative standard deviations of 0.70% and 0.78%, respectively. The interference of various ions has been studied and the method has been applied to the determination of the metals in various synthetic samples. Conditions have also been developed for the simultaneous determination of ruthenium and rhodium. (author)

Flameless atomic absorption determination of ruthenium using a ''Saturn-1'' spectrophotometer

International Nuclear Information System (INIS)

Pichkov, V.N.; Sinitsyn, N.M.; Sadikova, F.G.; Govorova, M.I.; Yakshinskij, A.I.

1980-01-01

A flameless atomic absorption method is suggested for determining ruthenium in samples of complicated composition using a ''Saturn-1'' spectrophotometer with a L'vov graphite cuvette. The method was used for determining ruthenium in a copper-based sample (10 -3 % Ru) and in electrolyte slurries (10 -3 -10 -2 %). The limit of detection Csub(min, 0.95) = 3.0x10 -3 μg Ru/ml. Other platinum metals do not interfere [ru

A New Homogeneous Catalyst for the Dehydrogenation of Dimethylamine Borane Starting with Ruthenium(III Acetylacetonate

Directory of Open Access Journals (Sweden)

Ebru Ünel Barın

2015-06-01

Full Text Available The catalytic activity of ruthenium(III acetylacetonate was investigated for the first time in the dehydrogenation of dimethylamine borane. During catalytic reaction, a new ruthenium(II species is formed in situ from the reduction of ruthenium(III and characterized using UV-Visible, Fourier transform infrared (FTIR, 1H NMR, and mass spectroscopy. The most likely structure suggested for the ruthenium(II species is mer-[Ru(N2Me43(acacH]. Mercury poisoning experiment indicates that the catalytic dehydrogenation of dimethylamine-borane is homogeneous catalysis. The kinetics of the catalytic dehydrogenation of dimethylamine borane starting with Ru(acac3 were studied depending on the catalyst concentration, substrate concentration and temperature. The hydrogen generation was found to be first-order with respect to catalyst concentration and zero-order regarding the substrate concentration. Evaluation of the kinetic data provides the activation parameters for the dehydrogenation reaction: the activation energy Ea = 85 ± 2 kJ·mol−1, the enthalpy of activation ∆H# = 82 ± 2 kJ·mol−1 and the entropy of activation; ∆S# = −85 ± 5 J·mol−1·K−1. The ruthenium(II catalyst formed from the reduction of ruthenium(III acetylacetonate provides 1700 turnovers over 100 hours in hydrogen generation from the dehydrogenation of dimethylamine borane before deactivation at 60 °C.

Mitigation of strontium and ruthenium release in the CANDU primary heat transport system

Energy Technology Data Exchange (ETDEWEB)

McFarlane, J

1998-03-01

In certain severe accident scenarios, low-volatility fission products can appear to contribute significantly to dose, if treated with undue conservatism. Hence a survey was performed, to see if factors that may mitigate release of strontium and ruthenium could be incorporated into safety analyses, to cover parameters such as location in the fuel matrix under normal operating conditions, release from fuel, transport and deposition in the primary heat transport system and chemistry. In addition chemical equilibrium calculations were performed to investigate the volatility of strontium and ruthenium in the presence of uranium and important fission products. Strontium is very soluble in the U0{sub 2} fuel, up to 12 atom %, and hence release is improbable, particularly under oxidizing conditions until volatilization of the fuel matrix itself occurs. Ruthenium, however, can be released at low temperatures, but only under oxidizing conditions. These may occur during a fuel-handling accident or as a result of an end-fitting failure. Under these conditions, the primary heat transport system cannot be credited for retention. The volatile form of ruthenium, RuO{sub 4}(g), is thermally unstable above 381 K and decomposes to RuO{sub 2}(s) and O{sub 2}(g) upon contact with surfaces, a factor that is likely to minimize the release of ruthenium into the environment. (author)

Ruthenium on chitosan: A recyclable heterogeneous catalyst for aqueous hydration of nitriles to amides

Science.gov (United States)

Ruthenium has been immobilized over chitosan by simply stirring an aqueous suspension of chitosan in water with ruthenium chloride and has been utilized for the oxidation of nitriles to amides; the hydration of nitriles occurs in high yield and excellent selectivity, which procee...

Rectifying behaviour of self assembled porphyrin/fullerene dyads on Au(111)

International Nuclear Information System (INIS)

Matino, F; Arima, V; Maruccio, G; Phaneuf, R J; Sole, R Del; Mele, G; Vasapollo, G; Cingolani, R; Rinaldi, R

2007-01-01

Here we present an Ultra High Vacuum Scanning Tunnelling Microscopy (UHVSTM) and Scanning Tunnelling Spectroscopy (STS) study of self assembled donor-acceptor conjugate dyads, consisting of fulleropyrrolidines and metallo-porphyrins immobilized on gold. The coverage in the fulleropyrrolidine layers was optimized up to obtain isolated protrusions which we identify with isolated dyads since their lateral dimensions are consistent with the fullerene size. The STS study reveals a diode-like asymmetric behaviour of the dyads, different from the surrounding areas. We investigate also the influence of the tunneling conditions on the rectifying ratio which is found to be dependent on the initial set point conditions and to increase by increasing the tip-sample distance

Rectifying behaviour of self assembled porphyrin/fullerene dyads on Au(111)

Energy Technology Data Exchange (ETDEWEB)

Matino, F [National Nanotechnology Laboratory (CNR-INFM)- Distretto Tecnologico ISUFI-Universita degli studi di Lecce - via Arnesano, 73100 Lecce (Italy); Arima, V [National Nanotechnology Laboratory (CNR-INFM)- Distretto Tecnologico ISUFI-Universita degli studi di Lecce - via Arnesano, 73100 Lecce (Italy); Maruccio, G [National Nanotechnology Laboratory (CNR-INFM)- Distretto Tecnologico ISUFI-Universita degli studi di Lecce - via Arnesano, 73100 Lecce (Italy); Phaneuf, R J [National Nanotechnology Laboratory (CNR-INFM)- Distretto Tecnologico ISUFI-Universita degli studi di Lecce - via Arnesano, 73100 Lecce (Italy); Sole, R Del [Dipartimento di Ingegneria dell' Innovazione - Universita degli Studi di Lecce- via Arnesano, 73100 Lecce (Italy); Mele, G [Dipartimento di Ingegneria dell' Innovazione - Universita degli Studi di Lecce- via Arnesano, 73100 Lecce (Italy); Vasapollo, G [Dipartimento di Ingegneria dell' Innovazione - Universita degli Studi di Lecce- via Arnesano, 73100 Lecce (Italy); Cingolani, R [National Nanotechnology Laboratory (CNR-INFM)- Distretto Tecnologico ISUFI-Universita degli studi di Lecce - via Arnesano, 73100 Lecce (Italy); Rinaldi, R [National Nanotechnology Laboratory (CNR-INFM)- Distretto Tecnologico ISUFI-Universita degli studi di Lecce - via Arnesano, 73100 Lecce (Italy)

2007-04-15

Here we present an Ultra High Vacuum Scanning Tunnelling Microscopy (UHVSTM) and Scanning Tunnelling Spectroscopy (STS) study of self assembled donor-acceptor conjugate dyads, consisting of fulleropyrrolidines and metallo-porphyrins immobilized on gold. The coverage in the fulleropyrrolidine layers was optimized up to obtain isolated protrusions which we identify with isolated dyads since their lateral dimensions are consistent with the fullerene size. The STS study reveals a diode-like asymmetric behaviour of the dyads, different from the surrounding areas. We investigate also the influence of the tunneling conditions on the rectifying ratio which is found to be dependent on the initial set point conditions and to increase by increasing the tip-sample distance.

Biological properties of novel ruthenium- and osmium-nitrosyl complexes with azole heterocycles

KAUST Repository

Novak, Maria S.; Bü chel, Gabriel E.; Keppler, Bernhard K.; Jakupec, Michael A.

2016-01-01

Since the discovery that nitric oxide (NO) is a physiologically relevant molecule, there has been great interest in the use of metal nitrosyl compounds as antitumor pharmaceuticals. Particularly interesting are those complexes which can deliver NO to biological targets. Ruthenium- and osmium-based compounds offer lower toxicity compared to other metals and show different mechanisms of action as well as different spectra of activity compared to platinum-based drugs. Novel ruthenium- and osmium-nitrosyl complexes with azole heterocycles were studied to elucidate their cytotoxicity and possible interactions with DNA. Apoptosis induction, changes of mitochondrial transmembrane potential and possible formation of reactive oxygen species were investigated as indicators of NO-mediated damage by flow cytometry. Results suggest that ruthenium- and osmium-nitrosyl complexes with the general formula (indazolium)[cis/trans-MCl4(NO)(1H-indazole)] have pronounced cytotoxic potency in cancer cell lines. Especially the more potent ruthenium complexes strongly induce apoptosis associated with depolarization of mitochondrial membranes, and elevated reactive oxygen species levels. Furthermore, a slight yet not unequivocal trend to accumulation of intracellular cyclic guanosine monophosphate attributable to NO-mediated effects was observed.

Biological properties of novel ruthenium- and osmium-nitrosyl complexes with azole heterocycles

KAUST Repository

Novak, Maria S.

2016-03-09

Since the discovery that nitric oxide (NO) is a physiologically relevant molecule, there has been great interest in the use of metal nitrosyl compounds as antitumor pharmaceuticals. Particularly interesting are those complexes which can deliver NO to biological targets. Ruthenium- and osmium-based compounds offer lower toxicity compared to other metals and show different mechanisms of action as well as different spectra of activity compared to platinum-based drugs. Novel ruthenium- and osmium-nitrosyl complexes with azole heterocycles were studied to elucidate their cytotoxicity and possible interactions with DNA. Apoptosis induction, changes of mitochondrial transmembrane potential and possible formation of reactive oxygen species were investigated as indicators of NO-mediated damage by flow cytometry. Results suggest that ruthenium- and osmium-nitrosyl complexes with the general formula (indazolium)[cis/trans-MCl4(NO)(1H-indazole)] have pronounced cytotoxic potency in cancer cell lines. Especially the more potent ruthenium complexes strongly induce apoptosis associated with depolarization of mitochondrial membranes, and elevated reactive oxygen species levels. Furthermore, a slight yet not unequivocal trend to accumulation of intracellular cyclic guanosine monophosphate attributable to NO-mediated effects was observed.

Structural, spectral, DFT and biological studies on macrocyclic mononuclear ruthenium (II) complexes

Science.gov (United States)

Muthukkumar, M.; Kamal, C.; Venkatesh, G.; Kaya, C.; Kaya, S.; Enoch, Israel V. M. V.; Vennila, P.; Rajavel, R.

2017-11-01

Macrocyclic mononuclear ruthenium (II) complexes have been synthesized by condensation method [Ru (L1, L2, L3) Cl2] L1 = (C36 H31 N9), L2= (C42H36N8), L3= (C32H32 N8)]. These ruthenium complexes have been established by elemental analyses and spectroscopic techniques (Fourier transform infrared spectroscopy (FT-IR), 1H- nuclear magnetic resonance (NMR), 13C- NMR and Electrospray ionization mass spectrometry (ESI-MS)). The coordination mode of the ligand has been confirmed and the octahedral geometry around the ruthenium ion has been revealed. Binding affinity and binding mode of ruthenium (II) complexes with Bovine serum Albumin (BSA) have been characterized by Emission spectra analysis. UV-Visible and fluorescence spectroscopic techniques have also been utilized to examine the interaction between ligand and its complexes L1, L2, & L3 with BSA. Chemical parameters and molecular structure of Ru (II) complexes L1H, L2H, & L3H have been determined by DFT coupled with B3LYP/6-311G** functional in both the gaseous and aqueous phases.

Structure and reactivity of Ruthenium nanoparticles

DEFF Research Database (Denmark)

Gavnholt, Jeppe; Schiøtz, Jakob

2008-01-01

We present a method for obtaining detailed structural information of ruthenium nanoparticles in at least the diameter range from 1.5 to 5 nm. The method is based on an ensemble approach where a large number of low-energy structures are collected in an ensemble, from which average properties can...

Synthesis of ruthenium (III) complexes with benzimidazole derivatives

International Nuclear Information System (INIS)

Vyas, P.C.; Chahar, Yogesh K.; Garg, Yajula; Seth, Gita

2003-01-01

Complexes of ruthenium with biologically important benzimidazole derivatives, viz. 2-(2'-hydroxyphenyl) benzimidazole (HOPBI), 2-2'- mercaptophenyl) benzimidazole (HSPBI), 2- (2'-hydroxynaphthyl) benzimidazole (HONBI) have been synthesized and characterized. (author)

Support Effect in Hydrodesulfurization over Ruthenium Sulfide

Czech Academy of Sciences Publication Activity Database

Gulková, Daniela; Kaluža, Luděk; Vít, Zdeněk; Zdražil, Miroslav

2009-01-01

Roč. 51, č. 2 (2009), s. 146-149 ISSN 1337-7027 R&D Projects: GA ČR GA104/06/0705 Institutional research plan: CEZ:AV0Z40720504 Keywords : ruthenium sulfide * hydrodesulfurization * support effect Subject RIV: CC - Organic Chemistry

Perceptions of vocational interest : Self- and other-reports in student-parent dyads

NARCIS (Netherlands)

Holtrop, Djurre; Born, Marise Ph.; de Vries, Reinout Everhard

2017-01-01

The current study investigated how self- and other-ratings of vocational interests converge among student–parent dyads. Using the Personal Globe Inventory–Short, we obtained data from a pooled sample of 271 (high school senior and university) student–parent dyads. Participants rated their own

Perceptions of vocational interest: Self- and other-reports in student-parent dyads

NARCIS (Netherlands)

Holtrop, Djurre; Born, Marise Ph; de Vries, Reinout E.

The current study investigated how self- and other-ratings of vocational interests converge among student–parent dyads. Using the Personal Globe Inventory–Short, we obtained data from a pooled sample of 271 (high school senior and university) student–parent dyads. Participants rated their own

BODIPY-pyrene and perylene dyads as heavy atom-free singlet oxygen sensitizers

KAUST Repository

Filatov, Mikhail A.

2018-02-23

Dyads combining BODIPY as an electron acceptor and pyrene or perylene as electron donor subunits were prepared and studied their photophysical properties studied by steady-state and transient spectroscopy. Depending on the structure of the subunits and polarity of the media, the dyads show either bright fluorescence or photo-induced electron transfer (PeT) in solution. Charge-transfer (CT) states formed as a result of PeT and were found to yield triplet excited states of the BODIPY. In the presence of molecular oxygen, the dyads sensitize singlet oxygen (1O2) with quantum yields of up to 0.75.

BODIPY-pyrene and perylene dyads as heavy atom-free singlet oxygen sensitizers

KAUST Repository

Filatov, Mikhail A.; Karuthedath, Safakath; Polestshuk, Pavel M.; Callaghan, Susan; Flanagan, Keith J.; Wiesner, Thomas; Laquai, Fré dé ric; Senge, Mathias O.

2018-01-01

Dyads combining BODIPY as an electron acceptor and pyrene or perylene as electron donor subunits were prepared and studied their photophysical properties studied by steady-state and transient spectroscopy. Depending on the structure of the subunits and polarity of the media, the dyads show either bright fluorescence or photo-induced electron transfer (PeT) in solution. Charge-transfer (CT) states formed as a result of PeT and were found to yield triplet excited states of the BODIPY. In the presence of molecular oxygen, the dyads sensitize singlet oxygen (1O2) with quantum yields of up to 0.75.

Electrochemical behavior of ruthenium (III), rhodium (III) and palladium (II) in 1-butyl-3-methylimidazolium chloride ionic liquid

Energy Technology Data Exchange (ETDEWEB)

Jayakumar, M.; Venkatesan, K.A. [Fuel Chemistry Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102 (India); Srinivasan, T.G. [Fuel Chemistry Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102 (India)], E-mail: tgs@igcar.gov.in; Vasudeva Rao, P.R. [Fuel Chemistry Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102 (India)

2009-11-01

Electrochemical behavior of ruthenium (III), rhodium (III) and palladium (II) in 1-butyl-3-methylimidazolium chloride (bmimCl) and their ternary and binary solutions in bmimCl was studied at various working electrodes at 373 K by cyclic voltammetry and chronoamperometry. Ruthenium (III) chloride forms a stable solution with bmimCl and the cyclic voltammogram of ruthenium (III) in bmimCl recorded at glassy carbon electrode consisted of several redox waves due to the complex nature of ruthenium to exist in several oxidation states. Electrolysis of ruthenium (III) chloride in bmimCl at the cathodic limit of bmimCl (-1.8 V (vs. Pd)) did not result in ruthenium metal deposition. However, it was deposited from bmimPF{sub 6} and bmimNTf{sub 2} room temperature ionic liquids at -0.8 V (vs. Pd). The electrochemical behavior of ruthenium (III) in bmimCl in the presence of palladium (II) and rhodium (III) was studied by cyclic voltammetry. The presence of palladium (II) in bmimCl favors underpotential deposition of ruthenium metal. The nuclear loop at -0.5 V (vs. Pd) was observed in all solutions when palladium (II) co-existed with other two metal ions. Nucleation and growth of the metal on glassy carbon working electrode was investigated by chronoamperometry. The growth and decay of chronocurrents has been found to follow the instantaneous nucleation model with three-dimensional growth of nuclei.

Amorphous carbon nanofibres inducing high specific capacitance of deposited hydrous ruthenium oxide

International Nuclear Information System (INIS)

Barranco, V.; Pico, F.; Ibanez, J.; Lillo-Rodenas, M.A.; Linares-Solano, A.; Kimura, M.; Oya, A.; Rojas, R.M.; Amarilla, J.M.; Rojo, J.M.

2009-01-01

Composites consisting of ruthenium oxide particles deposited on amorphous carbon nanofibres are prepared by a repetitive impregnation procedure. The choice of amorphous carbon nanofibres as support of amorphous ruthenium oxide leads to composites in which the deposited oxide consists of aggregates of extremely small primary particles (1-1.5 nm-size) and showing high porosity (specific surface area of 450 m 2 g -1 ). This special deposition of the oxide seems to favour: (i) high oxide capacitance (1000 Fg -1 ) at high oxide loadings (up to 20 wt%) and (ii) high capacitance retention (ca. 80% from the initial oxide capacitance) at high current densities (200 mA cm -2 ). Amorphous carbon nanofibres are suitable supports for amorphous ruthenium oxide and perhaps for other amorphous oxides acting as active electrode materials.

Catalytic water oxidation by ruthenium(II) quaterpyridine (qpy) complexes: evidence for ruthenium(III) qpy-N,N'''-dioxide as the real catalysts.

Science.gov (United States)

Liu, Yingying; Ng, Siu-Mui; Yiu, Shek-Man; Lam, William W Y; Wei, Xi-Guang; Lau, Kai-Chung; Lau, Tai-Chu

2014-12-22

Polypyridyl and related ligands have been widely used for the development of water oxidation catalysts. Supposedly these ligands are oxidation-resistant and can stabilize high-oxidation-state intermediates. In this work a series of ruthenium(II) complexes [Ru(qpy)(L)2 ](2+) (qpy=2,2':6',2'':6'',2'''-quaterpyridine; L=substituted pyridine) have been synthesized and found to catalyze Ce(IV) -driven water oxidation, with turnover numbers of up to 2100. However, these ruthenium complexes are found to function only as precatalysts; first, they have to be oxidized to the qpy-N,N'''-dioxide (ONNO) complexes [Ru(ONNO)(L)2 ](3+) which are the real catalysts for water oxidation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spectrophotometric determination of ruthenium (III) and rhodium (III) with 9,10-phenanthrenequinone monoxime after extraction into molten naphthalene

International Nuclear Information System (INIS)

Wasey, A.; Bansal, R.K.; Puri, B.K.; Satake, Masatada.

1983-01-01

9,10-Phenanthrenequinone monoxime has been used as a reagent for the spectrophotometric determination of ruthenium(III) and rhodium(III) after extraction into molten naphthalene. The extracted mixture of the metal complex and naphthalene was dissolved in chloroform and ruthenium and rhodium were determined spectrophotometrically. Beer's law holds in the concentration range of 0.2-4.1 μg/cm 3 for ruthenium and 0.3-5.3 μg/cm 3 for rhodium in 10 cm 3 of the final solution. The molar absorptivities and Sandell sensitivities are calculated to be 9.70 x 10 3 l mol -1 cm -1 and 0.01 μg/cmsup(2 ) (660 nm) for ruthenium and 1.13 x 10 4 l mol -1 cm -1 and 0.009 μg/cm 2 (410 nm) for rhodium respectively. Aliquots containing 2.0 μg of ruthenium and 4.1 μg of rhodium give mean absorbances of 0.192 and 0.451 with standard deviations of 0.0017 and 0.0039, respectively. Interference of various ions has been studied and the method has been applied to the determination of ruthenium and rhodium in various synthetic mixtures. This procedure is also applied to the simultaneous determination of ruthenium and rhodium present together in a solution. (author)

The effect of dyad versus individual simulation-based ultrasound training on skills transfer

DEFF Research Database (Denmark)

Tolsgaard, Martin G; Madsen, Mette E; Oxlund, Birgitte S

2015-01-01

: This study was conducted to compare the effectiveness of simulation-based ultrasound training in pairs (dyad practice) with that of training alone (single-student practice) on skills transfer. METHODS: In a non-inferiority trial, 30 ultrasound novices were randomised to dyad (n = 16) or single-student (n...... through pre-, post- and transfer tests. The transfer test involved the assessment of a transvaginal ultrasound scan by one of two clinicians using the Objective Structured Assessment of Ultrasound Skills (OSAUS). RESULTS: Thirty participants completed the simulation-based training and 24...... interactions between training type and performance (p = 0.59). The dyad group demonstrated higher training efficiency in terms of simulator score per number of attempts compared with the single-student group (p = 0.03). CONCLUSION: Dyad practice improves the efficiency of simulation-based training and is non...

Unsaturated carbone and allenylidene ruthenium complexes from alkynes

International Nuclear Information System (INIS)

Bozek, Yu.L.; Diznev, P.A.

1995-01-01

The author's studies aimed at activation of terminal alkynes by metal complexes, reactivity patterns and selective preparations of unsaturated carbene, allenylidene and cumulenylidene derivatives of (arene)ruthenium complexes are reviewed. 48 refs

Analysis of Participant Reactivity in Dyads Performing a Videotaped Conflict-Management Task.

Science.gov (United States)

Semeniuk, Yulia Y; Riesch, Susan K

2011-01-01

Videotaping is used frequently in nursing research. A threat to the validity of videotaping is participant reactivity, that is, being recorded by a camera may influence the behavior of interest. This paper's purpose is to report how youth ages 10 to 14 years old and their parent viewed participation in a videotaped conflict-management task. Five dyads, who were part of a randomized clinical trial testing an intervention to promote parent-child communication, participated in a structured interview. All parents were mothers. Youth were eighth graders. Three were boys and two were girls. Findings indicated that (a) dyads felt that the videotaped interaction had a progression of feeling unnatural in the beginning to feeling natural toward the end, (b) dyads found it relatively easy to choose a topic of discussion, and (c) dyads felt that the discussions were meaningful. Based on these data, recommendations for researchers to reduce participant reactivity are provided.

Identification of short-lived neutron-rich ruthenium and rhodium isotopes in fission

International Nuclear Information System (INIS)

Franz, G.; Herrmann, G.

1975-01-01

Short-lived ruthenium and rhodium isotopes ( 107 Ru, 108 Ru, 108 Rh, 109 Ru, 109 Rh, 110 Ru, 110 Rh, 111 Ru, 111 Rh, 112 Ru, 112 Rh, 113 Ru) have been separated from fission products by a rapid chemical procedure and identified by means of γ-ray spectroscopy. Nuclides with half-lives down to 3 sec were accessible. Ruthenium isotopes up to mass number 113 have been identified. (author)

Determination of oxygen diffusion kinetics during thin film ruthenium oxidation

Energy Technology Data Exchange (ETDEWEB)

Coloma Ribera, R., E-mail: r.colomaribera@utwente.nl; Kruijs, R. W. E. van de; Yakshin, A. E.; Bijkerk, F. [MESA+ Institute for Nanotechnology, University of Twente, P.O. Box 217, 7500 AE Enschede (Netherlands)

2015-08-07

In situ X-ray reflectivity was used to reveal oxygen diffusion kinetics for thermal oxidation of polycrystalline ruthenium thin films and accurate determination of activation energies for this process. Diffusion rates in nanometer thin RuO{sub 2} films were found to show Arrhenius behaviour. However, a gradual decrease in diffusion rates was observed with oxide growth, with the activation energy increasing from about 2.1 to 2.4 eV. Further exploration of the Arrhenius pre-exponential factor for diffusion process revealed that oxidation of polycrystalline ruthenium joins the class of materials that obey the Meyer-Neldel rule.

Electron transfer reactions of ruthenium(II) complexes with polyphenolic acids in micelles

Energy Technology Data Exchange (ETDEWEB)

Rajeswari, Angusamy [School of Chemistry, Madurai Kamaraj University, Madurai 625 021 (India); Department of Chemistry, Fatima College, Madurai 625 018 (India); Ramdass, Arumugam [School of Chemistry, Madurai Kamaraj University, Madurai 625 021 (India); Research Department of Chemistry, Aditanar College of Arts and Science, Tiruchendur 628 216 (India); Muthu Mareeswaran, Paulpandian [School of Chemistry, Madurai Kamaraj University, Madurai 625 021 (India); Department of Industrial Chemistry, Alagappa University, Karaikudi 630 003 (India); Rajagopal, Seenivasan, E-mail: rajagopalseenivasan@yahoo.com [School of Chemistry, Madurai Kamaraj University, Madurai 625 021 (India)

2016-02-15

The electron transfer in a microhetrogeneous system is a perfect mimic of biological electron transfer. The electron transfer between biologically important phenolic acids and ruthenium (II) complexes is systematically studied in the presence of anionic and cationic micelles. The photophysical properties of these ruthenium (II) complexes with anionic and cationic micelles and their binding abilities with these two type of micelles are also studies using absorption, emission and excited state lifetime spectral techniques. Pseudophase Ion Exchange (PIE) Model is applied to derive mechanism of electron transfer in two types of micelles. - Highlights: • Effect of microhetrogeneous system is studied using ruthenium (II) complexes and gallic acid is studied. • Pseudophase Ion exchange model is applied to derive the mechanism. • Binding constants are in the range of 10{sup 2}–10{sup 4} M{sup −1}.

Evaluation of radiolabeled ruthenium compounds as tumor-localizing agents

International Nuclear Information System (INIS)

Srivastava, S.C.; Richards, P.; Meinken, G.E.; Som, P.; Atkins, H.L.; Larson, S.M.; Grunbaum, Z.; Rasey, J.S.; Clarke, M.H.; Dowling, M.

1979-01-01

This work introduces a new class of radiopharmaceuticals based on ruthenium-97. The excellent physical properties of Ru-97, the high chemical reactivity of Ru, the potential antitumor activity of several Ru coordination compounds, and BLIP production of Ru-97, provide a unique combination for the application of this isotope in nuclear oncology. A systematic study was undertaken on the synthesis, characterization, and evaluation of a number of ruthenium-labeled compounds. In a variety of animal tumor models, several compounds show considerable promise as tumor-localizing agents when compared to gallium-67 citrate. The compounds studied (with Ru in different oxidation states) include ionic Ru, a number of hydrophilic and lipophilic chelates, and various ammine derivatives

Ruthenium, osmium and rhodium complexes of polypyridyl ligands ...

Indian Academy of Sciences (India)

Unknown

Discipline of Silicates and Catalysis, Central Salt and Marine Chemicals ... However, synthetic methods have also been developed to prepare complexes with ... 3.2 Synthesis and characterisation of ruthenium(II) and osmium(II) complexes18, ...

Behaviour of ruthenium in the case of shutdown of the cooling system of HLLW storage tanks

International Nuclear Information System (INIS)

Philippe, M.; Gue, J.P.; Mercier, J.P.

1990-12-01

The consequences of the failure of the cooling system of fission product storage tanks over a variable period were investigated as part of the safety analysis of the La Hague spent fuel reprocessing plant. Due to the considerable heat release, induced by the fission products, a prolonged shutdown of the tank cooling system could cause the progressive evaporation of the solutions to dryness, and culminate in the formation of volatile species of ruthenium and their release in the tank venting circuit. To determine the fraction of ruthenium likely to be transferred from the storage tanks in volatile or aerosol form during the failure, evaporation tests were conducted by evaporating samples of actual nitric acid solutions of fission products, obtained on the laboratory scale after the reprocessing of several kilograms of MOX fuels irradiated to 30.000 MW day ·t -1 . A distillation apparatus was designed to operate with small-volume solution samples, reproducing the heating conditions existing in the reprocessing plant within a storage tank for fission products. The main conclusions drawn from these experiments are as follows: - ruthenium is only volatilized in the final phase of evaporation, just before desiccation, - for a final temperature limited to 160 deg. C, the total fraction of volatilized ruthenium reaches 12%, - in the presence of H 2 O, HNO 3 , NO x and O 2 , the volatilized ruthenium recombines mainly in the form of ruthenium nitrosyl nitrates, or decomposes into ruthenium oxide (probably RuO 2 ) on the walls of the apparatus. Assuming a heating power density of 10 W/liter of concentrate, and a perfectly adiabatic storage system, the minimum time required to reach dryness can be estimated at 90 h, allowing substantial time to take action to restore a cooling source. It is probable that, in an industrial storage tank, the heat losses from the tank and the offgas discharge ducts will cause recondensation and internal reflux, which will commensurately delay

Enyne Metathesis Catalyzed by Ruthenium Carbene Complexes

DEFF Research Database (Denmark)

Poulsen, Carina Storm; Madsen, Robert

2003-01-01

Enyne metathesis combines an alkene and an alkyne into a 1,3-diene. The first enyne metathesis reaction catalyzed by a ruthenium carbene complex was reported in 1994. This review covers the advances in this transformation during the last eight years with particular emphasis on methodology...

Maternal Food-Related Practices, Quality of Diet, and Well-Being: Profiles of Chilean Mother-Adolescent Dyads.

Science.gov (United States)

Schnettler, Berta; Grunert, Klaus G; Lobos, Germán; Miranda-Zapata, Edgardo; Denegri, Marianela; Hueche, Clementina

2018-04-03

To identify mother-adolescent dyad profiles according to food-related parenting practices and to determine differences in diet quality, family meal frequency, life satisfaction, and sociodemographic characteristics. Cross-sectional study. Mothers and children were surveyed in their homes or at schools in Temuco, Chile. A total of 300 mothers (average age, 41.6 years) and their adolescent children (average age, 13.2 years; 48.7% female). Maternal feeding practices using the abbreviated Family Food Behavior Survey (AFFBS), life satisfaction, food-related and family life satisfaction, diet quality, and eating habits. Principal component factor analysis and confirmatory factor analysis were used to verify Family Food Behavior Survey components in mother and adolescent subsamples. Hierarchical cluster analysis was used to identify profiles. Three AFFBS components were detected: maternal control of child snacking behavior, maternal presence during eating, and child involvement in food consumption. Cluster analysis identified 3 mother-adolescent dyad profiles with different food-related parenting practices (P ≤ .001), mother (P ≤ .05) and child (P ≤ .001) diet quality, frequency of shared family meals (P ≤ .001), and mother (P ≤ .001) and child (P ≤ .05) life satisfaction levels. Results indicated that maternal well-being increased with an increased frequency of shared mealtime. Significantly, in contrast to the findings of previous studies, greater control over child eating habits was shown to affect adolescent well-being positively. These findings, among others, may contribute to the development of strategies for improving diet quality, overall well-being, and well-being in the food and family domains for all family members. Copyright © 2018 Society for Nutrition Education and Behavior. Published by Elsevier Inc. All rights reserved.

Committee's report on ruthenium fall-out incident

International Nuclear Information System (INIS)

Borkowski, C.J.; Crawford, J.H.; Livingston, R.; Ritchie, R.H.; Rupp, A.F.; Taylor, E.H.

1983-07-01

Investigations of the fall-out incident of November 11 and 12, 1959, by responsible parties (Health Physics Division and Operations Division personnel) established beyond reasonable doubt that the incident had its origin in the expulsion of particles, heavily contaminated with ruthenium, which had been detached from the walls of the electric fan housing and ducts in the off-gas system associated with the brick stack. All available evidence indicates that the particles were loosened during maintenance work on the exhaust damper and the bearings of the electric fan and were carried up the stack in two bursts as particulate fall-out when this fan was put back into service. Radiographic and chemical analysis showed the activity to be almost entirely ruthenium (Ru 106 ) and its daughter rhodium (Rh 106 ) with very little, if any, strontium being present. This report summarizes the findings and sets forth the conclusions and recommendations of the Committee asked to investigate the incident

Comparative genomics of Cluster O mycobacteriophages.

Science.gov (United States)

Cresawn, Steven G; Pope, Welkin H; Jacobs-Sera, Deborah; Bowman, Charles A; Russell, Daniel A; Dedrick, Rebekah M; Adair, Tamarah; Anders, Kirk R; Ball, Sarah; Bollivar, David; Breitenberger, Caroline; Burnett, Sandra H; Butela, Kristen; Byrnes, Deanna; Carzo, Sarah; Cornely, Kathleen A; Cross, Trevor; Daniels, Richard L; Dunbar, David; Findley, Ann M; Gissendanner, Chris R; Golebiewska, Urszula P; Hartzog, Grant A; Hatherill, J Robert; Hughes, Lee E; Jalloh, Chernoh S; De Los Santos, Carla; Ekanem, Kevin; Khambule, Sphindile L; King, Rodney A; King-Smith, Christina; Klyczek, Karen; Krukonis, Greg P; Laing, Christian; Lapin, Jonathan S; Lopez, A Javier; Mkhwanazi, Sipho M; Molloy, Sally D; Moran, Deborah; Munsamy, Vanisha; Pacey, Eddie; Plymale, Ruth; Poxleitner, Marianne; Reyna, Nathan; Schildbach, Joel F; Stukey, Joseph; Taylor, Sarah E; Ware, Vassie C; Wellmann, Amanda L; Westholm, Daniel; Wodarski, Donna; Zajko, Michelle; Zikalala, Thabiso S; Hendrix, Roger W; Hatfull, Graham F

2015-01-01

Mycobacteriophages--viruses of mycobacterial hosts--are genetically diverse but morphologically are all classified in the Caudovirales with double-stranded DNA and tails. We describe here a group of five closely related mycobacteriophages--Corndog, Catdawg, Dylan, Firecracker, and YungJamal--designated as Cluster O with long flexible tails but with unusual prolate capsids. Proteomic analysis of phage Corndog particles, Catdawg particles, and Corndog-infected cells confirms expression of half of the predicted gene products and indicates a non-canonical mechanism for translation of the Corndog tape measure protein. Bioinformatic analysis identifies 8-9 strongly predicted SigA promoters and all five Cluster O genomes contain more than 30 copies of a 17 bp repeat sequence with dyad symmetry located throughout the genomes. Comparison of the Cluster O phages provides insights into phage genome evolution including the processes of gene flux by horizontal genetic exchange.

Preliminary assessment of modified borosilicate glasses for chromium and ruthenium immobilization

Energy Technology Data Exchange (ETDEWEB)

Farid, Osama M. [Reactors Department, Nuclear Research Center, Atomic Energy Authority of Egypt, P.O. 13759, Inshas, Cairo (Egypt); Centre of Nuclear Engineering (CNE), Department of Materials, Imperial College London, London, SW7 2BP (United Kingdom); Abdel Rahman, R.O., E-mail: alaarehab@yahoo.com [Hot Laboratory Center, Atomic Energy Authority of Egypt, P.O. 13759, Inshas, Cairo (Egypt)

2017-01-15

The feasibility of using modified alkali borosilicate glasses for ruthenium and chromium immobilization is preliminary assessed by investigating the immobilization system structure under normal conditions. Within this context, reference alkali borosilicate, and simulated Magnox-modified glasses were prepared and studied. The results indicate that ruthenium is immobilized in the vitreous structure as encapsulated RuO{sub 2} crystallites that act as seeds for heterogeneous nucleation of other crystalline phases. The presence of Zn, as modifier, has contributed to chromium immobilization in zincochromite spinel structure, whereas Ca is accommodated in the vitreous structure. Immobilization performance was evaluated by conducting conservative static leach test and studying the leached glass. Leached glass morphology was altered, where near surface reference glass is leached over 400 nm and simulated Magnox-modified sample is altered over 300 nm. Normalized release rates are within normal range for borosilicate material. For simulated Magnox-modified sample, Ca and alkali structural element, i.e. Na and Li, are leached via ion-exchange reaction. The ion-exchanged fraction equals 1.06 × 10{sup −8} mol/m{sup 2} s and chromium has slightly lower normalized release rate value than ruthenium. - Highlights: • The presence of modifiers and waste oxides led to localized de-vitrification. • Ruthenium is encapsulated within the vitreous glass network as RuO{sub 2} crystals. • Chromium is immobilized within the zincochromite spinel structure. • Pitting and cracks induced by leaching did not affect the immobilization performance.

A framework for studying relationship marketing dyads

NARCIS (Netherlands)

Lindgreen, A.

2001-01-01

Although coined more than 15 years ago, relationship marketing remains an ambiguous concept with plenty of rhetoric but few publications on empirical evidence in support of a relationship marketing paradigm shift. A research project is currently studying marketing dyads in the international food

Synthesis and characterization of novel heteroleptic ruthenium sensitizer for nanocrystalline dye-sensitized solar cells

NARCIS (Netherlands)

Sivakumar, R.; Marcelis, A.T.M.; Anandan, S.

2009-01-01

A novel heteroleptic ruthenium complex of the type [Ru(bpin)(dcbpyH2)Cl]Cl (where bpin is 2,6-bis(pyrazol-1-yl)isonicotinic acid and dcbpyH2 is 4,4'-dicarboxy-2,2'-bipyridine) was synthesized and characterized for tuning the LUMO level of the ruthenium sensitizer to achieve greater stabilization in

Behavior of ruthenium in the case of shutdown of the cooling system of HLLW storage tanks

International Nuclear Information System (INIS)

Philippe, M.; Mercier, J.P.; Gue, J.P.

1990-01-01

The consequences of the failure of the cooling system of fission product storage tanks over a variable period were investigated as part of the safety analysis of the La Hague spent fuel reprocessing plant. Due to the considerable heat release, induced by the fission products, a prolonged shutdown of the tank cooling system could cause the progressive evaporation of the solutions to dryness, and culminate in the formation of volatile species of ruthenium and their release in the tank venting circuit. To determine the fraction of ruthenium likely to be transferred from the storage tanks in volatile or aerosol form during the failure, evaporation tests were conducted by evaporating samples of actual nitric acid solutions of fission products, obtained on the laboratory scale after the reprocessing of several kilograms of MOX fuels irradiated to 30,000 MWday.t -1 . A distillation apparatus was designed to operate with small volume solution samples, reproducing the heating conditions existing in the reprocessing plant within a storage tank for fission products. The main conclusions drawn from these experiments are as follows: - ruthenium is only volatilized in the final phase of evaporation, just before desiccation, - for a final temperature limited to 160 0 C, the total fraction of volatilized ruthenium reaches 12%, in the presence of H 2 0, HN0 3 , N0 x and 0 2 , the volatilized ruthenium recombines mainly in the form of ruthenium nitrosyl nitrates, or decomposes into ruthenium oxide on the walls of the apparatus. Assuming a heating power density of 10 W/liter of concentrate, and a perfectly adiabatic storage system, the minimum time required to reach dryness can be estimated at 90 h, allowing substantial time to take action to restore a cooling source

Behavior of ruthenium in the case of shutdown of the cooling system of HLLW storage tanks

International Nuclear Information System (INIS)

Philippe, M.; Mercier, J.P.; Gue, J.P.

1991-01-01

The consequences of the failure of the cooling system of fission product storage tanks over a variable period were investigated as part of the safety analysis of the La Hague spent fuel reprocessing plant. Due to the considerable heat release, induced by the fission products, a prolonged shutdown of the tank cooling system could cause the progressive evaporation of the solutions to dryness, and culminate in the formation of volatile species of ruthenium and their release in the tank venting circuit. To determine the fraction of ruthenium likely to be transferred from the storage tanks in volatile or aerosol form during the failure, evaporation tests were conducted by evaporating samples of actual nitric acid solutions of fission products, obtained on the laboratory scale after the reprocessing of several kilograms of MOX fuels irradiated to 30,000 MW day·t -1 . A distillation apparatus was designed to operate with small-volume solution samples, reproducing the heating conditions existing in the reprocessing plant within a storage tank for fission products. The main conclusions drawn from these experiments are as follows: ruthenium is only volatilized in the final phase of evaporation, just before desiccation; for a final temperature limited to 160 degree C, the total fraction of volatilized ruthenium reaches 12%; in the presence of H 2 O, HNO 3 , NO x and O 2 , the volatilized ruthenium recombines mainly in the form of ruthenium nitrosyl nitrates, or decomposes into ruthenium oxide (probably RuO 2 ) on the walls of the apparatus. Assuming a heating power density of 10 W/liter of concentrate, and a perfectly adiabatic storage system, the minimum time required to reach dryness can be estimated at 90 h, allowing substantial time to take action to restore a cooling source

Mechanism of ruthenium dioxide crystallization during high level waste vitrification

International Nuclear Information System (INIS)

Boucetta, H.

2012-01-01

Ruthenium, arising from the reprocessing of spent uranium oxide fuel, has a low solubility in glass melt. It crystallizes in the form of particles of RuO 2 of acicular or polyhedral morphology dispersed in fission product and actinides waste containment glass. Since the morphology of these particles strongly influences the physico-chemical properties, the knowledge and the control of their mechanism of formation are of major importance. The goal of this work is to determine the chemical reactions responsible for the formation of RuO 2 particles of acicular or polyhedral shape during glass synthesis. Using a simplification approach, the reactions between RuO 2 -NaNO 3 , and more complex calcine RuO 2 -Al 2 O 3 -Na 2 O and a sodium borosilicate glass are studied. In situ scanning electron microscopy and XANES at increasing temperatures are used to follow changes in composition, speciation and morphology of the ruthenium intermediate species. Those compounds are thoroughly characterised by SEM, XRD, HRTEM, and ruthenium K-edge X-ray absorption spectroscopy. This combined approach allows us to show that the ruthenium speciation modification during vitrification is the key of control of the morphology of RuO 2 particles in the glass. In particular, the formation of a specific intermediate compound (Na 3 RuO 4 ) is one of the main steps that lead to the precipitation of needle-shaped RuO 2 particles in the melt. The formation of polyhedral particles, on the contrary, results from the direct incorporation of RuO 2 crystals in the melt followed by an Ostwald ripening mechanism. (author) [fr

Analysis of flow fields, temperatures and ruthenium transport in the test facility

International Nuclear Information System (INIS)

Kaerkelae, T.; Pyykoenen, J.; Auvinen, A.; Jokiniemi, J.

2008-03-01

Ruthenium transport experiments were conducted at VTT during years 2002- 2006. Experiments gave information about ruthenium behaviour in air ingress accident conditions. This study complements those experiments with an analysis of the flows and thermal fields in the test system. Temperature profiles were measured at the walls of the experimental facility. Computational fluid dynamics (CFD) simulations used the measured profiles and provided predictions of flows and temperatures inside the furnace. Ruthenium transport was also modelled with CFD. Thermal characterisation of the reactor demonstrated that buoyancy has a significant role during the cooling after the furnace. A hypothesis of the dominant role of RuO2 and RuO3 condensation on reactor walls gave simulation results that are in accordance with radiotracer measurements of deposition in experiments conducted with furnace at 1500K. Actually, RuO3 does not condensate, but it thermal decomposes to RuO2. This does not seem to have effect on result. Particle formation around the furnace exit could be detected from the comparison of modelling results with the measured profiles. In several other experiments ruthenium behaviour is dominated by other issues. These are related to the complex ruthenium chemistry that includes various surface reactions. Thermal equilibrium indicates significant gaseous RuO4 concentration around 1300 K. It seems that seed particles decreased the catalytic decomposition activity of RuO4 to RuO2 around this temperature pushing the gas concentration towards the equilibrium, and further give rise to gaseous RuO4 transport to low temperatures. At higher temperature increasing mass flow rate of RuO2 particles is likely to catalyse (decomposition) reaction of RuO4 to RuO2. (au)

Analysis of flow fields, temperatures and ruthenium transport in the test facility

Energy Technology Data Exchange (ETDEWEB)

Kaerkelae, T.; Pyykoenen, J.; Auvinen, A.; Jokiniemi, J. [Technical Research Centre of Finland VTT (Finland)

2008-03-15

Ruthenium transport experiments were conducted at VTT during years 2002- 2006. Experiments gave information about ruthenium behaviour in air ingress accident conditions. This study complements those experiments with an analysis of the flows and thermal fields in the test system. Temperature profiles were measured at the walls of the experimental facility. Computational fluid dynamics (CFD) simulations used the measured profiles and provided predictions of flows and temperatures inside the furnace. Ruthenium transport was also modelled with CFD. Thermal characterisation of the reactor demonstrated that buoyancy has a significant role during the cooling after the furnace. A hypothesis of the dominant role of RuO2 and RuO3 condensation on reactor walls gave simulation results that are in accordance with radiotracer measurements of deposition in experiments conducted with furnace at 1500K. Actually, RuO3 does not condensate, but it thermal decomposes to RuO2. This does not seem to have effect on result. Particle formation around the furnace exit could be detected from the comparison of modelling results with the measured profiles. In several other experiments ruthenium behaviour is dominated by other issues. These are related to the complex ruthenium chemistry that includes various surface reactions. Thermal equilibrium indicates significant gaseous RuO4 concentration around 1300 K. It seems that seed particles decreased the catalytic decomposition activity of RuO4 to RuO2 around this temperature pushing the gas concentration towards the equilibrium, and further give rise to gaseous RuO4 transport to low temperatures. At higher temperature increasing mass flow rate of RuO2 particles is likely to catalyse (decomposition) reaction of RuO4 to RuO2. (au)

Synthesis and reactivity of compounds containing ruthenium-carbon, -nitrogen, and -oxygen bonds

International Nuclear Information System (INIS)

Hartwig, J.F.

1990-12-01

The products and mechanisms of the thermal reactions of several complexes of the general structure (PMe 3 ) 4 Ru(X)(Y) and (DMPM) 2 Ru(X)(Y) where X and Y are hydride, aryl, and benzyl groups, have been investigated. The mechanism of decomposition depends critically on the structure of the complex and the medium in which the thermolysis is carried out. The alkyl hydride complexes are do not react with alkane solvent, but undergo C-H activation processes with aromatic solvents by several different mechanisms. Thermolysis of (PMe 3 ) 4 Ru(Ph)(Me) or (PMe 3 ) 4 Ru(Ph) 2 leads to the ruthenium benzyne complex (PMe 3 ) 4 Ru(η 2 -C 6 H 4 ) (1) by a mechanism which involves reversible dissociation of phosphine. In many ways its chemistry is analogous to that of early rather than late organo transition metal complexes. The synthesis, structure, variable temperature NMR spectroscopy and reactivity of ruthenium complexes containing aryloxide or arylamide ligands are reported. These complexes undergo cleavage of a P-C bond in coordinated trimethylphosphine, insertion of CO and CO 2 and hydrogenolysis. Mechanistic studies on these reactions are described. The generation of a series of reactive ruthenium complexes of the general formula (PMe 3 ) 4 Ru(R)(enolate) is reported. Most of these enolates have been shown to bind to the ruthenium center through the oxygen atom. Two of the enolate complexes 8 and 9 exist in equilibrium between the O- and C-bound forms. The reactions of these compounds are reported, including reactions to form oxygen-containing metallacycles. The structure and reactivity of these ruthenium metallacycles is reported, including their thermal chemistry and reactivity toward protic acids, electrophiles, carbon monoxide, hydrogen and trimethylsilane. 243 refs., 10 tabs

Synthesis and reactivity of compounds containing ruthenium-carbon, -nitrogen, and -oxygen bonds

Energy Technology Data Exchange (ETDEWEB)

Hartwig, J.F.

1990-12-01

The products and mechanisms of the thermal reactions of several complexes of the general structure (PMe{sub 3}){sub 4}Ru(X)(Y) and (DMPM){sub 2}Ru(X)(Y) where X and Y are hydride, aryl, and benzyl groups, have been investigated. The mechanism of decomposition depends critically on the structure of the complex and the medium in which the thermolysis is carried out. The alkyl hydride complexes are do not react with alkane solvent, but undergo C-H activation processes with aromatic solvents by several different mechanisms. Thermolysis of (PMe{sub 3}){sub 4}Ru(Ph)(Me) or (PMe{sub 3}){sub 4}Ru(Ph){sub 2} leads to the ruthenium benzyne complex (PMe{sub 3}){sub 4}Ru({eta}{sup 2}-C{sub 6}H{sub 4}) (1) by a mechanism which involves reversible dissociation of phosphine. In many ways its chemistry is analogous to that of early rather than late organo transition metal complexes. The synthesis, structure, variable temperature NMR spectroscopy and reactivity of ruthenium complexes containing aryloxide or arylamide ligands are reported. These complexes undergo cleavage of a P-C bond in coordinated trimethylphosphine, insertion of CO and CO{sub 2} and hydrogenolysis. Mechanistic studies on these reactions are described. The generation of a series of reactive ruthenium complexes of the general formula (PMe{sub 3}){sub 4}Ru(R)(enolate) is reported. Most of these enolates have been shown to bind to the ruthenium center through the oxygen atom. Two of the enolate complexes 8 and 9 exist in equilibrium between the O- and C-bound forms. The reactions of these compounds are reported, including reactions to form oxygen-containing metallacycles. The structure and reactivity of these ruthenium metallacycles is reported, including their thermal chemistry and reactivity toward protic acids, electrophiles, carbon monoxide, hydrogen and trimethylsilane. 243 refs., 10 tabs.

Deposition and properties of cobalt- and ruthenium-based ultra-thin films

Science.gov (United States)

Henderson, Lucas Benjamin

Future copper interconnect systems will require replacement of the materials that currently comprise both the liner layer(s) and the capping layer. Ruthenium has previously been considered as a material that could function as a single material liner, however its poor ability to prevent copper diffusion makes it incompatible with liner requirements. A recently described chemical vapor deposition route to amorphous ruthenium-phosphorus alloy films could correct this problem by eliminating the grain boundaries found in pure ruthenium films. Bias-temperature stressing of capacitor structures using 5 nm ruthenium-phosphorus film as a barrier to copper diffusion and analysis of the times-to-failure at accelerated temperature and field conditions implies that ruthenium-phosphorus performs acceptably as a diffusion barrier for temperatures above 165°C. The future problems associated with the copper capping layer are primarily due to the poor adhesion between copper and the current Si-based capping layers. Cobalt, which adheres well to copper, has been widely proposed to replace the Si-based materials, but its ability to prevent copper diffusion must be improved if it is to be successfully implemented in the interconnect. Using a dual-source chemistry of dicobaltoctacarbonyl and trimethylphosphine at temperatures from 250-350°C, amorphous cobalt-phosphorus can be deposited by chemical vapor deposition. The films contain elemental cobalt and phosphorus, plus some carbon impurity, which is incorporated in the film as both graphitic and carbidic (bonded to cobalt) carbon. When deposited on copper, the adhesion between the two materials remains strong despite the presence of phosphorus and carbon at the interface, but the selectivity for growth on copper compared to silicon dioxide is poor and must be improved prior to consideration for application in interconnect systems. A single molecule precursor containing both cobalt and phosphorus atoms, tetrakis

Extraction and atomic absorption spectrophotometric determination of iron and ruthenium by using potassium xanthates

Energy Technology Data Exchange (ETDEWEB)

Aihara, M; Kiboku, M [Kinki Univ., Higashi-Osaka, Osaka (Japan)

1981-06-01

Potassium xanthates (potassium o-alkyl dithiocarbonate; KRX) react with many metal ions, and so the complex formation with iron (II, III) ion and the extraction of their complexes has been studied to some extent, but those of ruthenium (III) have not been. Iron-xanthate and ruthenium-xanthate complexes can be extracted into methyl isobutyl ketone (MIBK) from weakly acidic solution to weakly alkaline solution. For quantitative extraction of iron (20 ..mu..g/40 ml), KRX concentration should be above 2.0 x 10/sup -2/ mol dm/sup -3/ of KEtX, 1.0 x 10/sup -2/ mol dm/sup -3/ of KPrX, and 5.0 x 10/sup -3/ mol dm/sup -3/ of KBtX and KPeX, and for that of ruthenium (202 ..mu..g/40 ml), it should be above 2.0 x 10/sup -1/ mol dm/sup -3/ of KEtX and KPrX. Formation constant of ruthenium-xanthate complexes is presumed to be small. A 100-fold excess of Ni(II), Co(II), Cu(II), WO/sub 4//sup 2 -/, PO/sub 4//sup 3 -/, CrO/sub 4//sup 2 -/, and Cr/sub 2/O/sub 7//sup 2 -/ interfered with the determination of iron, however, the interferences are eliminated by adding 5 ml of 0.1 mol dm/sup -3/ ascorbic acid solution. For the determination of ruthenium, a 50-fold excess of Ag(I), Hg(II), Pb(II), Zn(II), Mn(II), Cr(III), and Pt(II), or a 100-fold excess of NO/sub 2//sup -/, S/sub 2/O/sub 3//sup 2 -/, CrO/sub 4//sup 2 -/ and Cr/sub 2/O/sub 7//sup 2 -/, respectively, interfered. The coefficient of variation after each ten runs, ranges from 0.9% to 3.2% in the determination of 10 ..mu..g, 20 ..mu..g, and 30 ..mu..g of iron, and from 1.4% to 4.3% in the determination of 100 ..mu..g, 200 ..mu..g, and 300 ..mu..g of ruthenium. The determination limit in aqueous samples is 0.02 ppm for iron and 0.2 ppm for ruthenium, when the volume ratio of aqueous phase to organic phase (MIBK) is 10:1.

Separation of carrier-free rhodium isotopes from ruthenium cyclotron targets by the extraction of nitrosylruthenium from hydrochloric acid solution

International Nuclear Information System (INIS)

Haasbroek, F.J.; Strelow, F.W.E.; Van der Walt, T.N.

1981-01-01

A method is presented for the separation of rhodium isotopes from ruthenium cyclotron targets. After bombardment with deuterons and dissolution of the target material, the ruthenium is converted into a nitrosyl complex by treatment with hydroxylammonium chloride. Aluminium and other elements which have been introduced in the dissolution step, are separated by cation exchange. Ruthenium is then separated by extraction with a mixture of tri-n-butyl phosphate and hexane (4:1), leaving the rhodium in the aqueous phase. No ruthenium is found in the rhodium fraction and the recovery of rhodium is better than 90 per cent [af

Rare earth-ruthenium-magnesium intermetallics

Energy Technology Data Exchange (ETDEWEB)

Stein, Sebastian; Kersting, Marcel; Heletta, Lukas; Poettgen, Rainer [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie

2017-07-01

Eight new intermetallic rare earth-ruthenium-magnesium compounds have been synthesized from the elements in sealed niobium ampoules using different annealing sequences in muffle furnaces. The compounds have been characterized by powder and single crystal X-ray diffraction. Sm{sub 9.2}Ru{sub 6}Mg{sub 17.8} (a=939.6(2), c=1779(1) pm), Gd{sub 11}Ru{sub 6}Mg{sub 16} (a=951.9(2), c=1756.8(8) pm), and Tb{sub 10.5}Ru{sub 6}Mg{sub 16.5} (a=942.5(1), c=1758.3(4) pm) crystallize with the tetragonal Nd{sub 9.34}Ru{sub 6}Mg{sub 17.66} type structure, space group I4/mmm. This structure exhibits a complex condensation pattern of square-prisms and square-antiprisms around the magnesium and ruthenium atoms, respectively. Y{sub 2}RuMg{sub 2} (a=344.0(1), c=2019(1) pm) and Tb{sub 2}RuMg{sub 2} (a=341.43(6), c=2054.2(7) pm) adopt the Er{sub 2}RuMg{sub 2} structure and Tm{sub 3}Ru{sub 2}Mg (a=337.72(9), c=1129.8(4) pm) is isotypic with Sc{sub 3}Ru{sub 2}Mg. Tm{sub 3}Ru{sub 2}Mg{sub 2} (a=337.35(9), c=2671(1) pm) and Lu{sub 3}Ru{sub 2}Mg{sub 2} (a=335.83(5), c=2652.2(5) pm) are the first ternary ordered variants of the Ti{sub 3}Cu{sub 4} type, space group I4/mmm. These five compounds belong to a large family of intermetallics which are completely ordered superstructures of the bcc subcell. The group-subgroup scheme for Lu{sub 3}Ru{sub 2}Mg{sub 2} is presented. The common structural motif of all three structure types are ruthenium-centered rare earth cubes reminicent of the CsCl type. Magnetic susceptibility measurements of Y{sub 2}RuMg{sub 2} and Lu{sub 3}Ru{sub 2}Mg{sub 2} samples revealed Pauli paramagnetism of the conduction electrons.

Amidines for versatile ruthenium(II)-catalyzed oxidative C-H activations with internal alkynes and acrylates.

Science.gov (United States)

Li, Jie; John, Michael; Ackermann, Lutz

2014-04-25

Cationic ruthenium complexes derived from KPF6 or AgOAc enabled efficient oxidative CH functionalizations on aryl and heteroaryl amidines. Thus, oxidative annulations of diversely decorated internal alkynes provided expedient access to 1-aminoisoquinolines, while catalyzed C-H activations with substituted acrylates gave rise to structurally novel 1-iminoisoindolines. The powerful ruthenium(II) catalysts displayed a remarkably high site-, regio- and, chemoselectivity. Therefore, the catalytic system proved tolerant of a variety of important electrophilic functional groups. Detailed mechanistic studies provided strong support for the cationic ruthenium(II) catalysts to operate by a facile, reversible C-H activation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ruthenium complexing during sorption by graft copolymer of polyacrylonitrile fibre with poly-2-methyl-5-vnylpyridine (PAN-MVP)

International Nuclear Information System (INIS)

Simanova, S.A.; Kolmakova, A.I.; Konovalov, L.V.; Kukushkin, Yu.N.; Lysenko, A.A.

1984-01-01

The sorption of ruthenium chlorocomplexes is studied on graft copolymer of polyacrylonitrile fibre with poly-2-methyl-5-vinylpyridine (PAN-MVP). The sorption has been performed under static conditions in the course of mixing at 20 and 98 deg from 0.1-2 OM HCl, 0.1-1 m NaCl solutions. The volume of the investigated solutions constituted 25 ml, fibre weight -0.1-0.3 g. Ruthenium concentration in solutions has been changed in the limits of 5x10 3 -2x10 -2 mol/l. The fibre has been preliminarily moistened by a solution containing no ruthenium. In all cases fresh-prepared ruthenium chlorocomplex solutions have been used. It has been found that with temperature increase the PAN-MVP sorption capacitance relative to ruthenium increases (at 20 deg-1.15 mmol/g, at 98 deg-1.70 mmol/g. The ruthenium chlorocomplex sorption by pyridine fibrous sorbent from salt-acid solutions occurs by anionoexchange mechanism and is related to the formation in the sorbent phase of onium chlorocomplexes - (RPyH) 2 [RuCl 6 ]. In the course of sorbents heating pyridine compounds are subject to Anderson regroupping with formation of compounds of diamine type-[Ru(RPy) 2 Cl 4

Gray Wolf (Canis lupus) dyad monthly association rates by demographic group.

Science.gov (United States)

Barber-Meyer, Shannon M.; Mech, L. David

2015-01-01

Preliminary data from GPS-collared wolves (Canis lupus) in the Superior National Forest of northeastern Minnesota indicated wolves had low association rates with packmates during summer. However, aerial-telemetry locations of very high frequency (VHF)-radioed wolves in this same area showed high associations among packmates during winter. We analyzed aerial-telemetry-location data from VHF-collared wolves in several packs (n=18 dyads) in this same area from 1994-2012 by month, and found lowest association rates occurred during June. While other studies have found low association among wolf packmates during summer, information on differences in association patterns depending on the wolf associates’ demographics is sparse. During May-July, association rates were greatest for breeding pairs, followed by sibling dyads, and lowest for parent– offspring dyads. Our findings improve our understanding of how individual wolf relationships affect monthly association rates. We highlight some important remaining questions regarding wolf packmate associations.

Curricular Goals and Personal Goals in Master's Thesis Projects: Dutch Student-Supervisor Dyads

Science.gov (United States)

de Kleijn, Renske A. M.; Meijer, Paulien C.; Brekelmans, Mieke; Pilot, Albert

2013-01-01

To be effective, feedback should be goal-related. In order to better understand goal-related feedback in Master's thesis projects, the present study explores the goals of supervisors and students in supervision dyads and similarities and differences within and between these dyads. Twelve supervisors and students were interviewed, and their goals…

Comparative genomics of Cluster O mycobacteriophages.

Directory of Open Access Journals (Sweden)

Steven G Cresawn

Full Text Available Mycobacteriophages--viruses of mycobacterial hosts--are genetically diverse but morphologically are all classified in the Caudovirales with double-stranded DNA and tails. We describe here a group of five closely related mycobacteriophages--Corndog, Catdawg, Dylan, Firecracker, and YungJamal--designated as Cluster O with long flexible tails but with unusual prolate capsids. Proteomic analysis of phage Corndog particles, Catdawg particles, and Corndog-infected cells confirms expression of half of the predicted gene products and indicates a non-canonical mechanism for translation of the Corndog tape measure protein. Bioinformatic analysis identifies 8-9 strongly predicted SigA promoters and all five Cluster O genomes contain more than 30 copies of a 17 bp repeat sequence with dyad symmetry located throughout the genomes. Comparison of the Cluster O phages provides insights into phage genome evolution including the processes of gene flux by horizontal genetic exchange.

Dye sensitized photovoltaic cells: Attaching conjugated polymers to zwitterionic ruthenium dyes

DEFF Research Database (Denmark)

Krebs, Frederik C; Biancardo, M.

2006-01-01

The synthesis of a zwitterionic ruthenium dye that binds to anatase surfaces and has a built-in functionality that allows for the attachment of a conjugated polymer chain is presented. The system was found to adsorb on the surface of anatase anchored by the ruthenium dye. Two types of devices were...... prepared: standard photoelectrochemical (PEC) solar cells and polymer solar cells. The PEC solar cells employed a sandwich geometry between TiO2 nanoporous photoanodes and Pt counter electrodes using LiI/I-2 in CH3CN as an electrolyte. The polymer solar cells employed planar anatase electrodes...

Ruthenium Complexes as NO Donors for Vascular Relaxation Induction

Directory of Open Access Journals (Sweden)

Renata Galvão de Lima

2014-07-01

Full Text Available Nitric oxide (NO donors are substances that can release NO. Vascular relaxation induction is among the several functions of NO, and the administration of NO donors is a pharmacological alternative to treat hypertension. This review will focus on the physicochemical description of ruthenium-derived NO donor complexes that release NO via reduction and light stimulation. In particular, we will discuss the complexes synthesized by our research group over the last ten years, and we will focus on the vasodilation and arterial pressure control elicited by these complexes. Soluble guanylyl cyclase (sGC and potassium channels are the main targets of the NO species released from the inorganic compounds. We will consider the importance of the chemical structure of the ruthenium complexes and their vascular effects.

Flotation-spectrophotometric determination of ruthenium in the Ru(IV)-chloride-rhodamine 6G-toluene system

International Nuclear Information System (INIS)

Balcerzak, M.

1985-01-01

The reduction of RuO 4 in hydrochloric acid has been examined. A sensitive flotation-spectrophotometric method of the determination of ruthenium based on the ion associate formed by the anionic chlorid complex of ruthenium RuCl 2- 6 with the basic dye Rhodamine 6G (R6G) has been developed. The solution of the ion associate obeys Beer's law up to the concentration of 0.25 μg Ru/ml. The ion associate precipitates when the aqueous solution is shaken with toluene. The separated compound is dissolved in acetone. The molar absorptivity (epsilon) at 530 nm is 5.1 x 10 5 l x mole -1 x cm -1 . The relative standard deviation is 3-7%. The mole ratio of Ru:R6G in the complex is 1:5. Osmium reacts similarly. The determination of ruthenium can be selective after the preliminary separation of osmium as OsO 4 . The method was applied to the determination of microgram amounts of ruthenium in crucible platinum. (Author)

Interaction of ruthenium (4) and osmium (4) with 2-mercaptobenzimidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole in the presence of edta

International Nuclear Information System (INIS)

Busev, A.I.; Ignat'eva, T.I.; Lomakina, L.N.

1975-01-01

Interaction of ruthenium (4) and osmium (4) with 2-mercaptobenzimidazole (2MBI), 2-mercaptobenzoxazole (2MBO) and 2-mercaptobenzothiazole (2MBT) in the presence of EDTA was studied. The interaction of ruthenium (4) and osmium (4) with EDTA was constidered. Ruthenium complex is formed with constant output at 2-4.5 pH after 30 min.heating. In the lowacid solution (pH 2-4) osmium reacts with EDTA forming soluble compound. Characteristics of ruthenium (4) compound with 2MBI, 2MBO and 2MBT produced in the presence of EDTA are presented. Osmium (4) in the presence of EDTA and above mentioned organic reagents and when heating forms lowsoluble compounds. Possibility of joint determination of ruthenium and osmium with help of 2MBI in the presence of EDTA under conditions of minimum complexing osmium with EDTA was investigated

Interaction of ruthenium (4) and osmium (4) with 2-mercaptobenzimidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole in the presence of EDTA

Energy Technology Data Exchange (ETDEWEB)

Busev, A I; Ignat' eva, T I; Lomakina, L N [Moskovskij Gosudarstvennyj Univ. (USSR). Kafedra Analiticheskoj Khimii

1975-05-01

Interaction of ruthenium (4) and osmium (4) with 2-mercaptobenzimidazole (2MBI), 2-mercaptobenzoxazole (2MBO) and 2-mercaptobenzothiazole (2MBT) in the presence of EDTA was studied. The interaction of ruthenium (4) and osmium (4) with EDTA was considered. Ruthenium complex is formed with constant output at 2-4.5 pH after 30 min. heating. In the low acid solution (pH 2-4) osmium reacts with EDTA forming soluble compound. Characteristics of ruthenium (4) compound with 2MBI, 2MBO and 2MBT produced in the presence of EDTA are presented. Osmium (4) in the presence of EDTA and above mentioned organic reagents and when heating forms low soluble compounds. Possibility of joint determination of ruthenium and osmium with help of 2MBI in the presence of EDTA under conditions of minimum complexing osmium with EDTA was investigated.

Dynamics of the contact between a ruthenium surface with a single nanoasperity and a flat ruthenium surface: Molecular dynamics simulations

International Nuclear Information System (INIS)

Barros de Oliveira, Alan; Fortini, Andrea; Buldyrev, Sergey V.; Srolovitz, David

2011-01-01

We study the dynamics of the contact between a pair of surfaces (with properties designed to mimic ruthenium) via molecular dynamics simulations. In particular, we study the contact between a ruthenium surface with a single nanoasperity and a flat ruthenium surface. The results of such simulations suggest that contact behavior is highly variable. The goal of this study is to investigate the source and degree of this variability. We find that during compression, the behavior of the contact force displacement curves is reproducible, while during contact separation, the behavior is highly variable. Examination of the contact surfaces suggests that two separation mechanisms are in operation and give rise to this variability. One mechanism corresponds to the formation of a bridge between the two surfaces that plastically stretches as the surfaces are drawn apart and eventually separate in shear. This leads to a morphology after separation in which there are opposing asperities on the two surfaces. This plastic separation/bridge formation mechanism leads to a large work of separation. The other mechanism is a more brittle-like mode in which a crack propagates across the base of the asperity (slightly below the asperity/substrate junction) leading to most of the asperity on one surface or the other after separation and a slight depression facing this asperity on the opposing surface. This failure mode corresponds to a smaller work of separation. This failure mode corresponds to a smaller work of separation. Furthermore, contacts made from materials that exhibit predominantly brittle-like behavior will tend to require lower work of separation than those made from ductile-like contact materials.

Supercapacitive performance of hydrous ruthenium oxide (RuO2 ...

Indian Academy of Sciences (India)

gel method have been employed to prepare ruthenium oxide thin films. Recently ... the potentiostat (263A EG&G, Princeton Applied Research. Potentiostat). .... is a mixed conductor that conducts protons and electrons in acidic solution (as ...

Dehydrogenative Coupling of Primary Alcohols To Form Esters Catalyzed by a Ruthenium N-Heterocyclic Carbene Complex

DEFF Research Database (Denmark)

Sølvhøj, Amanda Birgitte; Madsen, Robert

2011-01-01

The ruthenium complex [RuCl2(IiPr)(p-cymene)] catalyzes the direct condensation of primary alcohols into esters and lactones with the release of hydrogen gas. The reaction is most effective with linear aliphatic alcohols and 1,4-diols and is believed to proceed with a ruthenium dihydride...

One-pot hydrothermal synthesis of ruthenium oxide nanodots on reduced graphene oxide sheets for supercapacitors

Energy Technology Data Exchange (ETDEWEB)

Chen Yao [Institute of Electrical Engineering, Chinese Academy of Sciences, Beijing 100190 (China); Graduate University of Chinese Academy Sciences, Beijing 100049 (China); Zhang Xiong [Institute of Electrical Engineering, Chinese Academy of Sciences, Beijing 100190 (China); Zhang Dacheng [Institute of Electrical Engineering, Chinese Academy of Sciences, Beijing 100190 (China); Graduate University of Chinese Academy Sciences, Beijing 100049 (China); Ma Yanwei, E-mail: ywma@mail.iee.ac.cn [Institute of Electrical Engineering, Chinese Academy of Sciences, Beijing 100190 (China)

2012-01-15

Highlights: > Graphite oxide instead of graphene as precursor has been used to synthesize reduced graphene oxide/ruthenium oxide composites by a hydrothermal treatment. > Using NaOH solution to adjust pH of GO colloids leads to homogeneous ruthenium oxide deposited on reduced graphene oxide sheets. > A maximum capacitance of 471 F g{sup -1} is obtained at 0.5 A g{sup -1} for the composites when loading 40% of RuO{sub 2} and its life retention reaches 92% after 3000 cycles. - Abstract: Ruthenium oxide nanodots have been deposited on reduced graphene oxide (RGO) sheets homogeneously by hydrothermal and annealing methods. Adding NaOH solution in GO colloids prevents the restack and agglomeration of GO sheets when mixed with ruthenium chloride solution. Local crystallization of RuO{sub 2} in the composites is revealed by X-ray diffraction and transmission electron microscopy. The element mapping image demonstrates the uniform distribution of Ru on RGO sheets. Unlike the pure crystalline RuO{sub 2} exhibiting poor electrochemical performance, the composites present superior capacitive properties. The hydrothermal time is optimized and a maximum of 471 F g{sup -1} is measured in the composites at 0.5 A g{sup -1} when loaded with 45 wt% of RuO{sub 2}. After 3000 cycles, its specific capacitance remains 92% of the maximum capacitance. Our results suggest potential application of the reduced graphene oxide/ruthenium oxide composites to supercapacitors.

One-pot hydrothermal synthesis of ruthenium oxide nanodots on reduced graphene oxide sheets for supercapacitors

International Nuclear Information System (INIS)

Chen Yao; Zhang Xiong; Zhang Dacheng; Ma Yanwei

2012-01-01

Highlights: → Graphite oxide instead of graphene as precursor has been used to synthesize reduced graphene oxide/ruthenium oxide composites by a hydrothermal treatment. → Using NaOH solution to adjust pH of GO colloids leads to homogeneous ruthenium oxide deposited on reduced graphene oxide sheets. → A maximum capacitance of 471 F g -1 is obtained at 0.5 A g -1 for the composites when loading 40% of RuO 2 and its life retention reaches 92% after 3000 cycles. - Abstract: Ruthenium oxide nanodots have been deposited on reduced graphene oxide (RGO) sheets homogeneously by hydrothermal and annealing methods. Adding NaOH solution in GO colloids prevents the restack and agglomeration of GO sheets when mixed with ruthenium chloride solution. Local crystallization of RuO 2 in the composites is revealed by X-ray diffraction and transmission electron microscopy. The element mapping image demonstrates the uniform distribution of Ru on RGO sheets. Unlike the pure crystalline RuO 2 exhibiting poor electrochemical performance, the composites present superior capacitive properties. The hydrothermal time is optimized and a maximum of 471 F g -1 is measured in the composites at 0.5 A g -1 when loaded with 45 wt% of RuO 2 . After 3000 cycles, its specific capacitance remains 92% of the maximum capacitance. Our results suggest potential application of the reduced graphene oxide/ruthenium oxide composites to supercapacitors.

Homo- or Hetero- Triplet-Triplet Annihilation? A Case Study with Perylene-Bodipy Dyads/Triads

KAUST Repository

Cui, Xiaoneng; El-Zohry, Ahmed M.; Wang, Zhijia; Zhao, Jianzhang; Mohammed, Omar F.

2017-01-01

The photophysical processes of intramolecular ‘ping-pong’ energy transfers in the iodinated reference dyad BDP-I2-Py, as well as the uniodinated dyad BDP-Py and triad BDP-2Py, were studied. For BDP-I2-Py, a forward Förster resonance energy transfer

Selective deposition of nanostructured ruthenium oxide using Tobacco mosaic virus for micro-supercapacitors in solid Nafion electrolyte

Energy Technology Data Exchange (ETDEWEB)

Gnerlich, Markus; Ben-Yoav, Hadar; Culver, James N.; Ketchum, Douglas R.; Ghodssi, Reza

2015-10-01

A three-dimensional micro-supercapacitor has been developed using a novel bottom-up assembly method combining genetically modified Tobacco mosaic virus (TMV-1Cys), photolithographically defined micropillars and selective deposition of ruthenium oxide on multi-metallic microelectrodes. The three-dimensional microelectrodes consist of a titanium nitride current collector with two functionalized areas: (1) gold coating on the active electrode area promotes TMV-1Cys adhesion, and (2) sacrificial nickel pads dissolve in ruthenium tetroxide plating solution to produce ruthenium oxide on all electrically connected areas. The microfabricated electrodes are arranged in an interdigitated pattern, and the capacitance per electrode has been measured as high as 203 mF cm-2 with solid Nafion electrolyte. The process integration of bio-templated ruthenium oxide with microfabricated electrodes and solid electrolyte is an important advance towards the energy storage needs of mass produced self-sufficient micro-devices.

The Relations of Family Members’ Unique and Shared Perspectives of Family Dysfunction to Dyad Adjustment

Science.gov (United States)

Jager, Justin; Yuen, Cynthia X.; Bornstein, Marc H.; Putnick, Diane L.; Hendricks, Charlene

2017-01-01

Among a community sample of families (N = 128), this study examined how family members’ shared and unique perspectives of family dysfunction relate to dyad members’ shared views of dyad adjustment within adolescent-mother, adolescent-father, and mother-father dyads. Independent of a family’s family perspective (shared perspective of family dysfunction), the adolescent’s unique perspective was associated with lower security and higher conflict with both mother and father, the father’s unique perspective was associated with lower security and higher conflict with the adolescent as well as lower marital quality with mother, and the mother unique perspective was associated with lower marital quality with the father. Moreover, for adolescent-parent dyads, compared to the parent unique perspective, the adolescent unique perspective was more strongly associated with dyad adjustment. These findings indicate that both shared and unique views of the family system – the adolescent’s unique view in particular - independently relate to the health of family subsystems. They also suggest that research as well as therapeutic interventions that focus on just the shared view of the family may miss important elements of family dysfunction. PMID:24884682

Spectroscopic and electrochemical correlations in triangular ruthenium clusters containing N-heterocyclic ligands

International Nuclear Information System (INIS)

Cunha, C.J. da.

1989-01-01

A series of clusters of general formula [Ru sub(3) O (OOCCH sub(3)) sub(6) L sub(3)] sup(+), where L = N-heterocyclic ligands, were synthesized and characterized based on elemental analysis. UV-VIS and IR spectra. Voltametric studies revealed the existence of up to six acessible oxidation states, with a high degree of electronic delocalization. The Ru sub(3) O trigonal center possesses many delocalized electrons and can be visualized as a source of electrons. The ligands coordinated to the clusters tune their redox potentials, determine the differences in their electronic spectra, and are responsible for the special conditions required for their synthesis. (author)

Ruthenium-modified cytochrome c: temperature dependence of the rate of intramolecular electron transfer

International Nuclear Information System (INIS)

Isied, S.S.; Kuehn, C.; Worosila, G.

1984-01-01

The ruthenium-modified horse heart cytochrome c, Ru(III)-cyt c(III), where the ruthenium is bound to the histidines-33 residue has been synthesized and characterized by ruthenium analysis, UV-vis and CD spectra, and differential pulse polarography and cyclic voltammetry. The intermediate Ru(III)-cyt c(III) has been generated by pulse-radioanalysis with use of four different radicals, CO 2 -., (CH 3 )COH., (CH 2 OH) 3 CCHOH, and -OCCH(OH)C(OH)CO 2 -. The rate of intramolecular electron transfer within the Ru(III)-cyt c(III) complex and its temperature dependence were determined over a 40 0 C temperature range with the CO 2 -. radical. At 25 0 C, these values are k/sub u/=53 +/- s/sup -1/ (pH 7.01 M phosphate buffer, 0.1 M NaHCO 2 ), ΔH/sup +/=3.5 +/- 0.2 kcal mol/sup -1/, and ΔS/sup +/=-39 +/- 1 eu

Studying the effect of Ruthenium on High Temperature Mechanical Properties of Nickel Based Superalloys and Determining the Universal Behavior of Ruthenium at Atomic Scale with respect to alloying elements, Stress and Temperature

Directory of Open Access Journals (Sweden)

Sriswaroop Dasari

2016-10-01

Full Text Available Any property of a material is a function of its microstructure and microstructure is a function of material composition. So, to maximize the desired properties of a material, one has to understand the evolution of microstructure which in turn is nothing but the reflection of the role of alloying elements. Research has not been done to understand the universal behavior of a certain base/alloying element. Let’s take the example of Cl- ion in HCl, we all know that in general, chloride ion can only be replaced by Fluoride or oxygen ion and that no other ion can replace it. But when you consider a metal like Ni, Co, Cr, Fe etc. there is no establishment that it behaves only in a certain way. Though I concord to the fact that discovery of universal behavior of Ni is lot complex than chloride ion, I think that future research should be focused in this direction also. Superalloys are the candidate materials required to improve thermal efficiency of a gas turbine by allowing higher turbine inlet gas temperatures. Gas turbines are the heart of local power systems, next generation jet engines and high performance space rockets. Recent research in superalloys showed that addition of some alloying elements in minor quantities can result in drastic change in properties. Such an alloying element is Ruthenium (Ru. Addition of Ruthenium to superalloys has shown improvement in mechanical properties by an order of magnitude. However reasons for such improvement are not known yet. Hence, there is a need to identify its role and discover the universal behavior of ruthenium to utilize it efficiently. In this proposal, we study materials with different compositions that are derived based on one ruthenium containing superalloy, and different thermomechanical history. Based on the evolution of microstructures and results of mechanical testing, we plan to determine the exact role of Ruthenium and prediction of its behavior with respect to other elements in the material

The role of maternal factors in sibling relationship quality: a multilevel study of multiple dyads per family.

Science.gov (United States)

Jenkins, Jennifer; Rasbash, Jon; Leckie, George; Gass, Krista; Dunn, Judy

2012-06-01

  Although many children grow up with more than one sibling, we do not yet know if sibling dyads within families show similarities to one another on sibling affection and hostility. In the present study the hypotheses were tested that (a) there will be significant between family variation in change in sibling affection and hostility and (b) this between family variation will be explained by maternal affective climate, operationalized as positive and negative ambient parenting, differential parenting and maternal malaise.   A general population sample of families with single and multiple sibling dyads were visited twice, 2 years apart. Up to 2 children in a family acted as informants; 253 relationships were rated in 118 families. A cross-classified, multilevel model was fit to separate between-family and within-family variance in sibling relationships while simultaneously controlling for informant and partner influences.   Thirty-seven percent of the variance in change in sibling affection and 32% of the variance in change in sibling hostility was between family variance. The measured maternal affective climate including, maternal malaise and maternal ambient and differential hostility and affection explained between family differences.   Sibling relationship quality clusters in families and is partly explained by maternal affective climate. © 2011 The Authors. Journal of Child Psychology and Psychiatry © 2011 Association for Child and Adolescent Mental Health.

Reaction of a (Salen)ruthenium(VI) nitrido complex with thiols. C-H bond activation by (Salen)ruthenium(IV) sulfilamido species.

Science.gov (United States)

Man, Wai-Lun; Lam, William W Y; Kwong, Hoi-Ki; Peng, Shie-Ming; Wong, Wing-Tak; Lau, Tai-Chu

2010-01-04

The reaction of [Ru(VI)(N)(L)(MeOH)](PF(6)) [1; L = N,N'-bis(salicylidene)-o-cyclohexyldiamine dianion] with a stoichiometric amount of RSH in CH(3)CN gives the corresponding (salen)ruthenium(IV) sulfilamido species [Ru(IV){N(H)SR}(L)(NCCH(3))](PF(6)) (2a, R = (t)Bu; 2b, R = Ph). Metathesis of 2a with NaN(3) in methanol affords [Ru(IV){N(H)S(t)Bu}(L)(N(3))] (2c). 2a undergoes further reaction with 1 equiv of RSH to afford a (salen)ruthenium(III) sulfilamine species, [Ru(III){N(H)(2)S(t)Bu}(L)(NCCH(3))](PF(6)) (3). On the other hand, 2b reacts with 2 equiv of PhSH to give a (salen)ruthenium(III) ammine species [Ru(III)(NH(3))(L)(NCCH(3))](PF(6)) (4); this species can also be prepared by treatment of 1 with 3 equiv of PhSH. The X-ray structures of 2c and 4 have been determined. Kinetic studies of the reaction of 1 with excess RSH indicate the following schemes: 1 --> 2a --> 3 (R = (t)Bu), 1 --> 2b --> 4 (R = Ph). The conversion of 1 to 2 probably involves nucleophilic attack of RSH at the nitrido ligand, followed by a proton shift. The conversions of 2a to 3 and 2b to 4 are proposed to involve rate-limiting H-atom abstraction from RSH by 2a or 2b. 2a and 2b are also able to abstract H atoms from hydrocarbons with weak C-H bonds. These reactions occur with large deuterium isotope effects; the kinetic isotope effect values for the oxidation of 9,10-dihydroanthracene, 1,4-cyclohexadiene, and fluorene by 2a are 51, 56, and 11, respectively.

Mathematical modelling of brittle phase precipitation in complex ruthenium containing nickel-based superalloys

International Nuclear Information System (INIS)

Rettig, Ralf

2010-01-01

A new model has been developed in this work which is capable of simulating the precipitation kinetics of brittle phases, especially TCP-phases (topologically close packed phases) in ruthenium containing superalloys. The model simultaneously simulates the nucleation and the growth stage of precipitation for any number of precipitating phases. The CALPHAD method (Calculation of Phase Diagrams) is employed to calculate thermodynamic properties, such as the driving force or phase compositions in equilibrium. For calculation of diffusion coefficients, kinetic mobility databases which are also based on the CALPHAD-method are used. The model is fully capable of handling multicomponent effects, which are common in complex superalloys. Metastable phases can be treated and will automatically be dissolved if they get unstable. As the model is based on the general CALPHAD method, it can be applied to a broad range of precipitation processes in different alloys as long as the relevant thermodynamic and kinetic databases are available. The developed model proves that the TCP-phases precipitate in a sequence of phases. The first phase that is often formed is the metastable σ-phase because it has the lowest interface energy due to low-energy planes at the interface between matrix and precipitate. After several hundred hours the stable μ- and P-phases start to precipitate by nucleating at the σ-phase which is energetically favourable. During the growth of these stable phases the sigma-phase is continuously dissolved. It can be shown by thermodynamic CALPHAD calculations that the sigma-phase has a lower Gibbs free enthalpy than the μ- and P-phase. All required parameters of the model, such as interface energy and nucleate densities, have been estimated. The mechanisms of suppression of TCP-phase precipitation in the presence of ruthenium in superalloys were investigated with the newly developed model. It is shown by the simulations that ruthenium mostly affects the nucleation

Behaviour of ruthenium dioxide particles in borosilicate glasses and melts

Energy Technology Data Exchange (ETDEWEB)

Pflieger, Rachel [DEN/DTCD-SCDV/CEA Valrho, Centre de Marcoule, BP17171, 30207 Bagnols-sur-Ceze (France); Institut de Chimie Separative de Marcoule, UMR5257, Centre de Marcoule, BP17171, 30207 Bagnols-sur-Ceze Cedex (France)], E-mail: rachel_pflieger@yahoo.fr; Lefebvre, Leila [DEN/DTCD-SCDV/CEA Valrho, Centre de Marcoule, BP17171, 30207 Bagnols-sur-Ceze (France); Malki, Mohammed [CNRS/CEMHTI-1D Av. de la Recherche Scientifique, 45701 Orleans cedex 2 (France); Polytech Orleans, Universite d' Orleans, 8 rue Leonard de Vinci, 45072 Orleans cedex 2 (France); Allix, Mathieu [CNRS/CEMHTI-1D Av. de la Recherche Scientifique, 45701 Orleans cedex 2 (France); Grandjean, Agnes [DEN/DTCD-SCDV/CEA Valrho, Centre de Marcoule, BP17171, 30207 Bagnols-sur-Ceze (France); Institut de Chimie Separative de Marcoule, UMR5257, Centre de Marcoule, BP17171, 30207 Bagnols-sur-Ceze Cedex (France)

2009-06-01

Ruthenium-glass systems are formed during the vitrification of nuclear waste. They are also widely used in micro-electronics because of their unique electrical properties. However, the interaction of this element with the glass matrix remains poorly understood. This work focuses on a RuO{sub 2} particles-nuclear alumino-borosilicate glass system in which the electrical conductivity is known to vary considerably with the RuO{sub 2} content and to become electronic above about 0.5-0.7 vol.% RuO{sub 2} [R. Pflieger, M. Malki, Y. Guari, J. Larionova, A. Grandjean, J. Am. Ceram. Soc., accepted for publication]. Some RuO{sub 2} segregation was observed in SEM/TEM investigations but no continuous chain of RuO{sub 2} particles could be seen. Electron relays between the particles are then necessary for a low-rate percolation, such as the nanoclusters suggested by Adachi et al. [K. Adachi, S. Iida, K. Hayashi, J. Mater. Res. 9 (7) (1994) 1866; K. Adachi, H. Kuno, J. Am. Ceram. Soc. 83 (10) (2000) 2441], which could consist in dissolved ruthenium. Indeed, several observations made here clearly indicate the presence of dissolved ruthenium in the glass matrix, like the modification of the glass density in presence of RuO{sub 2} particles or the diffusion-limited growth of RuO{sub 2} particles in the melt.

Application of the ruthenium and technetium thermodynamic data bases used in the EQ3/6 geochemical codes

Energy Technology Data Exchange (ETDEWEB)

Isherwood, D.

1985-04-01

Based on a critical review of the available thermodynamic data, computerized data bases for technetium and ruthenium were created for use with the EQ3/6 geochemical computer codes. The technetium data base contains thermodynamic data for 8 aqueous species and 15 solids; 26 aqueous species and 9 solids were included in the ruthenium data base. The EQ3NR code was used to calculate solubility limits for ruthenium (8 x 10{sup -16} M) in ground water from Yucca Mountain, a potential nuclear waste repository site near the Nevada Test Site (NTS). The code confirmed the essentially unlimited solubility of technetium in oxidizing conditions, such as those that are believed to exist in the unsaturated zone at Yucca Mountain and the Cambric Nuclear event site at the NTS. Ruthenium migration observed from the Cambric site was evaluated. The solubility limit for ruthenium (as the aqueous species RuO{sub 4}{sup -}) when constrained by RuO{sub 2} is approximately equal to the concentration of ruthenium found in the cavity ground water (i.e., 2.1 x 10{sup -11} vs 4.5 x 10{sup -11} M). Differences in ruthenium solubility limits between Yucca Mountain and Cambric are primarily due to differences in ground-water pH. Technetium solubility (3 x 10{sup -8} M) for moderately reducing conditions (Eh = -0.1 V) using the metastable oxide, TcO{sub 2}.2H{sub 2}O, as the solubility constraint is within the range of experimental values recently published in a study of technetium sorption on basalt. Previously published technetium solubilities of 10{sup -12} to 10{sup -16} M were apparently based on a technetium data base that did not include aqueous species other than TcO{sub 4}{sup -}. When TcO(OH){sub 2}{sup 0} is included in the data base, the calculated values are much closer to the experimental results. Eh-pH diagrams were also generated for a variety of conditions using the SOLUPLOT code.

Application of the ruthenium and technetium thermodynamic data bases used in the EQ3/6 geochemical codes

International Nuclear Information System (INIS)

Isherwood, D.

1985-04-01

Based on a critical review of the available thermodynamic data, computerized data bases for technetium and ruthenium were created for use with the EQ3/6 geochemical computer codes. The technetium data base contains thermodynamic data for 8 aqueous species and 15 solids; 26 aqueous species and 9 solids were included in the ruthenium data base. The EQ3NR code was used to calculate solubility limits for ruthenium (8 x 10 -16 M) in ground water from Yucca Mountain, a potential nuclear waste repository site near the Nevada Test Site (NTS). The code confirmed the essentially unlimited solubility of technetium in oxidizing conditions, such as those that are believed to exist in the unsaturated zone at Yucca Mountain and the Cambric Nuclear event site at the NTS. Ruthenium migration observed from the Cambric site was evaluated. The solubility limit for ruthenium (as the aqueous species RuO 4 - ) when constrained by RuO 2 is approximately equal to the concentration of ruthenium found in the cavity ground water (i.e., 2.1 x 10 -11 vs 4.5 x 10 -11 M). Differences in ruthenium solubility limits between Yucca Mountain and Cambric are primarily due to differences in ground-water pH. Technetium solubility (3 x 10 -8 M) for moderately reducing conditions (Eh = -0.1 V) using the metastable oxide, TcO 2 .2H 2 O, as the solubility constraint is within the range of experimental values recently published in a study of technetium sorption on basalt. Previously published technetium solubilities of 10 -12 to 10 -16 M were apparently based on a technetium data base that did not include aqueous species other than TcO 4 - . When TcO(OH) 2 0 is included in the data base, the calculated values are much closer to the experimental results. Eh-pH diagrams were also generated for a variety of conditions using the SOLUPLOT code

Ruthenium release modelling in air and steam atmospheres under severe accident conditions using the MAAP4 code

International Nuclear Information System (INIS)

Beuzet, Emilie; Lamy, Jean-Sylvestre; Perron, Hadrien; Simoni, Eric; Ducros, Gérard

2012-01-01

Highlights: ► We developed a new modelling of fuel oxidation and ruthenium release in the EDF version of the MAAP4 code. ► We validated this model against some VERCORS experiments. ► Ruthenium release prediction quantitatively and qualitatively well reproduced under air and steam atmospheres. - Abstract: In a nuclear power plant (NPP), a severe accident is a low probability sequence that can lead to core fusion and fission product (FP) release to the environment (source term). For instance during a loss-of-coolant accident, water vaporization and core uncovery can occur due to decay heat. These phenomena enhance core degradation and, subsequently, molten materials can relocate to the lower head of the vessel. Heat exchange between the debris and the vessel may cause its rupture and air ingress. After lower head failure, steam and air entering in the vessel can lead to degradation and oxidation of materials that are still intact in the core. Indeed, Zircaloy-4 cladding oxidation is very exothermic and fuel interaction with the cladding material can decrease its melting temperature by several hundred of Kelvin. FP release can thus be increased, noticeably that of ruthenium under oxidizing conditions. Ruthenium is of particular interest because of its high radio-toxicity due to 103 Ru and 106 Ru isotopes and its ability to form highly volatile compounds, even at room temperature, such as gaseous ruthenium tetra-oxide (RuO 4 ). It is consequently of great need to understand phenomena governing steam and air oxidation of the fuel and ruthenium release as prerequisites for the source term issues. A review of existing data on these phenomena shows relatively good understanding. In terms of oxygen affinity, the fuel is oxidized before ruthenium, from UO 2 to UO 2+x . Its oxidation is a rate-controlling surface exchange reaction with the atmosphere, so that the stoichiometric deviation and oxygen partial pressure increase. High temperatures combined with the presence

Cytogenotoxic effects of two potential anticancer Ruthenium(III Schiff Bases complexes

Directory of Open Access Journals (Sweden)

Izet Eminovic

2016-10-01

Full Text Available Introduction: Treatment of cancer has been subject of great interest. Researchers are continuously searching for new medicines. In this sense, ruthenium complexes have big potential. Some evidences suggest that ruthenium compounds possess anticancer activities. We synthesized two recently published ruthenium(III complexes with bidentate O,N and tridentate O,O,N Schiff bases derived from 5-substituted salicylaldehyde and aminophenol or anilineare. These compounds showed affinity for binding to the DNA molecule, however, insufficient data are available regarding their possible toxic effects on biological systems.Methods: In the present study we evaluated genotoxic, cytotoxic, and cytostatic effects of Na[RuCl2(L12] and Na[Ru(L22], using the Allium cepa assay.Results: Different toxic effects were observed depending on the substance, tested concentration, and endpoint measured. In general, the tested compounds significantly lowered the root growth and mitotic index values as compared to the control group. Additionally, a wide range of abnormal mitotic stages, both clastogenic and non-clastogenic were observed in the treated cells. Na[RuCl2(L12] significantly increased the frequency of sticky metaphases, chromosome bridges, micronuclei, impaired chromosome segregation, as well as number of apoptotic and necrotic cells over the controls. In contrast, Na[Ru(L22] did not show significant evidence of genotoxicity with regard to chromosome aberrations and micronuclei, however, significant differences were detected in the number of apoptotic and necrotic cells when the highest concentration was applied.Conclusions: In this study we demonstrated antiproliferative effects of Na[RuCl2(L12] and Na[Ru(L22]. At clinical level, these results could be interesting for further studies on anticancer potential of the ruthenium(III complexes using animal models.

Ruthenium(II)- bipyridyl with extended π-system: Improved thermo ...

Indian Academy of Sciences (India)

aInorganic and Physical Chemistry Division, Indian Institute of Chemical Technology, Uppal Road, Tarnaka, ... A new extended thermo-stable high molar extinction coefficient bipyridyl ruthenium(II) complex ... cyanines and metal free organic sensitizers have been ..... Iodide-based ionic liquids are more viscous than.

Chemical vapor deposition of amorphous ruthenium-phosphorus alloy films

International Nuclear Information System (INIS)

Shin Jinhong; Waheed, Abdul; Winkenwerder, Wyatt A.; Kim, Hyun-Woo; Agapiou, Kyriacos; Jones, Richard A.; Hwang, Gyeong S.; Ekerdt, John G.

2007-01-01

Chemical vapor deposition growth of amorphous ruthenium-phosphorus films on SiO 2 containing ∼ 15% phosphorus is reported. cis-Ruthenium(II)dihydridotetrakis-(trimethylphosphine), cis-RuH 2 (PMe 3 ) 4 (Me = CH 3 ) was used at growth temperatures ranging from 525 to 575 K. Both Ru and P are zero-valent. The films are metastable, becoming increasingly more polycrystalline upon annealing to 775 and 975 K. Surface studies illustrate that demethylation is quite efficient near 560 K. Precursor adsorption at 135 K or 210 K and heating reveal the precursor undergoes a complex decomposition process in which the hydride and trimethylphosphine ligands are lost at temperatures as low at 280 K. Phosphorus and its manner of incorporation appear responsible for the amorphous-like character. Molecular dynamics simulations are presented to suggest the local structure in the films and the causes for phosphorus stabilizing the amorphous phase

Stable tracer investigations in humans for assessing the biokinetics of ruthenium and zirconium radionuclides

International Nuclear Information System (INIS)

Veronese, I.; Cantone, M.C.; Giussani, A.; Maggioni, T.; Birattari, C.; Bondardi, M.; Groppi, F.; Garlaschelli, I.; Werner, E.; Roth, P.; Hoellriegl, V.; Louvat, P.; Felgenhauer, N.; Zilker, Th.

2003-01-01

The interest in the biokinetics of ruthenium and zirconium in humans is justified by the potential radiological risk represented by their radionuclides. Only a few data related to the biokinetics of ruthenium and zirconium in humans are available and, accordingly, the biokinetic models currently recommended by the ICRP for these elements are mainly based on data from animal experiments. The use of stable isotopes as tracers, coupled with a proper analytical technique (nuclear activation analysis with protons) for their determination in biological samples, represents an ethically acceptable methodology for biokinetic investigations, being free from any radiation risk for the volunteer subjects. In this work, the results obtained in eight biokinetic investigations for ruthenium, conducted on a total of three healthy volunteers, and six for zirconium, performed on a total of three subjects, are presented and compared to the predictions of the ICRP models. (author)

Synthesis of mesogenic phthalocyanine-C60 donor–acceptor dyads designed for molecular heterojunction photovoltaic devices

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Yves Henri Geerts

2009-10-01

Full Text Available A series of phthalocyanine-C60 dyads 2a–d was synthesized. Key steps in their synthesis are preparation of the low symmetry phthalocyanine intermediate by the statistical condensation of two phthalonitriles, and the final esterification of the fullerene derivative bearing a free COOH group. Structural characterization of the molecules in solution was performed by NMR spectroscopy, UV–vis spectroscopy and cyclic voltammetry. Preliminary studies suggest formation of liquid crystalline (LC mesophases for some of the prepared dyads. To the best of our knowledge, this is the first example of LC phthalocyanine-C60 dyads.

Tailoring Ruthenium Exposure to Enhance the Performance of fcc Platinum@Ruthenium Core-Shell Electrocatalysts in the Oxygen Evolution Reaction

KAUST Repository

AlYami, Noktan

2016-05-17

The catalytic properties of noble metal nanocrystals are a function of their size, structure, and surface composition. In particular, achieving high activity without sacrificing stability is essential for designing commercially viable catalysts. A major challenge in designing state-of-the-art Ru-based catalysts for the oxygen evolution reaction (OER), which is a key step in water splitting, is the poor stability and surface tailorability of these catalysts. In this study, we designed rapidly synthesizable size-controlled, morphology-selective, and surface-tailored platinum-ruthenium core-shell (Pt@Ru) and alloy (PtRu) nanocatalysts in a scalable continuous-flow reactor. These core-shell nanoparticles with atomically precise shells were produced in a single synthetic step with carbon monoxide as the reducing agent. By varying the metal precursor concentration, a dendritic or layer-by-layer ruthenium shell can be grown. The catalytic activities of the synthesized Pt@Ru and PtRu nanoparticles exhibit noticeably higher electrocatalytic activity in the OER compared to that of pure Pt and Ru nanoparticles. Promisingly, Pt@Ru nanocrystals with a ~2-3 atomic layer Ru cuboctahedral shell surpass conventional Ru nanoparticles in terms of both durability and activity.

Tailoring Ruthenium Exposure to Enhance the Performance of fcc Platinum@Ruthenium Core-Shell Electrocatalysts in the Oxygen Evolution Reaction

KAUST Repository

AlYami, Noktan; LaGrow, Alec P.; Joya, khurram; Hwang, Jinyeon; Katsiev, Khabiboulakh; Anjum, Dalaver H.; Losovyj, Yaroslav; Sinatra, Lutfan; Kim, Jin Young; Bakr, Osman

2016-01-01

The catalytic properties of noble metal nanocrystals are a function of their size, structure, and surface composition. In particular, achieving high activity without sacrificing stability is essential for designing commercially viable catalysts. A major challenge in designing state-of-the-art Ru-based catalysts for the oxygen evolution reaction (OER), which is a key step in water splitting, is the poor stability and surface tailorability of these catalysts. In this study, we designed rapidly synthesizable size-controlled, morphology-selective, and surface-tailored platinum-ruthenium core-shell (Pt@Ru) and alloy (PtRu) nanocatalysts in a scalable continuous-flow reactor. These core-shell nanoparticles with atomically precise shells were produced in a single synthetic step with carbon monoxide as the reducing agent. By varying the metal precursor concentration, a dendritic or layer-by-layer ruthenium shell can be grown. The catalytic activities of the synthesized Pt@Ru and PtRu nanoparticles exhibit noticeably higher electrocatalytic activity in the OER compared to that of pure Pt and Ru nanoparticles. Promisingly, Pt@Ru nanocrystals with a ~2-3 atomic layer Ru cuboctahedral shell surpass conventional Ru nanoparticles in terms of both durability and activity.

Symmetry-breaking intramolecular charge transfer in the excited state of meso-linked BODIPY dyads

KAUST Repository

Whited, Matthew T.; Patel, Niral M.; Roberts, Sean T.; Allen, Kathryn; Djurovich, Peter I.; Bradforth, Stephen E.; Thompson, Mark E.

2012-01-01

We report the synthesis and characterization of symmetric BODIPY dyads where the chromophores are attached at the meso position, using either a phenylene bridge or direct linkage. Both molecules undergo symmetry-breaking intramolecular charge transfer in the excited state, and the directly linked dyad serves as a visible-light-absorbing analogue of 9,9′-bianthryl.

Polystyrene with pendant mixed functional ruthenium(II)-terpyridine complexes

NARCIS (Netherlands)

Heller, M.; Schubert, U.S.

2002-01-01

A vinyl substituted 2,2:6,2-terpyridine and a mixed, bifunctional ruthenium(II)-terpyridine complex bearing a vinyl and a hydroxymethyl group are utilized as comonomers for radical copolymerization with styrene. The resulting polymers are characterized by means of UV-vis spectroscopy and gel

Spectroscopic and electrochemical study of polynuclear clusters from ruthenium acetate

International Nuclear Information System (INIS)

Cipriano, C.

1989-01-01

The chemistry of the trinuclear clusters [Ru sub(3) O (CH sub(3) CO sub(2)) sub(4) L sub(3)] where L = imidazole, pyridine or pyrazine type of ligands, was investigated based on spectroscopic and electrochemical techniques. These complexes are of great interest from the point of view of their electronic and redox properties, providing multisite species for electron transfer processes. They were isolated in solid state, and characterized by means of elementary analyses and infrared spectra. The electrochemical behaviour in acetonitrile solution was typically reversible; the cyclic voltammograms exhibited a series of four or five mono electronic waves ascribed to the sucessive Ru sup(IV) Ru sup(III) Ru sup(III) / Ru sup(III) Ru sup(III) Ru sup(III)/ --- Ru sup(II) Ru sup(II) Ru sup(II) redox couples. The differences between the successive redox potentials were about 1 V, indicating strong metal-metal interaction in the trinuclear Ru sub(3) centre. The E values were strongly sensitive to the nature of the N-heterocyclic ligand, increasing with the pi-acceptor properties of the pyridine and pyrazine derivatives, but in a much less pronounced way in the case of the imidazole derivatives. Resonance Raman studies for the pyrazine cluster showed selective intensification of the vibrational modes of the Ru-pyrazine chromophore, and the trinuclear centre, using excitation wavelengths coinciding with the metal-to-pyrazine and metal-metal bands, respectively. (author)

A facile one-pot synthesis of ruthenium hydroxide nanoparticles on magnetic silica: Aqueous hydration of nitriles to amides

Science.gov (United States)

One-pot synthesis of ruthenium hydroxide nanoparticles on magnetic silica is described which involve the in situ generation of magnetic silica (Fe3O4@ SiO2) and ruthenium hydroxide immobilization; the hydration of nitriles occurs in high yield and excellent selectivity using this...

Adolescent-Parent Dyad Descriptions of the Decision to Start the HPV Vaccine Series.

Science.gov (United States)

Chang, Jane; Ipp, Lisa S; de Roche, Ariel M; Catallozzi, Marina; Breitkopf, Carmen Radecki; Rosenthal, Susan L

2018-02-01

To examine how adolescent-parent dyads describe decision-making regarding initiation of the human papillomavirus (HPV) vaccine series, specifically who they viewed as making the final decision. Semistructured interviews with adolescent-parent dyads were audio-recorded and transcribed. Responses to the question: "How did you make a decision about whether or not to receive the HPV vaccine series?" were content-coded for each individual member of the dyad. Adolescent medicine clinics of 2 large urban medical centers and through snowball sampling. Adolescents 14-17 years of age and a parent (N = 262). Qualitative analyses were conducted for those who agreed that they were offered and started the HPV vaccine series (n = 109). None. Descriptions of the decision-making included 1 person (adolescent or parent) making the decision or joint decision-making by the adolescent and parent together. More than half of the dyads did not agree on who made the decision to start the vaccine. Most adolescents and parents described a similar account about when they were offered the HPV vaccine, although the interpretation of the event in terms of the decision-maker might have differed. More than half of adolescents and parents individually mentioned the health care provider in their description of the HPV vaccine decision-making process even though they were not queried about the role of the provider. Understanding the range of descriptions of these dyads is helpful to guide interventions to promote vaccine uptake in a manner that balances provider expertise, adolescent autonomy, and parental involvement. Copyright © 2017 North American Society for Pediatric and Adolescent Gynecology. Published by Elsevier Inc. All rights reserved.

High-pressure catalytic chemical vapor deposition of ferromagnetic ruthenium-containing carbon nanostructures

Energy Technology Data Exchange (ETDEWEB)

Khavrus, Vyacheslav O., E-mail: V.Khavrus@ifw-dresden.de; Ibrahim, E. M. M.; Bachmatiuk, Alicja; Ruemmeli, Mark H.; Wolter, A. U. B.; Hampel, Silke; Leonhardt, Albrecht [IFW Dresden (Germany)

2012-06-15

We report on the high-pressure catalytic chemical vapor deposition (CCVD) of ruthenium nanoparticles (NPs) and single-walled carbon nanotubes (SWCNTs) by means of gas-phase decomposition of acetonitrile and ruthenocene in a tubular quartz flow reactor at 950 Degree-Sign C and at elevated pressures (between 2 and 8 bar). The deposited material consists of Ru metal cores with sizes ranging between 1 and 3 nm surrounded by a carbon matrix. The high-pressure CCVD seems to be an effective route to obtain composite materials containing metallic NPs, Ru in this work, inside a nanostructured carbon matrix protecting them from oxidation in ambient air. We find that in contradiction to the weak paramagnetic properties characterizing bulk ruthenium, the synthesized samples are ferromagnetic as predicted for nanosized particles of nonmagnetic materials. At low pressure, the very small ruthenium catalyst particles are able to catalyze growth of SWCNTs. Their yield decreases with increasing reaction pressure. Transmission electron microscopy, selected area energy-dispersive X-ray analysis, Raman spectroscopy, and magnetic measurements were used to analyze and confirm properties of the synthesized NPs and nanotubes. A discussion on the growth mechanism of the Ru-containing nanostructures is presented.

Synthesis, photo-, and electrochemistry of ruthenium bis(bipyridine) complexes comprising a N-heterocyclic carbene ligand.

Science.gov (United States)

Leigh, Vivienne; Ghattas, Wadih; Lalrempuia, Ralte; Müller-Bunz, Helge; Pryce, Mary T; Albrecht, Martin

2013-05-06

Analogues of [Ru(bpy)3](2+) were prepared in which one pyridine ligand site is substituted by a N-heterocyclic carbene (NHC) ligand, that is, either by an imidazolylidene with a variable wingtip group R (R = Me, 3a; R = Et, 3b; R = iPr, 3c), or by a benzimidazolylidene (Me wingtip group, 3d), or by a 1,2,3-triazolylidene (Me wingtip group, 3e). All complexes were characterized spectroscopically, photophysically, and electrochemically. An increase of the size of the wingtip groups from Me to Et or iPr groups distorts the octahedral geometry (NMR spectroscopy) and curtails the reversibility of the ruthenium oxidation. NHC ligands with methyl wingtip groups display reversible ruthenium oxidation at a potential that reflects the donor properties of the NHC ligand (triazolylidene > imidazolylidene > benzimidazolylidene). The most attractive properties were measured for the triazolylidene ruthenium complex 3e, featuring the smallest gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) in the series (2.41 eV), a slightly red-shifted absorption profile, and reasonable excited-state lifetime (188 ns) when compared to [Ru(bpy)3](2+). These features demonstrate the potential utility of triazolylidene ruthenium complexes as photosensitizers for solar energy conversion.

Cosensitization Properties of Glutathione-Protected Au25 Cluster on Ruthenium Dye-Sensitized TiO2 Photoelectrode

Directory of Open Access Journals (Sweden)

Kazuya Nakata

2013-01-01

Full Text Available Cosensitization by glutathione-protected Au25 clusters on Ru complex, N719-sensitized TiO2 photoelectrodes is demonstrated. Glutathione-protected Au25 clusters showed no significant changes in properties after adsorption onto TiO2 particles, as confirmed by optical absorption spectroscopy, transmission electron microscopy, and laser desorption/ionization mass spectrometry. Adsorption property of the glutathione-protected Au25 clusters depends on the pH, which affects the incident photon-to-current conversion efficiency (IPCE of the TiO2 photoelectrode containing Au25 clusters. When pH 7. The IPCE of a TiO2 photoelectrode sensitized by both glutathione-protected Au25 clusters and N719 was increased compared with photoelectrodes containing either glutathione-protected Au25 clusters or N719, which suggests that glutathione-protected Au25 clusters act as a coadsorbent for N719 on TiO2 photoelectrodes. This is also supported by the results that the IPCE of N719-sensitized TiO2 photoelectrodes increased upon addition of glutathione. Furthermore, cosensitization by glutathione-protected Au25 clusters on N719-sensitized TiO2 photoelectrodes allows that wavelength of photoelectric conversion was extended to the near infrared (NIR region. These results suggest that glutathione-protected Au25 clusters act not only as a coadsorbent to increase IPCE but also as an NIR-active sensitizer.

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.

Effect of solvent on Se-modified ruthenium/carbon catalyst for oxygen reduction

Directory of Open Access Journals (Sweden)

Chuanxiang Zhang

2014-12-01

Full Text Available Se-modified ruthenium supporting on carbon (Sex–Ru/C electrocatalyst was prepared by solvothermal one-step synthesis method. The reaction mechanism was revealed after discussing impact of different solvents (i-propanol and EG in solvotermal reaction. The result showed that the grain size of Se-modified ruthenium electrocatalyst was as small as 1 to 3 nm and highly dispersed on carbon surface. X-ray photoelectron spectroscopy (XPS presented that selenium mainly existed in the catalyst in the form of elemental selenium and selenium oxides when the solvent was EG and i-propanol, respectively. The oxygen reduction reaction (ORR performance was improved by appearance of selenium oxides.

About the value of Ruthenium 106 brachytherapy in the treatment of uveal melanomas

International Nuclear Information System (INIS)

Langmann, G.; Mosboeck, G.; Stuecklschwaiger, G.; Muellner, K.; Lechner, H.; Faulborn, J.

2002-01-01

Background: to investigate the clinical course, sequelae and visual function of uveal melanomas treated with Ruthenium 106 brachytherapy. Patients and method: 47 patients who underwent Ruthenium 106 brachytherapy between 1985 and 2000 were evaluated using Kaplan Meier statistical method. Mean follow up interval was 22 month (range 8 - 152 months). Results: Local tumor control rate was 85 %, 5 years possibility to avoid enucleation was 75 %. The most important sequelae were radiation optic neuropathy (29 %), maculopathy (37 %) and radiation retinopathy (32 %). After terminating the study the 34 % of the patients achieved a visual acuity of 20/40 and more, another 34 % had a visual function of 20/200 and lower. Conclusion: Ruthenium 106 brachytherapy is our method of choice in small medium sized uveal melanomas and a maximum tumor prominence of 6 mm. Tumors have to be located in the midperiphery and outer periphery of the fundus including the ciliary body. In addition to the indications introduced by Lommatzsch we treated ciliary body melanomas with a tumor base more than 3 clock hours (by shifting the plaque) as an alternative therapy to enucleation. (author)

Oxidative dissolution of ruthenium deposits onto stainless steel by permanganate ions in alkaline medium

Energy Technology Data Exchange (ETDEWEB)

Floquet, S.; Eysseric, C.; Maurel, D. [Commissariat a l' Energie Atomique (CEA/Valrho), Bagnols-sur-Ceze (France)

2008-07-01

During spent nuclear fuel reprocessing ruthenium is liable to form black ruthenium deposits on the stainless steel walls of process equipments. These deposits promote corrosion and can eventually obstruct the off-gas lines. The results of decontamination of 304L stainless steel test specimens covered with RuO(OH){sub 2} . xH{sub 2}O deposits by permanganate ions in alkaline medium are described. The ruthenium deposits were dissolved by oxidation of RuO(OH){sub 2} to RuO{sub 4}{sup 2-} ions, while the permanganate ions were reduced to MnO{sub 4}{sup 2-} ions and then to manganese dioxide MnO{sub 2}. The parameters affecting the kinetics of oxidative dissolution of these deposits were examined. The results indicate that the oxidative dissolution kinetics depends on the instantaneous surface area of the deposit, and that the dissolution rate increases with the concentrations of MnO{sub 4}{sup -} and OH{sup -} ions. (orig.)

Through-Space Paramagnetic NMR Effects in Host-Guest Complexes: Potential Ruthenium(III) Metallodrugs with Macrocyclic Carriers.

Science.gov (United States)

Chyba, Jan; Novák, Martin; Munzarová, Petra; Novotný, Jan; Marek, Radek

2018-04-05

The potential of paramagnetic ruthenium(III) compounds for use as anticancer metallodrugs has been investigated extensively during the past several decades. However, the means by which these ruthenium compounds are transported and distributed in living bodies remain relatively unexplored. In this work, we prepared several novel ruthenium(III) compounds with the general structure Na + [ trans-Ru III Cl 4 (DMSO)(L)] - (DMSO = dimethyl sulfoxide), where L stands for pyridine or imidazole linked with adamantane, a hydrophobic chemophore. The supramolecular interactions of these compounds with macrocyclic carriers of the cyclodextrin (CD) and cucurbit[ n]uril (CB) families were investigated by NMR spectroscopy, X-ray diffraction analysis, isothermal titration calorimetry, and relativistic DFT methods. The long-range hyperfine NMR effects of the paramagnetic guest on the host macrocycle are related to the distance between them and their relative orientation in the host-guest complex. The CD and CB macrocyclic carriers being studied in this account can be attached to a vector that attracts the drug-carrier system to a specific biological target and our investigation thus introduces a new possibility in the field of targeted delivery of anticancer metallodrugs based on ruthenium(III) compounds.

3-Methylindole-Based Tripodal Tetraphosphine Ruthenium Complexes in N2 Coordination and Reduction and Formic Acid Dehydrogenation

Directory of Open Access Journals (Sweden)

Fenna F. van de Watering

2017-10-01

Full Text Available The ruthenium(II complexes RuCl2L1H, RuCl2L1CF3, RuCl2L1OMe and RuCl2L2H were synthesized from [Ru(η6-benzeneCl(μ-Cl]2 and the corresponding tripodal tris-3-methylindolephosphine-based ligands L1H, L1CF3, L1OMe, and L2H. Stoichiometric reduction of these complexes with KC8 yielded the corresponding ruthenium(0 dinitrogen complexes. The latter complexes were studied in the N2 reduction with chlorosilanes and KC8, yielding stoichiometric amounts of the silylamines. The synthesized ruthenium(II complexes are also active catalysts for the formic acid dehydrogenation reaction.

Conceptual Diagnosis Model Based on Distinct Knowledge Dyads for Interdisciplinary Environments

Directory of Open Access Journals (Sweden)

Cristian VIZITIU

2014-06-01

Full Text Available The present paper has a synergic dual purpose of bringing a psychological and neuroscience related perspective oriented towards decision making and knowledge creation diagnosis in the frame of Knowledge Management. !e conceptual model is built by means ofCognitive-Emotional and Explicit-Tacit knowledge dyads and structured on Analytic Hierarchy Process (AHP according to the hypothesis which designates the first dyad as an accessing mechanism of knowledge stored in the second dyad. Due to the well acknowledged needsconcerning new advanced decision making instruments and enhanced knowledge creation processes in the field of technical space projects emphasized by a high level of complexity, the herein study tries also to prove the relevance of the proposed conceptual diagnosis modelin Systems Engineering (SE methodology which foresees at its turn concurrent engineering within interdisciplinary working environments. !e theoretical model, entitled DiagnoSE, has the potential to provide practical implications to space/space related business sector butnot merely, and on the other hand, to trigger and inspire other knowledge management related researches for refining and testing the proposed instrument in SE or other similar decision making based working environment.

Ruthenium phosphine complexes as catalysts for alternating co-polymerization of ethylene and CO

International Nuclear Information System (INIS)

Gusev, O.V.; Kal'sin, A.M.; Peganov, T.A.; Petrovskij, P.V.; Belov, G.P.; Novikova, E.V.

2000-01-01

Ruthenium (2) complexes, [Ru(dppe) 2 (OTs) 2 ] and [Ru(PhP(CH 2 CH 2 CH 2 PPh 2 ) 2 )(OTs) 2 ], where dppe (diphenylphosphino)ethane; OTs = tosylate, were synthesized with the yield of 67 and 76%, respectively, and characterized by 31 P NMR. The properties of the above complexes as catalysts of alternating co-polymerization of ethylene and carbon monoxide were studied. A considerable increase in catalytic activity of the complexes was established in the presence of trifluoroacetic acid and 1,4-benzoquinone. These compounds are the first example of ruthenium complexes that catalyse co-polymerization of ethylene and CO [ru

Estimation of very low concentrations of Ruthenium by spectrophotometric method using barbituric acid as complexing agent

International Nuclear Information System (INIS)

Ramakrishna Reddy, S.; Srinivasan, R.; Mallika, C.; Kamachi Mudali, U.; Natarajan, R.

2012-01-01

Spectrophotometric method employing numerous chromogenic reagents like thiourea, 1,10-phenanthroline, thiocyanate and tropolone is reported in the literature for the estimation of very low concentrations of Ru. A sensitive spectrophotometric method has been developed for the determination of ruthenium in the concentration range 1.5 to 6.5 ppm in the present work. This method is based on the reaction of ruthenium with barbituric acid to produce ruthenium(ll)tris-violurate, (Ru(H 2 Va) 3 ) -1 complex which gives a stable deep-red coloured solution. The maximum absorption of the complex is at 491 nm due to the inverted t 2g → Π(L-L ligand) electron - transfer transition. The molar absorptivity of the coloured species is 9,851 dm 3 mol -1 cm -1

Study on volatilization mechanism of ruthenium tetroxide from nitrosyl ruthenium nitrate by using mass spectrometer

Energy Technology Data Exchange (ETDEWEB)

Kato, Tetsuya, E-mail: tkato@criepi.denken.or.jp [Nuclear Technology Research Laboratory, Central Research Institute of Electric Power Industry, 2-11-1 Iwado-kita, Komae-shi, Tokyo 201-8511 (Japan); Usami, Tsuyoshi; Tsukada, Takeshi [Nuclear Technology Research Laboratory, Central Research Institute of Electric Power Industry, 2-11-1 Iwado-kita, Komae-shi, Tokyo 201-8511 (Japan); Shibata, Yuki; Kodama, Takashi [Safety Technology Division, Japan Nuclear Fuel Ltd., Obuchi, Rokkasho-mura, Aomori 039-3212 (Japan)

2016-10-15

In a cooling malfunction accident of a high-level liquid waste (HLLW) tank, behavior of ruthenium (Ru) attracts much attention, since Ru could be oxidized to a volatile chemical form in the boiling and drying of HLLW, and part of radioactive Ru can potentially be released to the environment. In this study, nitrosyl Ru nitrate (Ru(NO)(NO{sub 3}){sub 3}) dissolved in nitric acid (HNO{sub 3}), which is commonly contained in a simulated HLLW, was dried and heated up to 723 K, and the evolved gas was introduced into a mass spectrometer. The well-known volatile species, ruthenium tetroxide (RuO{sub 4}) was detected in a temperature range between 390 K and 500 K with the peak top around 440 K. Various gases such as HNO{sub 3}, nitrogen dioxide (NO{sub 2}), nitrogen monoxide (NO) also evolved due to evaporation of the nitric acid and decomposition of the nitrate ions. The ion current of RuO{sub 4} seems to increase with the increasing decomposition of nitrate, while the evaporation of HNO{sub 3} decreases. More volatilization of RuO{sub 4} was observed from the HNO{sub 3} solution containing not only Ru(NO)(NO{sub 3}){sub 3} but also cerium nitrate (Ce(NO{sub 3}){sub 3}·6H{sub 2}O) which was added for extra supply of nitrate ion, compared with that from the HNO{sub 3} solution containing only Ru(NO)(NO{sub 3}){sub 3}. These experimental results suggest that Ru could be oxidized to form RuO{sub 4} by the nitrate ion as well as HNO{sub 3}. - Graphical abstract: Ion current intensities of the mass numbers corresponding to O, NO, O{sub 2}, NO{sub 2}, HNO{sub 3}, and RuO{sub 4} obtained in mass spectrometry for dried nitric acid solution containing Ru(NO)(NO{sub 3}){sub 3}. Heating rate: 5 K min{sup −1}, sample solution weight: 6.61 mg, contained Ru weight: 0.56 mg. The ion current of RuO{sub 4} increases with the increasing decomposition of nitrate, while the evaporation of HNO{sub 3} decreases. - Highlights: • Nitrosyl Ru nitrate (Ru(NO)(NO{sub 3}){sub 3}) dissolved in

Kinetic method of ruthenium ion traces determination, basing on the reaction of oxidation of direct blue 6B, by means of hydrogen peroxide

International Nuclear Information System (INIS)

Suwinska, T.; Gregorowicz, A.; Matysek-Majewska, D.

1980-01-01

A sensitive and selective method of determination of ruthenium ion traces (1.10 - 3 μg/cm 3 ) has been worked out. The method is based on oxidation of direct blue 6B by hydrogen peroxide under acidic conditions at pH = 0,8 - 1,2 in the presence of ruthenium ions as catalyst. The method has been applied for determination of ruthenium traces in Pt, PdCl 2 , PtCl 4 and RhCl 3 .n H 2 O. In these materials ruthenium has been determined within the range of 1,10 - 2 % - 5,10 - 4 %. (author)

Evaluative Language Used by Mandarin-Chinese-Speaking Dyads in Personal Narratives: Age and Socioeconomic Differences

Science.gov (United States)

Lai, Wen-Feng; Chen, Yen-Yu

2016-01-01

The aim of this study was to determine the effects of age and family socioeconomic status (SES) on the evaluative language performance of Mandarin-Chinese-speaking young children and their mothers. The participants were 65 mother-child dyads recruited in Taiwan. Thirty-four of these dyads were from middle-class families and 31 were from…

Electric field dependent photocurrent generation in a thin-film organic photovoltaic device with a [70]fullerene-benzodifuranone dyad.

Science.gov (United States)

Ulmann, Pirmin A; Tanaka, Hideyuki; Matsuo, Yutaka; Xiao, Zuo; Soga, Iwao; Nakamura, Eiichi

2011-12-21

A [70]fullerene-benzodifuranone acceptor dyad synthesized by a Ag⁺-mediated coupling reaction was used to construct a thin-film organic solar cell. The fullerene and the benzodifuranone dye in the dyad have close-lying LUMO levels in the range of 3.7-3.9 eV, so that energy transfer from the dye to the fullerene can take place. A p-n heterojunction photovoltaic device consisting of a tetrabenzoporphyrin and a [70]fullerene-benzodifuranone dyad showed a weak but discernible contribution from light absorption of the dyad to the photocurrent under both a positive and a negative effective bias. These results indicate that the benzodifuranone moiety attached to the acceptor contributes to light-harvesting by energy transfer.

Analysis of Relational Communication in Dyads: New Measurement Procedures.

Science.gov (United States)

Rogers, L. Edna; Farace, Richard

Relational communication refers to the control or dominance aspects of message exchange in dyads--distinguishing it from the report or referential aspects of communication. In relational communicational analysis, messages as transactions are emphasized; major theoretical concepts which emerge are symmetry, transitoriness, and complementarity of…

Surface and sub-surface thermal oxidation of ruthenium thin films

NARCIS (Netherlands)

Coloma Ribera, R.; van de Kruijs, Robbert Wilhelmus Elisabeth; Zoethout, E.; Yakshin, Andrey; Bijkerk, Frederik

2014-01-01

For next generation Extreme UV photolithography, multilayer coatings may require protective capping layers against surface contamination. Ruthenium, as a low-oxidation metal, is often used as a reference material. The oxidation behaviour of Ru thin films has been studied using X-ray reflectometry

Recruitment of Older Adult Patient-Caregiver Dyads for an Online Caregiver Resource Program: Lessons Learned.

Science.gov (United States)

Nahm, Eun-Shim; Orwig, Denise; Resnick, Barbara; Magaziner, Jay; Bellantoni, Michele; Sterling, Robert

2012-01-12

Hip fracture is a significant health problem for older adults and generally requires surgery followed by intensive rehabilitation. Informal caregivers (CGs) can provide vital assistance to older adults recovering from hip fracture. Caregiving is a dyadic process that affects both CGs and care recipients (CRs). In a feasibility study, we assessed the effects of using a theory-based online hip fracture resource program for CGs on both CGs and CRs. In this article, we discuss our recruitment process and the lessons learned. Participants were recruited from six acute hospitals, and CGs used the online resource program for 8 weeks. A total of 256 hip fracture patients were screened, and 164 CRs were ineligible. CG screening was initiated when CRs were determined to be eligible. Among 41 eligible dyads, 36 dyads were recruited. Several challenges to the recruitment of these dyads for online studies were identified, including a low number of eligible dyads in certain hospitals and difficulty recruiting both the CR and the CG during the short hospital stay. Field nurses often had to make multiple trips to the hospital to meet with both the CR and the CG. Thus, when a subject unit is a dyad recruited from acute settings, the resources required for the recruitment may be more than doubled. These challenges could be successfully alleviated with careful planning, competent field staff members, collaboration with hospital staff members, and efficient field operations.

Investigation of Ruthenium Dissolution in Advanced Membrane Electrode Assemblies for Direct Methanol Based Fuel Cell Stacks

Science.gov (United States)

Valdez, Thomas I.; Firdosy, S.; Koel, B. E.; Narayanan, S. R.

2005-01-01

Dissolution of ruthenium was observed in the 80-cell stack. Duration testing was performed in single cell MEAs to determine the pathway of cell degradation. EDAX analysis on each of the single cell MEAs has shown that the Johnson Matthey commercial catalyst is stable in DMFC operation for 250 hours, no ruthenium dissolution was observed. Changes in the hydrophobicity of the cathode backing papers was minimum. Electrode polarization analysis revealed that the MEA performance loss is attributed to changes in the cathode catalyst layer. Ruthenium migration does not seem to occur during cell operation but can occur when methanol is absent from the anode compartment, the cathode compartment has access to air, and the cells in the stack are electrically connected to a load (Shunt Currents). The open-to-air cathode stack design allowed for: a) The MEAs to have continual access to oxygen; and b) The stack to sustain shunt currents. Ruthenium dissolution in a DMFC stack can be prevented by: a) Developing an internally manifolded stacks that seal reactant compartments when not in operation; b) Bringing the cell voltages to zero quickly when not in operation; and c) Limiting the total number of cells to 25 in an effort to limit shunt currents.

Mixed-ligand complexes of ruthenium(II) incorporating a diazo ...

Indian Academy of Sciences (India)

Unknown

Dedicated to the memory of the late Professor Bhaskar G Maiya. *For correspondence. Mixed-ligand complexes of ruthenium(II) incorporating a diazo ligand: Synthesis .... water (1 : 1) for 5 h to give a dark red solution. The solution was cooled to room temperature. After eva- poration of the solvent, the solid was collected,.

Homo- or Hetero- Triplet-Triplet Annihilation? A Case Study with Perylene-Bodipy Dyads/Triads

KAUST Repository

Cui, Xiaoneng

2017-07-06

The photophysical processes of intramolecular ‘ping-pong’ energy transfers in the iodinated reference dyad BDP-I2-Py, as well as the uniodinated dyad BDP-Py and triad BDP-2Py, were studied. For BDP-I2-Py, a forward Förster resonance energy transfer (FRET) from the perylene (Py) unit to the diiodoBDP unit (7 ps) and a backward triplet energy transfer (TTET, 3 ns) from the diiodoBDP unit to the Py unit were observed. For the BDP-Py and BDP-2Py systems, a FRET (5 ~ 8 ps) and a photo-induced electron transfer (PET) (1-1.5 ns) were observed in acetonitrile. The uniodinated dyad and triad were used as the triplet energy acceptor and emitter for a TTA upconversion with palladium tetraphenyltetrabenzoporphyrin as the triplet photosensitizer. A maximum upconversion quantum yield of 12.6 % was measured. Given that the dyad (BDP-Py) contains one BDP unit and one Py unit, while the triad (BDP-2Py) contains two Py units and one BDP unit, and based on the results from steady-state femtosecond and nanosecond transient optical spectroscopies, it is concluded that neither intramolecular homo- triplet-triplet annihilation (TTA) nor intramolecular hetero-TTA is possible during a TTA upconversion for those upconversion systems.

Study of some properties of the ruthenium (II) trans-tetra-ammines with nitrogened aromatic heterocyclic ligands

International Nuclear Information System (INIS)

Bento, M.L.

1985-01-01

The ruthenium (II) complexes trans [Ru(NH 3 ) 4 LL'] (BF 4 ) 2 , where L and L' are 4-picoline, pyridine, isonicatinamide, pyrazine or 4-acetylpyridine are studied. The U.V-visible range spectra, bands in the U.V. and in the visible range is analysed. The spectra and the bands by comparison with other ruthenium (II) ammines are discussed, and a qualitative molecular orbital model is used. (M.J.C.) [pt

Surface heterogeneity and ionization of Cs promoter in carbon-based ruthenium catalyst for ammonia synthesis

International Nuclear Information System (INIS)

Kotarba, Andrzej; Dmytrzyk, Jaromir; Rarog-Pilecka, Wioletta; Kowalczyk, Zbigniew

2003-01-01

Second-generation ammonia synthesis cesium-doped ruthenium catalyst supported on turbostratic carbon was investigated by the species resolved thermal alkali desorption method (SR-TAD). Energetic barriers for cesium ions (2.86 eV), ground state (1.96 eV) and electronically excited atoms (5.76 eV) desorbing from the Cs-Ru/C catalyst were determined. In the case of ruthenium-free Cs/C system, cesium desorbs as ground state atoms only, with an energy barrier of 2.87 eV. The work functions determined by the thermionic emission of electrons from Cs/C and Cs-Ru/C were of the same value (2.9 eV). It was concluded that ruthenium induces heterogeneous distribution of cesium on the catalyst surface. The promoter stability is reduced on low work function areas and its surface ionization on high work function areas opens the ionic desorption channel. The Cs desorption from the catalyst is discussed in terms of the literature data for the cesium/graphite system

Variation of the Sterical Properties of the N-Heterocyclic Carbene Coligand in Thermally Triggerable Ruthenium-Based Olefin Metathesis Precatalysts/Initiators

KAUST Repository

Pump, Eva; Leitgeb, Anita; Kozłowska, Anna; Torvisco, Ana; Falivene, Laura; Cavallo, Luigi; Grela, Karol; Slugovc, Christian

2015-01-01

A series of ruthenium complexes based on the κ(C,N)-(2-(benzo[h]quinolin-10-yl)methylidene ruthenium dichloride fragment featuring different neutral coligands L (L = 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazol-2-ylidene (SIPr), 1,3-bis(2

Behaviour of ruthenium (3) bromocomplexes in nonaqueous solvents

International Nuclear Information System (INIS)

Rudnitskaya, O.V.; Miroshnichenko, I.V.; Pichkov, V.N.

1989-01-01

Behaviour of K 3 [RuBr 6 ] · H 2 O and K 3 [Ru 2 Br 9 ] in solutions of dimethylsulfoxide and dimethylformamide is investigated by absorption and ESR spectroscopy. Complexes are shown to be labile in solutions, interact easily with solvents. Formation of ruthenium (3) and (2) bromide-dimethylsulfoxide complexes occurs gradually in DMSO, final product is trans-[Ru(DMSO) 4 Br 2

THE SYNTHESIS AND THE REACTIVITY OF ARENE RUTHENIUM ...

African Journals Online (AJOL)

a

[RuCl(η6-p-cymene)(η2-dppm)][PF6] ruthenium complexes with C2O4(Me4N)2 in the ... the Service de Microanalyse du CNRS (Vernaison/France). .... Once bonded to the Ru(II), the characterization of the oxalato ligand by infrared .... The 1H NMR spectrum shows signals of the aromatic proton resonances at 5.45 and 5.15,.

The trans influence in mer-trichloronitridobis(triphenylarsine)ruthenium(VI)

DEFF Research Database (Denmark)

Magnussen, Magnus; Bendix, Jesper

2003-01-01

The title compound, mer-[RuCl(3)N(C(18)H(15)As)(2)], is the first structurally characterized example of a nitride complex in which ruthenium is six-coordinated to monodentate ligands only. The Ru[triple-bond]N bond length [1.6161 (15) A] is relatively long, and the trans influence of the nitride...

Control of triplet state generation in heavy atom-free BODIPY-anthracene dyads by media polarity and structural factors

KAUST Repository

Filatov, Mikhail A.

2018-02-12

A family of heavy atom-free BODIPY-anthracene dyads (BADs) exhibiting triplet excited state formation from charge-transfer states is reported. Four types of BODIPY scaffolds, different in the alkyl substitution pattern, and four anthracene derivatives have been used to access BADs. The fluorescence and intersystem crossing (ISC) in these dyads depend on donor-acceptor couplings and can be accurately controlled by the substitution or media polarity. Under conditions that do not allow charge transfer (CT), the dyads exhibit fluorescence with high quantum yields. Formation of charge-transfer states triggers ISC and the formation of long-lived triplet excited states in the dyads. The excited state properties were studied by steady-state techniques and ultrafast pump-probe spectroscopy to determine the parameters of the observed processes. Structural information for various BADs was derived from single crystal X-ray structure determinations alongside DFT molecular geometry optimization, revealing the effects of mutual orientation of subunits on the photophysical properties. The calculations showed that alkyl substituents on the BODIPY destabilize CT states in the dyads, thus controlling the charge transfer between the subunits. The effect of the dyad structure on the ISC efficiency was considered at M06-2X level of theory and a correlation between mutual orientation of the subunits and the energy gap between singlet and triplet CT states was studied using multireference CASSCF method.

Control of triplet state generation in heavy atom-free BODIPY-anthracene dyads by media polarity and structural factors

KAUST Repository

Filatov, Mikhail A.; Karuthedath, Safakath; Polestshuk, Pavel M; Callaghan, Susan; Flanagan, Keith; Telitchko, Maxime; Wiesner, Thomas; Laquai, Fré dé ric; Senge, Mathias O

2018-01-01

A family of heavy atom-free BODIPY-anthracene dyads (BADs) exhibiting triplet excited state formation from charge-transfer states is reported. Four types of BODIPY scaffolds, different in the alkyl substitution pattern, and four anthracene derivatives have been used to access BADs. The fluorescence and intersystem crossing (ISC) in these dyads depend on donor-acceptor couplings and can be accurately controlled by the substitution or media polarity. Under conditions that do not allow charge transfer (CT), the dyads exhibit fluorescence with high quantum yields. Formation of charge-transfer states triggers ISC and the formation of long-lived triplet excited states in the dyads. The excited state properties were studied by steady-state techniques and ultrafast pump-probe spectroscopy to determine the parameters of the observed processes. Structural information for various BADs was derived from single crystal X-ray structure determinations alongside DFT molecular geometry optimization, revealing the effects of mutual orientation of subunits on the photophysical properties. The calculations showed that alkyl substituents on the BODIPY destabilize CT states in the dyads, thus controlling the charge transfer between the subunits. The effect of the dyad structure on the ISC efficiency was considered at M06-2X level of theory and a correlation between mutual orientation of the subunits and the energy gap between singlet and triplet CT states was studied using multireference CASSCF method.

Structure of health-care dyad leadership: an organization's experience.

Science.gov (United States)

Saxena, Anurag; Davies, Maura; Philippon, Don

2018-05-08

Purpose This study aims to explore the structural aspects (roles, responsibilities and reporting) of dyad leadership in one health-care organization (HCO). Design/methodology/approach The perceptions of 32 leaders (17 physician leaders and 15 dyad co-leaders) in formal leadership positions (six first-level with formal authority limited to teams or divisions, 23 middle-level with wider departmental or program responsibility and three senior-level with institution-wide authority) were obtained through focus groups and surveys. In addition, five senior leaders were interviewed. Descriptive statistics was used for quantitative data, and qualitative data were analyzed for themes by coding and categorization. Findings There are a large number of shared responsibilities in the hybrid model, as most activities in HCOs bridge administrative and professional spheres. These span the leadership (e.g. global performance and quality improvement) and management (e.g. human resources, budgets and education delivery) domains. The individual responsibilities, except for staff and physician engagement are in the management domain (e.g. operations and patient care). Both partners are responsible for joint decision-making, projecting a united front and joint reporting through a quadrat format. The mutual relationship and joint accountability are key characteristics and are critical to addressing potential conflicts and contradictions and achieving coherence. Practical implications Clarity of role will assist development of standardized job descriptions and required competencies, recruitment and leadership development. Originality/value This is an original empirical study presenting an integrated view of dyad leaders and senior leadership, meaningful expansion of shared responsibilities including academic functions and developing mutual relationship and emphasizing the central role of stability generating management functions.

Determination of the protonation state of the Asp dyad: conventional molecular dynamics versus thermodynamic integration.

Science.gov (United States)

Huang, Jinfeng; Zhu, Yali; Sun, Bin; Yao, Yuan; Liu, Junjun

2016-03-01

The protonation state of the Asp dyad is important as it can reveal enzymatic mechanisms, and the information this provides can be used in the development of drugs for proteins such as memapsin 2 (BACE-1), HIV-1 protease, and rennin. Conventional molecular dynamics (MD) simulations have been successfully used to determine the preferred protonation state of the Asp dyad. In the present work, we demonstrate that the results obtained from conventional MD simulations can be greatly influenced by the particular force field applied or the values used for control parameters. In principle, free-energy changes between possible protonation states can be used to determine the protonation state. We show that protonation state prediction by the thermodynamic integration (TI) method is insensitive to force field version or to the cutoff for calculating nonbonded interactions (a control parameter). In the present study, the protonation state of the Asp dyad predicted by TI calculations was the same regardless of the force field and cutoff value applied. Contrary to the intuition that conventional MD is more efficient, our results clearly show that the TI method is actually more efficient and more reliable for determining the protonation state of the Asp dyad.

Daily Associations of Stress and Eating in Mother-Child Dyads.

Science.gov (United States)

Dunton, Genevieve F; Dzubur, Eldin; Huh, Jimi; Belcher, Britni R; Maher, Jaclyn P; O'Connor, Sydney; Margolin, Gayla

2017-06-01

This study used Ecological Momentary Assessment (EMA) in mother-child dyads to examine the day-level associations of stress and eating. Mothers and their 8- to 12-year-old children ( N = 167 dyads) completed between three (weekday) and eight (weekend) EMA survey prompts per day at random nonschool times across 8 days. EMA measured perceived stress, and past 2-hour healthy (i.e., fruit and vegetables) and unhealthy (e.g., pastries/sweets, soda/energy drinks) eating. Children reported more healthy and unhealthy eating on days when their mothers also engaged in more healthy and unhealthy eating, respectively. On days when mothers' perceived stress was greater than usual, they reported more healthy eating. Eating behaviors were coupled between mothers and children at the day level. Mothers' stress was related to their own eating but not to children's eating.

Preparations and characterization of some carbonyl-(1-cyanoethyl)ruthenium(II) complexes

Energy Technology Data Exchange (ETDEWEB)

Hiraki, Katsuma; Ochi, Naoyuki; Kitamura, Tsuneyuki; Sasada, Yoko [Nagasaki Univ. (Japan); Shinoda, Sumio

1982-08-01

A hydridoruthenium(II) complex (RuClH(CO)(PPh/sub 3/)/sub 3/) reacted easily with acrylonitrile and fumaronitrile to give chloro-bridged binuclear (1-cyanoethyl)ruthenium(II) complexes, ((Ru(MeCHCN)Cl(CO)(PPh/sub 3/)/sub 2/)/sub 2/) (2) and ((Ru(NCCH/sub 2/CHCN)Cl(CO)(PPh/sub 3/)/sub 2/)/sub 2/), respectively. Complex 2 reacted with 4-picoline (pic), Na(BHPz/sub 3/) (Pz = 1-pyrazolyl), Na(BPz/sub 4/), and Na(Et/sub 2/NCS/sub 2/).3H/sub 2/O to afford the corresponding (1-cyanoethyl)ruthenium(II) complexes, ((Ru(MeCHCN)Cl(CO)(pic)(PPh/sub 3/))/sub 2/) (3), (Ru(MeCHCN)(BHPz/sub 3/)(CO)(PPh/sub 3/)) (accompanied by a small amount of (Ru/sub 2/(MeCHCN)/sub 2/Cl(BHPz/sub 3/)(CO)/sub 2/(PPh/sub 3/)/sub 4/)), (Ru/sub 2/(MeCHCN)/sub 2/Cl(BPz/sub 4/)(CO)/sub 2/(PPh/sub 3/)/sub 2/), and Na(Ru(MeCHCN)Cl(Et/sub 2/NCS/sub 2/)(CO)(PPh/sub 3/)), respectively. Complex 3 reacted with thallium (I) acetylacetonate (Tl(acac)), resulting in the formation of ((Ru(MeCHCN)(acac)(CO)(PPh/sub 3/))/sub 2/) and (Ru(MeCHCN)(acad)(CO)(pic)(PPh/sub 3/)). These new complexes were characterized by means of elemental analysis and spectroscopic data. The diastereoisomerism was also discussed as regards these (1-cyanoethyl)ruthenium(II) complexes.

Design and synthesis of ruthenium(II) OCO pincer type NHC ...

Indian Academy of Sciences (India)

The tridentate nature of the tBu(OCO)2− ligand as well as some level of steric protection ... our previous results of ruthenium(II) o-hydroxyaryl sub- stituted bidentate NHC ...... (a) Ribelin T, Katz C E, English D G, Smith S,. Manukyan A K, Day ...

Determination of oxygen diffusion kinetics during thin film ruthenium oxidation

NARCIS (Netherlands)

Coloma Ribera, R.; van de Kruijs, Robbert Wilhelmus Elisabeth; Yakshin, Andrey; Bijkerk, Frederik

2015-01-01

In situ X-ray reflectivity was used to reveal oxygen diffusion kinetics for thermal oxidation of polycrystalline ruthenium thin films and accurate determination of activation energies for this process. Diffusion rates in nanometer thin RuO2 films were found to show Arrhenius behaviour. However, a

TBP 20% - diluent/HNO3/H2O liquid-liquid extraction system: equilibrium normalization data of nitric acid, ruthenium and zirconium

International Nuclear Information System (INIS)

Oliveira, C.A.L.G. de.

1984-01-01

The extraction behaviour of nitric acid, nitrosyl-ruthenium nitrate and zirconium hydroxide nitrate in the system tri-n-butyl phosphate (TBP) 20% - diluent was studied. The main purpose was to obtain enough data to elaborate process flowsheets for the treatment of irradiated uranium fuels. During the runs, the equilibrium diagrams of nitric acid, ruthenium and zirconium were settled. From the achieved data, the influence of nitric acid, ruthenium, zirconium and nitrate ions concentration in the aqueous phase was checked. Furthermore, the density and the surface tension of the aqueous and organic phases were determined, gathering the interfacial tension after the contact between the phases. A comparison among the obtained equilibrium data and the existing one from literature allowed the elaboration of mathematical models to express the distribution behaviour of nitric acid, ruthenium and zirconium as a function of nitrate ions concentration in the aqueous phase. The reduction of TBP concentration from 30% v/v (normally used) to 20% v/v, has shown no influence in the extraction behaviour of the elements. A decreasing in the distribution values was observed and that means an important factor during the decontamination of uranium from its contaminants, ruthenium and zirconium. (Author) [pt

Relational uncertainty in service dyads

DEFF Research Database (Denmark)

Kreye, Melanie

2017-01-01

in service dyads and how they resolve it through suitable organisational responses to increase the level of service quality. Design/methodology/approach: We apply the overall logic of Organisational Information-Processing Theory (OIPT) and present empirical insights from two industrial case studies collected...... the relational uncertainty increased the functional quality while resolving the partner’s organisational uncertainty increased the technical quality of the delivered service. Originality: We make two contributions. First, we introduce relational uncertainty to the OM literature as the inability to predict...... and explain the actions of a partnering organisation due to a lack of knowledge about their abilities and intentions. Second, we present suitable organisational responses to relational uncertainty and their effect on service quality....

A parent-child dyad approach to the assessment of health status and health-related quality of life in children with asthma.

Science.gov (United States)

Ungar, Wendy J; Boydell, Katherine; Dell, Sharon; Feldman, Brian M; Marshall, Deborah; Willan, Andrew; Wright, James G

2012-08-01

Assessment of health state and health-related quality of life (HR-QOL) are limited by a child's age and cognitive ability. Parent-proxy reports are known to differ from children's reports. Simultaneous assessment using a parent-child dyad is an alternative approach. Our objective was to assess the validity, reliability and responsiveness of a parent-child dyad approach to utility and HR-QOL assessment of paediatric asthma health states. The setting was specialist care in a hospital-based asthma clinic. Participants were 91 girls and boys with asthma aged 8 to 17 years and 91 parents. The intervention employed was parent-child dyad administration of the Health Utilities Index (HUI) 2 and 3, the Pediatric Quality of Life Inventory™ (PedsQL™) Core and Asthma modules, and the Pediatric Asthma Quality of Life Questionnaire (PAQLQ). Questionnaires were administered by interview to children and parents separately and then together as a dyad to assess the child's health state. The dyad interview was repeated at the next clinic visit. Dyad-child agreement was measured by intra-class correlation (ICC) coefficient; Spearman correlations were used to assess convergent validity. Test-retest reliability was assessed in 28 children who remained clinically stable between visits with a two-way ICC coefficient. Responsiveness to change from baseline was assessed with Spearman coefficients in 30 children who demonstrated clinical change between visits. There was no significant agreement between parent and child for the HUI2 or HUI3 whereas agreement between dyad and child was 0.55 (95% confidence interval [CI] 0.36, 0.69) for the HUI2 and 0.74 (95% CI 0.61, 0.82) for the HUI3 overall. With respect to dyad performance characteristics, both HUI2 and HUI3 overall scores demonstrated moderate convergent validity with the generic PedsQL™ Core domains (range r = 0.30-0.52; p  0.4; p < 0.05) was observed for dyad HUI2 total score change over time as correlated with dyad

Some factors influencing the absorption, retention and elimination of ruthenium; Facteurs agissant sur l'absorption, la retention et l'elimination du ruthenium; Nekotorye faktory, vliyakshchie na vsasyvanie, zaderzhku i vydelenie ruteniya; Factores que influyen sobre la absorcion, retencion y eliminacion de rutenio

Energy Technology Data Exchange (ETDEWEB)

Bruce, R. S. [Radiobiological Research Council, Medical Research Council, Harwell (United Kingdom)

1963-02-15

The radioactive isotopes of ruthenium, Ru{sup 103} (t1/2 = 40 d) and Ru{sup 106}(t1/2 = 1 yr), are formed in relatively high yield as a result of nuclear fission of U{sup 235}. There is almost no information on the metabolism of ruthenium by man and the following considerations are based on investigations with rats and rabbits. The nature and extent of the hazard from radioruthenium will depend not only on the circumstances of contamination but also on the physical and chemical state of the ruthenium; Ru{sup 106} administered orally as the dioxide is absorbed from the gastro-intestinal tract to a negligible extent when it is in a particulate form with carrier present but when given as a colloid in the absence of carrier, uptake is similar to that which follows administration of the chloride (3-5%). Nitrato-derivatives of nitrosyl ruthenium may be absorbed to an even greater extent (an average of 13% is absorbed by rabbits). Absorption by rats, which are not fasted, is complete within one hour of an intragastric dose. The limited period of absorption may be explained in terms of the rate of gastric emptying and combination of ruthenium with the contents of the gut. When rats are fasted overnight before the ruthenium is administered, absorption is increased threefold-and continues over a longer period. Nitrato derivatives of nitrosyl-ruthenium, in contrast to other compounds tested, react with the wall of the upper small intestine where up to 20% of an oral dose may be retained for several hours. Although the chemical state of ruthenium influences the degree of absorption, the subsequent distribution is not greatly affected. Approximately half of the absorbed ruthenium is excreted in the urine during the first 24 h. After one month, 5 to 20% of the absorbed fraction is retained with a long biological half-life. The ruthenium is distributed throughout the body with the concentrations in the various organs seldem differing by a factor of more than five, though the

Emotional Availability and Touch in Deaf and Hearing Dyads

Science.gov (United States)

Paradis, Grace; Koester, Lynne Sanford

2015-01-01

In recent years, increasing attention has been given to the development of deaf children, though few studies have included Deaf parents. The present study examined emotional availability (EA) and functions of touch used by Deaf or hearing parents with hearing or deaf infants during free play. Sixty dyads representing four hearing status groups…

Charge-transfer state and large first hyperpolarizability constant in a highly electronically coupled zinc and gold porphyrin dyad.

Science.gov (United States)

Fortage, Jérôme; Scarpaci, Annabelle; Viau, Lydie; Pellegrin, Yann; Blart, Errol; Falkenström, Magnus; Hammarström, Leif; Asselberghs, Inge; Kellens, Ruben; Libaers, Wim; Clays, Koen; Eng, Mattias P; Odobel, Fabrice

2009-09-14

We report the synthesis and the characterizations of a novel dyad composed of a zinc porphyrin (ZnP) linked to a gold porphyrin (AuP) through an ethynyl spacer. The UV/Vis absorption spectrum and the electrochemical properties clearly reveal that this dyad exhibits a strong electronic coupling in the ground state as evidenced by shifted redox potentials and the appearance of an intense charge-transfer band localized at lambda = 739 nm in dichloromethane. A spectroelectrochemical study of the dyad along with the parent homometallic system (i.e., ZnP-ZnP and AuP-AuP) was undertaken to determine the spectra of the reduced and oxidized porphyrin units. Femtosecond transient absorption spectroscopic analysis showed that the photoexcitation of the heterometallic dyad leads to an ultrafast formation of a charge-separated state ((+)ZnP-AuP(*)) that displays a particularly long lifetime (tau = 4 ns in toluene) for such a short separation distance. The molecular orbitals of the dyad were determined by DFT quantum-chemical calculations. This theoretical study confirms that the observed intense band at lambda = 739 nm corresponds to an interporphyrin charge-transfer transition from the HOMO orbital localized on the zinc porphyrin to LUMO orbitals localized on the gold porphyrin. Finally, a Hyper-Rayleigh scattering study shows that the dyad possesses a large first molecular hyperpolarizability coefficient (beta = 2100x10(-30) esu at lambda = 1064 nm), thus highlighting the valuable nonlinear optical properties of this new type of push-pull porphyrin system.

A Multi-Addressable Dyad with Switchable CMY Colors for Full-Color Rewritable Papers.

Science.gov (United States)

Qin, Tianyou; Han, Jiaqi; Geng, Yue; Ju, Le; Sheng, Lan; Zhang, Sean Xiao-An

2018-06-23

Reversible multicolor displays on solid media using single molecule pigments have been a long-awaited goal. Herein, a new and simple molecular dyad, which can undergo switchable CMY color changes both in solution and solid substrate upon exposure to light, water/acid, and nucleophiles, is designed and synthesized. The stimuli used in this work can be applied independent of each other, which is beneficial for color changes without mutual interference. As a comparison, the mixtures of the two molecular switching motifs forming the basis of the dyad were also studied. The dyad greatly outperforms the corresponding mixed system with respect to reversible color-switching on the paper substrate. Its potential for full-color rewritable paper with excellent reversibility has been demonstrated. Legible multicolor prints, that is, high color contrast and resolution, good dispersion, excellent reversibility, were achieved using common water-jet and light-based printers. This work provides a very promising approach for further development of full-color switchable molecules, materials and displays. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ceria-supported ruthenium nanoparticles as highly active and long-lived catalysts in hydrogen generation from the hydrolysis of ammonia borane.

Science.gov (United States)

Akbayrak, Serdar; Tonbul, Yalçın; Özkar, Saim

2016-07-05

Ruthenium(0) nanoparticles supported on ceria (Ru(0)/CeO2) were in situ generated from the reduction of ruthenium(iii) ions impregnated on ceria during the hydrolysis of ammonia borane. Ru(0)/CeO2 was isolated from the reaction solution by centrifugation and characterized by ICP-OES, BET, XRD, TEM, SEM-EDS and XPS techniques. All the results reveal that ruthenium(0) nanoparticles were successfully supported on ceria and the resulting Ru(0)/CeO2 is a highly active, reusable and long-lived catalyst for hydrogen generation from the hydrolysis of ammonia borane with a turnover frequency value of 361 min(-1). The reusability tests reveal that Ru(0)/CeO2 is still active in the subsequent runs of hydrolysis of ammonia borane preserving 60% of the initial catalytic activity even after the fifth run. Ru(0)/CeO2 provides a superior catalytic lifetime (TTO = 135 100) in hydrogen generation from the hydrolysis of ammonia borane at 25.0 ± 0.1 °C before deactivation. The work reported here includes the formation kinetics of ruthenium(0) nanoparticles. The rate constants for the slow nucleation and autocatalytic surface growth of ruthenium(0) nanoparticles were obtained using hydrogen evolution as a reporter reaction. An evaluation of rate constants at various temperatures enabled the estimation of activation energies for both the reactions, Ea = 60 ± 7 kJ mol(-1) for the nucleation and Ea = 47 ± 2 kJ mol(-1) for the autocatalytic surface growth of ruthenium(0) nanoparticles, as well as the activation energy of Ea = 51 ± 2 kJ mol(-1) for the catalytic hydrolysis of ammonia borane.

Congruence of therapeutic bond perceptions and its relation to treatment outcome: Within- and between-dyad effects.

Science.gov (United States)

Rubel, Julian A; Bar-Kalifa, Eran; Atzil-Slonim, Dana; Schmidt, Sebastian; Lutz, Wolfgang

2018-04-01

The present study investigates the association between congruence of patients' and therapists' perceptions of the therapeutic bond and symptom improvement. Bond congruence-outcome associations were examined on the within- and between-dyad level for 580 patients (mainly depression and anxiety) receiving cognitive-behavioral therapy. Symptom change was assessed on a session-to-session level as well as from pre- to posttreatment. For the between-dyad analyses, the truth and bias model was applied. For the within-dyad analyses, polynomial regression and response surface analysis were conducted. On the between-dyad level, higher temporal congruence between patients' and therapists' bond ratings (i.e., their correlation) was associated with better treatment outcomes. Additionally, the average discrepancy between therapists' and patients' bond ratings showed a significant quadratic association with treatment outcome. A tendency for therapists to moderately rate the bond lower than their patients' showed lowest posttreatment symptom scores. On the within-dyad level, we found that when patients' and therapists' ratings were in "agreement," higher bond scores were associated with fewer next-session symptoms. For "disagreement," the results showed that if therapists rated the bond as weak, whereas their patients rated it as strong, higher subsequent symptom distress was observed than if patients rated the bond as weak and their therapists rated it as strong. The present study highlights the importance of therapists being vigilant to session-to-session changes in the therapeutic bond to adjust their interventions accordingly. (PsycINFO Database Record (c) 2018 APA, all rights reserved).

Antipyrilquinoneimine dye formation by coupling aniline derivatives with 4-aminoantipyrine in the presence of ruthenium nanoparticles

International Nuclear Information System (INIS)

Kasthuri, J.; Santhanalakshmi, J.; Rajendiran, N.

2008-01-01

The coupling of 4-aminoantipyrine with aniline derivatives catalyzed by ruthenium nanoparticles has been studied by UV-Vis spectroscopy in aqueous medium. The rate constant for antipyrilquinoneimine dye formation depends on the nature of the aniline substituent and the p H, ionic strength and temperature of the reaction medium. The maximum rate constant of the dye formation reaction is observed at p H 3.6. Aniline derivatives with electron donating substituents show higher rate constant values than those with electron withdrawing substituents, with increasing rate constant values in the order: N,N-dimethyl aniline> a-toluidine> o-chloroaniline > m-chloroaniline. With pseudo first order kinetics, the total order is 1.0 + 1.0 + 1.0 = 3.0, which includes the orders with respect to amine, 4-aminoantipyrine and ruthenium nanoparticles. Studies on these effects help to complete the kinetic analysis as well as propose the reaction pathway. Furthermore, TEM measurement confirms that the nano scalar size of the ruthenium nanoparticles is 7 nm

Electrochemical behavior of ruthenium-hexacyanoferrate modified glassy carbon electrode and catalytic activity towards ethanol electro oxidation

Energy Technology Data Exchange (ETDEWEB)

Costa, Wendell M.; Marques, Aldalea L.B., E-mail: aldalea.ufma@hotmail.com [Universidade Federal do Maranhao (UFMA), Sao Luis, MA (Brazil). Departamento de Quimica Tecnologica; Cardoso, William S.; Marques, Edmar P.; Bezerra, Cicero W.B. [Universidade Federal do Maranhao (UFMA), Sao Luis, MA (Brazil). Departamento de Qumica; Ferreira, Antonio Ap. P. [Universidade Estadual Paulista Julio de Mesquita Filho (UNESP), Araraquara, SP (Brazil). Instituto de Quimica; Song, Chaojie; Zhang, Jiujun [Energy, Mining and Environment Portfolio, National Research Council of Canada, Vancouver, BC (Canada)

2013-04-15

Ruthenium-based hexacyanoferrate (RuHCF) thin film modified glassy carbon electrode was prepared by drop evaporation method. The RuHCF modified electrode exhibited four redox couples in strong acidic solution (pH 1.5) attributed to Fe(CN){sub 6}{sup 3-} ion and three ruthenium forms (Ru(II), Ru(III) and Ru(IV)), characteristic of ruthenium oxide compounds. The modified electrode displayed excellent electrocatalytic activity towards ethanol oxidation in the potential region where electrochemical processes Ru(III)-O-Ru(IV) and Ru(IV)-O-Ru(VI) occur. Impedance spectroscopy data indicated that the charge transfer resistance decreased with the increase of the applied potential and ethanol concentration, indicating the use of the RuHCF modified electrode as an ethanol sensor. Under optimized conditions, the sensor responded linearly and rapidly to ethanol concentration between 0.03 and 0.4 mol L{sup -1} with a limit of detection of 0.76 mmol L{sup -1}, suggesting an adequate sensitivity in ethanol analyses. (author)

Brush Polymer of Donor-Accepter Dyads via Adduct Formation between Lewis Base Polymer Donor and All Carbon Lewis Acid Acceptor

Directory of Open Access Journals (Sweden)

Yang Wang

2017-09-01

Full Text Available A synthetic method that taps into the facile Lewis base (LB→Lewis acid (LA adduct forming reaction between the semiconducting polymeric LB and all carbon LA C60 for the construction of covalently linked donor-acceptor dyads and brush polymer of dyads is reported. The polymeric LB is built on poly(3-hexylthiophene (P3HT macromers containing either an alkyl or vinyl imidazolium end group that can be readily converted into the N-heterocyclic carbene (NHC LB site, while the brush polymer architecture is conveniently constructed via radical polymerization of the macromer P3HT with the vinyl imidazolium chain end. Simply mixing of such donor polymeric LB with C60 rapidly creates linked P3HT-C60 dyads and brush polymer of dyads in which C60 is covalently linked to the NHC junction connecting the vinyl polymer main chain and the brush P3HT side chains. Thermal behaviors, electronic absorption and emission properties of the resulting P3HT-C60 dyads and brush polymer of dyads have been investigated. The results show that a change of the topology of the P3HT-C60 dyad from linear to brush architecture enhances the crystallinity and Tm of the P3HT domain and, along with other findings, they indicate that the brush polymer architecture of donor-acceptor domains provides a promising approach to improve performances of polymer-based solar cells.

Tris(2,2'-bipyridyl) ruthenium(II)-bisoprolol-based electrochemiluminescence coupled with capillary zone electrophoresis

Energy Technology Data Exchange (ETDEWEB)

Wang Jingwu [Department of Chemistry, Nanchang University, Nanchang 330031 (China)], E-mail: wangjingwu@ncu.edu.cn; Zhang Xiaojun; Pi Fangfang [Department of Chemistry, Nanchang University, Nanchang 330031 (China); Wang Xiaoxia [Graduate School of Engineering, University of Fukui, Fukui 910-8507 (Japan); Yang Nianjun [Diamond Research Center, National Institute of Advanced Industrial Science and Technology (AIST), Central 2-13, 1-1-1 Umezono, Tsukuba 305-8568 (Japan)], E-mail: nianjun.yang@iaf.fraunhofer.de

2009-03-01

Capillary zone electrophoresis (CZE) coupled with tris(2,2'-bipyridyl) ruthenium(II)-based end-column electrogenerated chemiluminescence (ECL) has been utilized to detect bisoprolol in drugs and tablets after its separation from metoprolol. Tetrahydrofuran was used as an additive in the running buffer to obtain the absolute ECL peak of bisoprolol. Bisoprolol reacts as a co-reactant in tris(2,2'-bipyridyl) ruthenium(II) ECL system. Under the optimized experimental conditions, bisoprolol was separated successfully and efficiently from metoprolol and other co-existed materials in tablets and urine samples. The ECL intensity of tris(2,2'-bipyridyl) ruthenium(II)-bisoprolol-based system is linear with the concentration of bisoprolol from 1.5 {mu}M to 0.3 mM with a detection limit of 0.3 {mu}M. Relative standard derivations of the ECL intensity are 2.58% for the detection of 15 {mu}M bisoprolol. This method is a simple, rapid, selective, and sensitive. It was applied successfully for the monitoring of bisoprolol in market available tablets and human urine samples.

Tracking the Oxygen Status in the Cell Nucleus with a Hoechst-Tagged Phosphorescent Ruthenium Complex.

Science.gov (United States)

Hara, Daiki; Umehara, Yui; Son, Aoi; Asahi, Wataru; Misu, Sotaro; Kurihara, Ryohsuke; Kondo, Teruyuki; Tanabe, Kazuhito

2018-05-04

Molecular oxygen in living cells is distributed and consumed inhomogeneously, depending on the activity of each organelle. Therefore, tractable methods that can be used to monitor the oxygen status in each organelle are needed to understand cellular function. Here we report the design of a new oxygen-sensing probe for use in the cell nucleus. We prepared "Ru-Hoechsts", each consisting of a phosphorescent ruthenium complex linked to a Hoechst 33258 moiety, and characterized their properties as oxygen sensors. The Hoechst unit shows strong DNA-binding properties in the nucleus, and the ruthenium complex shows oxygen-dependent phosphorescence. Thus, Ru-Hoechsts accumulated in the cell nucleus and showed oxygen-dependent signals that could be monitored. Of the Ru-Hoechsts prepared in this study, Ru-Hoechst b, in which the ruthenium complex and the Hoechst unit were linked through a hexyl chain, showed the most suitable properties for monitoring the oxygen status. Ru-Hoechsts are probes with high potential for visualizing oxygen fluctuations in the nucleus. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Long Term Follow-Up after a Randomized Integrated Educational and Psychosocial Intervention in Patient-Partner Dyads Affected by Heart Failure.

Directory of Open Access Journals (Sweden)

Maria Liljeroos

Full Text Available To date, contemporary heart failure care remains patient-focused, but awareness of the partners' and families' situation is increasing. Randomized studies have mainly evaluated the short-term effects of dyadic interventions. Therefore, the aim of this study was to determine the 24-month effects of an intervention with psych-educational support in dyads of heart failure patients and their partners.This study used a randomized study design and 155 patient-partner dyads were enrolled. The intervention included a nurse-led program of three sessions addressing psychoeducational support.The intervention did not have any effect on health, depressive symptoms or perceived control among the patient-partner dyads after 24 months. Furthermore, time to first event did not differ significantly between the intervention group and the control patients.This study may be regarded as a first step in trying to understand dyads' need for supportive care. Individualized and more targeted interventions seem necessary to achieve a higher impact on dyad outcomes.ClinicalTrials.gov NCT02398799.

Electrocatalytic studies of osmium-ruthenium carbonyl cluster compounds for their application as methanol-tolerant cathodes for oxygen reduction reaction and carbon monoxide-tolerant anodes for hydrogen oxidation reaction

Energy Technology Data Exchange (ETDEWEB)

Borja-Arco, E.; Uribe-Godinez, J.; Castellanos, R.H. [Centro de Investigacion y Desarrollo Tecnologico en Electroquimica, Escobedo (Mexico); Altamirano-Gutierrez, A.; Jimenez-Sandoval, O. [Centro de Investigacion y de Estudios Avanzados del Inst. Politecnico Nacional, Querataro (Mexico)

2006-07-01

This paper provided details of an electrokinetic study of novel electrocatalytic materials capable of performing both the oxygen reduction reaction (ORR) and the hydrogen oxidation reaction (HOR). Osmium-ruthenium carbonyl cluster compounds (Os{sub x}Ru{sub 3}(CO){sub n}) were synthesized by chemical condensation in non-polar organic solvents at different boiling points and refluxing temperatures. Three different non-polar organic solvents were used: (1) n-nonane; o-xylene; and 1,2-dichlorobenzene. The electrocatalysts were characterized by Fourier Transform Infra-red (FTIR) spectroscopy, scanning electron microscopy (SEM) and X-ray diffraction (XRD). A rotating disk electrode technique was used to analyze the materials. Results of the analysis showed that the materials performed ORR in both the presence and absence of carbon monoxide (CO), and that electrocatalysts were not poisoned by the presence of CO. Cyclic voltamperometry for the disk electrodes showed that the electrochemical behaviour of the compounds in the acid electrolyte was similar in the presence or absence of methanol. The Tafel slope, exchange current density and the transfer coefficient were also investigated. The electrokinetic parameters for the ORR indicated that the materials with the highest electrocatalytic activity were synthesized in 1,2-dichlorobenzene. Electrocatalytic activity during HOR were prepared in n-nonane. It was concluded that the new materials are good candidates for use as both a cathode and an anode in proton exchange membrane fuel cells (PEMFCs) and direct methanol fuel cells (DMFCs). 7 refs., 2 tabs., 7 figs.

Thermodynamic assessment of the rhodium-ruthenium-oxygen (Rh-Ru-O) system

Science.gov (United States)

Gossé, S.; Bordier, S.; Guéneau, C.; Brackx, E.; Domenger, R.; Rogez, J.

2018-03-01

Ruthenium (Ru) and rhodium (Rh) are abundant platinum-group metals formed during burn-up of nuclear fuels. Under normal operating conditions, Rh and Ru accumulate and predominantly form metallic precipitates with other fission products like Mo, Pd and Tc. In the framework of vitrification of high-level nuclear waste, these fission products are poorly soluble in molten glasses. They precipitate as metallic particles and oxide phases. Moreover, these Ru and Rh rich phases strongly depend on temperature and the oxygen fugacity of the glass melt. In case of severe accidental conditions with air ingress, oxidation of the Ru and Rh is possible. At low temperatures (T 1422 K for rhodium sesquioxide and T > 1815 K for ruthenium dioxide), they may decompose into (Rh)-FCC or (Ru)-HCP metallic phases and radiotoxic volatile gaseous species. A thermodynamic assessment of the Rh-Ru-O system will enable the prediction of: (1) the metallic and oxide phases that form during the vitrification of high-level nuclear wastes and (2) the release of volatile gaseous species during a severe accident. The Calphad method developed herein employs a thermodynamic approach in the investigation of the thermochemistry of rhodium and ruthenium at high temperatures. Current literature on the thermodynamic properties and phase diagram data enables preliminary thermodynamic assessments of the Rh-O and Ru-O systems. Additionally, select compositions in the ternary Rh-Ru-O system underwent experimental tests to complement data found in literature and to establish the phase equilibria in the ternary system.

Nanoengineering of Ruthenium and Platinum-based Nanocatalysts by Continuous-Flow Chemistry for Renewable Energy Applications

KAUST Repository

AlYami, Noktan Mohammed

2017-04-15

This thesis presents an integrated study of nanocatalysts for heterogenous catalytic and electrochemical processes using pure ruthenium (Ru) with mixed-phase and platinum-based nanomaterials synthesized by continuous-flow chemistry. There are three major challenges to the application of nanomaterials in heterogenous catalytic reactions and electrocatalytic processes in acidic solution. These challenges are the following: (i) controlling the size, shape and crystallography of nanoparticles to give the best catalytic properties, (ii) scaling these nanoparticles up to a commercial quantity (kg per day) and (iii) making stable nanoparticles that can be used catalytically without degrading in acidic electrolytes. Some crucial limitations of these nanostructured materials in energy conversion and storage applications were overcome by continuous-flow chemistry. By using a continuous-flow reactor, the creation of scalable nanoparticle systems was achieved and their functionality was modified to control the nanoparticles’ physical and chemical characteristics. The nanoparticles were also tested for long-term stability, to make sure these nanoparticles were feasible under realistic working conditions. These nanoparticles are (1) shape- and crystallography-controlled ruthenium (Ru) nanoparticles, (2) size-controlled platinum-metal (Pt-M= nickel (Ni) & copper (Cu)) nanooctahedra (while maintaining morphology) and (3) core-shell platinum@ruthenium (Pt@Ru) nanoparticles where an ultrathin ruthenium shell was templated onto the platinum core. Thus, a complete experimental validation of the formation of a scalable amount of these nanoparticles and their catalytic activity and stability towards the oxygen evolution reaction (OER) in acid medium, hydrolysis of ammonia borane (AB) along with plausible explanations were provided.

Synthesis and properties of mixed-ligand ruthenium(II) complexes containing 2-(2-pyridyl)-benzimidazole and related ligands

International Nuclear Information System (INIS)

Haga, Masaaki; Tanaka, Toshio.

1979-01-01

Mixed-ligand ruthenium(II) complexes of the [Ru(bpy) 2 L]sup(n+) (ClO 4 )sub(n) type, where bpy= 2,2'-bipyridine; L= 2-(2-pyridyl)-benzimidazole (PBImH) when n= 2, and L= 2-(2-pyridyl)-benzimidazolate (PBIm) and 2-(o-hydroxyphenyl)-benzimidazole (OBImH) when n= 1, were prepared. Anodic peak potentials and ruthenium-to-bipyridine charge transfer bands of these complexes are rationalized in terms of the donor ability of L. (author)

Synthesis and properties of mixed-ligand ruthenium(II) complexes containing 2-(2-pyridyl)-benzimidazole and related ligands

Energy Technology Data Exchange (ETDEWEB)

Haga, M [Mie Univ., Tsu (Japan); Tanaka, T

1979-07-01

Mixed-ligand ruthenium(II) complexes of the (Ru(bpy)/sub 2/L)sup(n+) (ClO/sub 4/)sub(n) type, where bpy= 2,2'-bipyridine; L= 2-(2-pyridyl)-benzimidazole (PBImH) when n= 2, and L= 2-(2-pyridyl)-benzimidazolate (PBIm) and 2-(o-hydroxyphenyl)-benzimidazole (OBImH) when n= 1, were prepared. Anodic peak potentials and ruthenium-to-bipyridine charge transfer bands of these complexes are rationalized in terms of the donor ability of L.

Selective catalytic reduction system and process for treating NOx emissions using a palladium and rhodium or ruthenium catalyst

Science.gov (United States)

Sobolevskiy, Anatoly [Orlando, FL; Rossin, Joseph A [Columbus, OH; Knapke, Michael J [Columbus, OH

2011-07-12

A process for the catalytic reduction of nitrogen oxides (NOx) in a gas stream (29) in the presence of H.sub.2 is provided. The process comprises contacting the gas stream with a catalyst system (38) comprising zirconia-silica washcoat particles (41), a pre-sulfated zirconia binder (44), and a catalyst combination (40) comprising palladium and at least one of rhodium, ruthenium, or a mixture of ruthenium and rhodium.

Ruthenium behaviour in severe nuclear accident conditions - Progress report

International Nuclear Information System (INIS)

Backman, U.; Lipponen, M.; Zilliacus, R.; Auvinen, A.; Jokiniemi, J.

2004-03-01

In order to prevent the radioactive ruthenium from spreading in gaseous form in case of an accident in a nuclear power plant it is of interest to know how it is formed and how it behaves. In the experiments the behaviour of ruthenium in oxidising atmosphere at high temperatures is studied. The methods for trapping and analysing RuO4 has been studied. It was found that 1M NaOH is capable of trapping RuO4 totally. The determination of Ru from the solution can be made using ICP-MS (inductively coupled plasma mass spectrometry) and from the reduced precipitates on filters by INAA (instrumental neutron activation analysis). The results of the experiments carried out so far is reported. A significant difference in the decomposition rate of gaseous RuO4 depending on the tube material was found. In all experiments only a minor fraction of Ru remained in gaseous form until the bubbler. In order to achieve a better mass balance an experiment using radioactive tracer was carried out. In the decomposition of gaseous Ru needle-shaped RuO2 crystallites were formed. (au)

Quality of life in stroke survivor-caregiver dyads: a new conceptual framework and longitudinal study protocol.

Science.gov (United States)

Savini, Serenella; Buck, Harleah G; Dickson, Victoria Vaughan; Simeone, Silvio; Pucciarelli, Gianluca; Fida, Roberta; Matarese, Maria; Alvaro, Rosaria; Vellone, Ercole

2015-03-01

To describe a new conceptual framework and the research protocol of a study designed to examine the quality of life in stroke survivor-caregiver dyads. Stroke has a significant impact on the patient-caregiver dyad. Few studies have been guided by a specific conceptual framework which considers the interactions among pre-existing situations prior to stroke, the new situation caused by the stroke and the moderating effects of environmental and caregiver-related variables. Longitudinal study. A sample of stroke survivor-caregiver dyads will be enrolled at patient discharge from rehabilitation hospitals and will be surveyed every 3 months for 1-year. Hypotheses generated from the conceptual framework will test predictors, mediators and moderators of stroke survivor and caregiver quality of life from the pre-existing situation prior to the stroke, the new situation mediation poststroke and situation moderators. The study is supported by a grant from the Centre of Excellence for Nursing Scholarship, Rome, December 2013. This study seeks to identify variables in the pre-existing situation prior to the stroke (e.g. living condition), the new situation mediation poststroke (e.g. type of stroke and caregiver burden) as well as situation moderators (e.g. social support) that influence stroke survivor-caregiver dyad's quality of life across the stroke trajectory. Also, the study will inform clinical practice and research by identifying variables that are potentially modifiable and therefore amenable to intervention. The proposed framework will also be helpful for future research focused on stroke survivor-caregiver dyads. © 2014 John Wiley & Sons Ltd.

Dansyl-naphthalimide dyads as molecular probes: effect of spacer group on metal ion binding properties.

Science.gov (United States)

Shankar, Balaraman H; Ramaiah, Danaboyina

2011-11-17

Interaction of a few dansyl-naphthalimide conjugates 1a-e linked through polymethylene spacer groups with various metal ions was investigated through absorption, fluorescence, NMR, isothermal calorimetric (ITC), and laser flash photolysis techniques. The characteristic feature of these dyads is that they exhibit competing singlet-singlet energy transfer (SSET) and photoinduced electron transfer (PET) processes, both of which decrease with the increase in spacer length. Depending on the spacer group, these dyads interact selectively with divalent Cu(2+) and Zn(2+) ions, as compared to other mono- and divalent metal ions. Jobs plot analysis showed that these dyads form 2:3 complexes with Cu(2+) ions, while 1:1 complexes were observed with Zn(2+) ions. The association constants for the Zn(2+) and Cu(2+) complexes were determined and are found to be in the order 10(3)-10(5) M(-1). Irrespective of the length of the spacer group, these dyads interestingly act as fluorescence ratiometric molecular probes for Cu(2+) ions by altering the emission intensity of both dansyl and naphthalimide chromophores. In contrast, only the fluorescence intensity of the naphthalimide chromophore of the lower homologues (n = 1-3) was altered by Zn(2+) ions. (1)H NMR and ITC measurements confirmed the involvement of both sulfonamide and dimethylamine groups in the complexation with Cu(2+) ions, while only the latter group was involved with Zn(2+) ions. Laser excitation of the dyads 1a-e showed formation of a transient absorption which can be attributed to the radical cation of the naphthalimide chromophore, whereas only the triplet excited state of the dyads 1a-e was observed in the presence of Cu(2+) ions. Uniquely, the complexation of 1a-e with Cu(2+) ions affects both PET and SSET processes, while only the PET process was partially inhibited by Zn(2+) ions in the lower homologues (n = 1-3) and the higher homologues exhibited negligible changes in their emission properties. Our results

A study of ruthenium complexes of some biologically relevant a-N ...

Indian Academy of Sciences (India)

Home; Journals; Journal of Chemical Sciences; Volume 112; Issue 3. A study of ruthenium complexes of some biologically relevant ∙ -N-heterocyclic ... Author Affiliations. P Sengupta1 S Ghosh1. Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, Jadavpur, Calcutta 700 032, India ...

Pretreatment with U(IV) solution for improving the decontamination of ruthenium

International Nuclear Information System (INIS)

Huang Haoxin; Qi Zhanshun; Zhu Guohui

1993-01-01

The ruthenium decontamination factor in Purex process falls quickly in successive TBP cycles. So, it is necessary to change the chemical states of RuNO complexes in order to improve DF Ru in the uranium purification cycle. Hydrazine nitrate is being used to transform RuNO complexes into in-extractable Ru(III)and Ru(IV). However, hydrazine nitrate may be inverted into hydrazoic acid which is dangerous and can bring an unstable factor. Pretreatment using U(IV) solution provides another method to improve the decontamination of ruthenium in Purex process. 0.02 mol/lU(IV) solution can transform RuNO complexes into inextricable species by heating in water bath. The D Ru can be decreased by a factor of 10-20. U(IV) pretreatment does not bring any harmful chemical in process. The acidity has a very large influence on the effect of pretreatment. The higher the acidity is, the worse the effect will be

Mechanistic studies of the oxidation of soluble species of ruthenium in nitric acid solutions. Application to the removal of ruthenium from nuclear fuel dissolution solutions

International Nuclear Information System (INIS)

Carron, V.

2001-01-01

Ruthenium is one of the most troublesome fission products during nuclear fuel reprocessing. His removal from nitric acid fuel dissolution solutions, above the PUREX process, is under consideration. Electro-volatilization could be a possible way to eliminate this element. It consists in the oxidation of soluble ruthenium species coupled with the volatilization of formed RuO 4 . Soluble species are nitrate and nitro complexes of nitrosyl ruthenium RuNO 3+ . The first part of this work deals with the direct oxidation of RuNO 3+ at a golden or a platinum anode. It has been investigated by cyclic voltammetry and infrared and UV-visible reflectance spectroscopy. The oxidation of RuNO 3+ begins with an adsorption step, which precedes the formation of RuO 4 . Then a reaction between RuO 4 and RuNO 3+ occurs to produce a Ru IV compound, which is also electro-oxidized to RuO 4 . The second part concerns potentiostatic electro-volatilization experiences. The rate of electro-volatilization decreases with increasing HNO 3 concentration. At low concentrations, kinetic is controlled by the volatilization of RuO 4 . The rate-determining step is the oxidation of RuNO 3+ at concentrations higher than 1 M. In HNO 3 4 M, the addition of AgNO 3 is required to accelerate the oxidation of RuNO 3+ . The last part is devoted to the study of the indirect oxidation of RuNO 3+ . The electrocatalytic power of electro-generated Ag II is illustrated by voltammetric techniques and potentiostatic electrolysis. The existence of a limit concentration of AgNO 3 is shown (which value depends on experimental conditions) beyond which kinetic is controlled by the RuO 4 volatilization step. These results indicate that the electro-volatilization kinetic could be increased by optimizing the volatilization conditions. (author)

The liquid-liquid extraction of chloro-(trichlorostannato)-rhodium(I/III) and -ruthenium (II) complexes from dilute hydrochloric acid into 4-methylpentan-2-one

International Nuclear Information System (INIS)

Wyrley-Birch, J.M.

1984-10-01

The effect of stannous chloride on the liquid-liquid extraction of rhodium and ruthenium from hydrochloric acid solutions into 4-methyl-pentan-2-one (MIBK)/hexane mixtures was studied in detail. Stannous chloride concentrations were found to considerably increase the efficiency of the extraction of rhodium and ruthenium into the organic phase. Chloro-(trichlorostannato)-rhodium (I/III) complexes were formed at room temperature. The rate of chloro-(trichlorostannato)-ruthenium (II) complex formation was extremely slow at room temperature, but increased on heating of the aqueous solutions. The amount of rhodium and ruthenium extracted into the organic phase depend on the Sn(II):M molar ratio, the HCl, H sup(+) and Cl sup(-) concentrations, as well as the equilibration time. A 119 Sn NMR study of the MIBK extracts, showed that the stoichiometry of the chloro-(trichlorostannato)-rhodium (I/III) complexes extracted into the organic phase was dependent on the Sn(II):Rh(III) molar ratio as well as the HCl, H sup(+) and Cl sup(-) concentrations in the aqueous phase. The predominant species observed in the organic phase from HCl solutions containing Sn(II):Rh(III) ratios >= 5:1, was shown to be an hydrido complex having the form [RhH(SnCl 3 ) 4 Cl] 3 sup(-) or [RhH(SnCl 3 ) 4 ]2 sup(-). An essentially quantitative separation of rhodium and ruthenium was achieved utilising the variation in the rates of rhodium-tin and ruthenium-tin complex formation

Sequential Electrodeposition of Platinum-Ruthenium at Boron-Doped Diamond Electrodes for Methanol Oxidation

Directory of Open Access Journals (Sweden)

Ileana González-González

2011-01-01

Full Text Available Sequential electrodeposition of Pt and Ru on boron-doped diamond (BDD films, in 0.5 M H2SO4 by cyclic voltammetry, has been prepared. The potential cycling, in the aqueous solutions of the respective metals, was between 0.00 and 1.00 V versus Ag/AgCl. The catalyst composites, Pt and PtRu, deposited on BDD film substrates, were tested for methanol oxidation. The modified diamond surfaces were also characterized by scanning electron microscopy-X-ray fluorescence-energy dispersive spectroscopy, X-ray photoelectron spectroscopy, and Auger electron spectroscopy. The scanning Auger electron spectroscopy mapping showed the ruthenium signal only in areas where platinum was electrodeposited. Ruthenium does not deposit on the oxidized diamond surface of the boron-doped diamond. Particles with 5–10% of ruthenium with respect to platinum exhibited better performance for methanol oxidation in terms of methanol oxidation peak current and chronoamperometric current stability. The electrogenerated •OH radicals on BDD may interact with Pt surface, participating in the methanol oxidation as shown in oxidation current and the shift in the peak position. The conductive diamond surface is a good candidate as the support for the platinum electrocatalyst, because it ensures catalytic activity, which compares with the used carbon, and higher stability under severe anodic and cathodic conditions.

Ruthenium complexing in sorption by granulated sorbents with ethylene diamine and diethyl amine groups

International Nuclear Information System (INIS)

Simanova, S.A.; Kolmakova, A.I.; Konovalov, L.V.; Kukushkin, Yu.N.; Kalalova, E.

1986-01-01

The sorption process of ruthenium (4) chlorocomplexes - K 2 (RuCl 6 ) macroporous granulated copolymers of glycidylmethacrylate ethylene dimethacrylate with ethylene diamine and diethyl amine has been studied. Sorption has been carried out under the static conditions (at 20 and 98 deg C) from 0.1-2.0 MxHCl and 1.0 M NaCl solutions. It is established that the sorption from acidic solutions proceeds according to anion exchange mechanism with formation of onium chlorocomplexes in the sorbent phase, subjecting to Anderson regrouping during the heating. During the sorption from neutral solutions the second-sphere coordination of polymer amino groups accirs near ruthenium atom and amino-chloride complexes are formed in the sorbent phase

Electroerosion method for preparation of saturated solutions of ruthenium hydroxochloride

International Nuclear Information System (INIS)

Mikhalev, V.A.; Andrianov, G.A.; Zhadanov, B.V.; Ryazanov, A.I.

1987-01-01

A pilot plant for carrying out electroerosion processes using pulse current of high unit power is developed. The solution process of metallic Ru in concentrated HCl is investigated. The possibility of preparation of ruthenium hydroxochloride solutions of 300 g/l concentration is established; it gives the possibility of Ru solution under conditions similar to the process of salting out

Allenylidene Complexes of Ruthenium: Synthesis, Spectroscopy and Electron Transfer Properties

Czech Academy of Sciences Publication Activity Database

Winter, R. F.; Záliš, Stanislav

2004-01-01

Roč. 248, 15/16 (2004), s. 1565-1583 ISSN 0010-8545 R&D Projects: GA ČR GA203/03/0821; GA MŠk OC D14.20 Institutional research plan: CEZ:AV0Z4040901 Keywords : spectroscopy * allenylidine complexes of ruthenium * electron transfer Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 6.446, year: 2004

Designing of an artificial light energy converter in the form of short-chain dyad when combined with core-shell gold/silver nanocomposites.

Science.gov (United States)

Dutta Pal, Gopa; Paul, Somnath; Bardhan, Munmun; De, Asish; Ganguly, Tapan

2017-06-05

UV-vis absorption, steady state and time resolved fluorescence and absorption spectroscopic investigations demonstrate that the short chain dyad MNTMA when combined with gold-silver core-shell (Au@Ag) nanocomposite , forms elongated conformers in the excited state whereas for the dyad - Ag (spherical) system the majority of dyads remains in a folded conformation. In the dyad-core-shell nanocomposite system, energy wasting charge recombination rate slows down primarily due to elongated conformation and thus it may be anticipated that this hybrid nanocomposite system may serve as a better light energy conversion device. Copyright © 2017 Elsevier B.V. All rights reserved.

Antecedents of Toddler Aggression: Dysfunctional Parenting in Mother-Toddler Dyads

Science.gov (United States)

Del Vecchio, Tamara; O'Leary, Susan G.

2006-01-01

Aggression is stable as early as 2 years of age and predicts many negative adult outcomes. Although longitudinal predictors of child aggression have been identified, information is lacking regarding the proximal precursors of toddlers' aggression. During a 30-min interaction, 54 mother-toddler dyads were observed. Toddlers were categorized as…

Nitrile-functionalized ruthenium nanoparticles: charge delocalization through Ru − N ≡ C interface

International Nuclear Information System (INIS)

Zhang, Fengqi; Huang, Lin; Zou, Jiasui; Yan, Jinwu; Zhu, Jiaying; Kang, Xiongwu; Chen, Shaowei

2017-01-01

Ruthenium nanoparticles (2.06 ± 0.46 nm in diameter) were stabilized by the self-assembly of nitrile molecules onto the ruthenium colloid surface by virtue of the formation of Ru−N≡C interfacial bonding linkages. Thermogravimetric analysis showed that there were about 63 nitrile ligands per nanoparticle, corresponding to an average molecular footprint of 22.4 Å 2 . Proton nuclear magnetic resonance (NMR) studies suggested an end-on configuration of the nitrile moiety on the metal core surface. Meanwhile, infrared measurements showed that the C≡N stretch red-shifted from 2246 to 1944 cm −1 upon adsorption on the nanoparticle surfaces, as confirmed by 15 N isotopic labeling. This apparent red-shift suggests extensive intraparticle charge delocalization, which was further manifested by photoluminescence measurements of 1-cyanopyrene-functionalized ruthenium nanoparticles that exhibited a red shift of 40 nm of the emission maximum, in comparison to that of free monomers. The results further highlight the significance of metal−organic contacts in the manipulation of the dynamics of intraparticle charge transfer and the nanoparticle optical and electronic properties.

Spectral sensitization of SrTiO3 photoanodes with binuclear 1,10-phenanthroline bis(2,2'-bipyridine) complexes of ruthenium(II) and tris(2,2'-bipyridine) ruthenium(II)

NARCIS (Netherlands)

Tinnemans, A.H.A.; Mackor, A.

1981-01-01

A single crystal of strontium titanate, used as a photoanode for the photoelectrolysis of water, has been sensitized by mono‐ and binuclear ruthenium(II) complexes in acidic solution for visible light. The dependence of the photocurrent density on light intensity, dye concentration, wavelength and

In-situ XPS analysis of oxidized and reduced plasma deposited ruthenium-based thin catalytic films

Science.gov (United States)

Balcerzak, Jacek; Redzynia, Wiktor; Tyczkowski, Jacek

2017-12-01

A novel in-situ study of the surface molecular structure of catalytically active ruthenium-based films subjected to the oxidation (in oxygen) and reduction (in hydrogen) was performed in a Cat-Cell reactor combined with a XPS spectrometer. The films were produced by the plasma deposition method (PEMOCVD). It was found that the films contained ruthenium at different oxidation states: metallic (Ru0), RuO2 (Ru+4), and other RuOx (Ru+x), of which content could be changed by the oxidation or reduction, depending on the process temperature. These results allow to predict the behavior of the Ru-based catalysts in different redox environments.

Role of ligands in controlling the regioselectivity in ruthenium ...

Indian Academy of Sciences (India)

of Hay and Wadt (LANL2DZ)11 for ruthenium atom and 6-31G(d)12 for other .... C2 atom in 3x/3′ x. To understand the wider role of lig- ands in modulating the regio-selectivity of product for- mation, we have studied the benzoic acid addition to the selected .... at C1 and the localization of electron density in the. M=C double ...

Dehydrogenative Synthesis of Imines from Alcohols and Amines Catalyzed by a Ruthenium N-Heterocyclic Carbene Complex

DEFF Research Database (Denmark)

Maggi, Agnese; Madsen, Robert

2012-01-01

A new method for the direct synthesis of imines from alcohols and amines is described where hydrogen gas is liberated. The reaction is catalyzed by the ruthenium N-heterocyclic carbene complex [RuCl2(IiPr)(p-cymene)] in the presence of the ligand DABCO and molecular sieves. The imination can...... be applied to a variety of primary alcohols and amines and can be combined with a subsequent addition reaction. A deuterium labeling experiment indicates that the catalytically active species is a ruthenium dihydride. The reaction is believed to proceed by initial dehydrogenation of the alcohol...

Electrodeposited nano-scale islands of ruthenium oxide as a bifunctional electrocatalyst for simultaneous catalytic oxidation of hydrazine and hydroxylamine

Energy Technology Data Exchange (ETDEWEB)

Zare, Hamid R., E-mail: hrzare@yazduni.ac.ir [Department of Chemistry, Yazd University, P.O. Box 89195-741, Yazd (Iran, Islamic Republic of); Nanotechnology Research Center, Yazd University, P.O. Box 89195-741, Yazd (Iran, Islamic Republic of); Hashemi, S. Hossein; Benvidi, Ali [Department of Chemistry, Yazd University, P.O. Box 89195-741, Yazd (Iran, Islamic Republic of)

2010-06-04

For the first time, an electrodeposited nano-scale islands of ruthenium oxide (ruthenium oxide nanoparticles), as an excellent bifunctional electrocatalyst, was successfully used for hydrazine and hydroxylamine electrocatalytic oxidation. The results show that, at the present bifunctional modified electrode, two different redox couples of ruthenium oxides serve as electrocatalysts for simultaneous electrocatalytic oxidation of hydrazine and hydroxylamine. At the modified electrode surface, the peaks of differential pulse voltammetry (DPV) for hydrazine and hydroxylamine oxidation were clearly separated from each other when they co-exited in solution. Thus, it was possible to simultaneously determine hydrazine and hydroxylamine in the samples at a ruthenium oxide nanoparticles modified glassy carbon electrode (RuON-GCE). Linear calibration curves were obtained for 2.0-268.3 {mu}M and 268.3-417.3 {mu}M of hydrazine and for 4.0-33.8 {mu}M and 33.8-78.3 {mu}M of hydroxylamine at the modified electrode surface using an amperometric method. The amperometric method also exhibited the detection limits of 0.15 {mu}M and 0.45 {mu}M for hydrazine and hydroxylamine respectively. RuON-GCE was satisfactorily used for determination of spiked hydrazine in two water samples. Moreover, the studied bifunctional modified electrode exhibited high sensitivity, good repeatability, wide linear range and long-term stability.

A mixed ruthenium polypyridyl complex containing a PEG-bipyridine macroligand

Energy Technology Data Exchange (ETDEWEB)

Marin, Veronica; Holder, Elisabeth; Meier, Michael A.R.; Hoogenboom, Richard; Schubert, Ulrich S. [Laboratory of Macromolecular Chemistry and Nanoscience, Eindhoven University of Technology and Dutch Polymer Institute (DPI), P. O. Box 513, 5600 MB Eindhoven (Netherlands)

2004-04-06

An amino-functionalized bipyridine ligand was prepared in order to serve as a bridging unit to an activated low-molecular-weight monomethyl ether of poly(ethylene glycol) (PEG). Coordination of a ruthenium(II) phenantroline precursor onto the formed PEG-containing bipyridine ligand yielded a metal-containing polymer which shows interesting properties for solar cell applications. (Abstract Copyright [2004], Wiley Periodicals, Inc.)

Preparation and characterization of nickel-caffeine and ruthenium-arborine complexes

International Nuclear Information System (INIS)

Rusmidah Ali

1998-01-01

In this study, two types of complexes were synthesised, namely, nickel-cafeine and ruthenium-arborine by using NiCl 2 6H 2 O and RuCl 3 3H 2 O as starting materials. The complexes were characterised using far- and near infrared and CHN analysis. The proposed complexes were (Ni(kaf)Cl 2 ) 4 and (RuCl 3 Ab)EtOH

The Broader Autism Phenotype and Friendships in Non-Clinical Dyads

Science.gov (United States)

Wainer, Allison L.; Block, Nicole; Donnellan, M. Brent; Ingersoll, Brooke

2013-01-01

The broader autism phenotype (BAP) is a set of subclinical traits qualitatively similar to those observed in autism spectrum disorders. The current study sought to elucidate the association between self- and informant-reports of the BAP and friendships, in a non-clinical sample of college student dyads. Self-informant agreement of the BAP and…

Ruthenium-Catalyzed Dehydrogenative Decarbonylation of Primary Alcohols

DEFF Research Database (Denmark)

Mazziotta, Andrea; Madsen, Robert

2017-01-01

Dehydrogenative decarbonylation of a primary alcohol involves the release of both dihydrogen and carbon monoxide to afford the one-carbon shorter product. The transformation has now been achieved with a ruthenium-catalyzed protocol by using the complex Ru(COD)Cl2 and the hindered monodentate ligand...... P(o-tolyl)3 in refluxing p-cymene. The reaction can be applied to both benzylic and long chain linear aliphatic alcohols. The intermediate aldehyde can be observed during the transformation, which is therefore believed to proceed through two separate catalytic cycles involving first dehydrogenation...... of the alcohol and then decarbonylation of the resulting aldehyde....

The Biological Side of Water-Soluble Arene Ruthenium Assemblies

OpenAIRE

Therrien, Bruno; Furrer, Julien

2014-01-01

This review article covers the synthetic strategies, structural aspects, and host-guest properties of ruthenium metalla-assemblies, with a special focus on their use as drug delivery vectors. The two-dimensional metalla-rectangles show interesting host-guest possibilities but seem less appropriate for being used as drug carriers. On the other hand, metalla-prisms allow encapsulation and possible targeted release of bioactive molecules and consequently show some potential as drug delivery vect...

Synthesis and characterization of ruthenium fluorides and oxide fluorides with high oxidation states

International Nuclear Information System (INIS)

Meublat, L.

1989-10-01

The synthesis of ruthenium fluorides and oxide fluorides with high oxidation states was attempted from dioxide RuO 2 and tetroxide RuO 4 . Three fluorinating agents were used: fluorine, chlorine trifluoride and krypton difluoride. The reactions were achieved in anhydrous hydrogen fluoride at room temperature. Thus, the reaction of RuO 4 with CIF 3 enabled us to prepare chloryl hexafluororuthenate (V), CIO 2 + RuF 6 - , a new compound well identified by vibrational spectroscopy (infra-red and Raman), the structure of which was determined. The reaction of KrF 2 with RuO 4 gave the oxide tetrafluoride RuOF 4 , the previously published syntheses and properties of which were not in agreement with each other. This compound was definitely characterized here by chemical analysis, infra-red spectroscopy and X-ray powder diffraction. The product of thermal decomposition (70 0 C) of RuOF 4 is presumably RuF 4 since only oxygen is liberated during this decomposition. At last, the reaction of KrF 2 with RuO 2 probably leads to the formation of the new oxide fluoride RuO 2 F 4 . Indeed, no oxygen is given off during this reaction, the chemical analysis of the red-orange coloured solid residue is almost in agreement with the one proposed and its infra-red absorption spectrum indicates the presence of ruthenium-oxygen and ruthenium-terminal and bridging fluorine bonds [fr

Synthesis and characterization of ruthenium fluorides and oxide fluorides with high oxidation states

International Nuclear Information System (INIS)

Meublat, L.

1989-01-01

The synthesis of ruthenium fluorides and oxide fluorides with high oxidation states was attempted from dioxide RuO 2 and tetroxide RuO 4 . Three fluorinating agents were used: fluorine, chlorine trifluoride and krypton difluoride. The reactions were achieved in anhydrous hydrogen fluoride at room temperature. Thus, the reaction of RuO 4 with CIF 3 enabled us to prepare chloryl hexafluororuthenate (V), ClO 2 + RuF 6 - , a new compound well idendified by vibrational spectroscopy (infra-red and Raman), the structure of which was determined. The reaction of KrF 2 with RuO 4 gave the oxide tetrafluoride RuOF 4 , the previously published syntheses and properties of which were not in agreement with each other. This compound was definitely characterized here by chemical analysis, infra-red spectroscopy and X-ray powder diffraction. The product of thermal decomposition (70 0 C) of RuOF 4 is presumably RuF 4 since only oxygen is liberated during this decomposition. At last, the reaction of KrF 2 with RuO 2 probably leads to the formation of the new oxide fluoride RuO 2 F 4 . Indeed, no oxygen is given off during this reaction, the chemical analysis of the red-orange coloured solid residue is almost in agreement with the one proposed and its infra-red absorption spectrum indicates the presence of ruthenium-oxygen and ruthenium-terminal and bridging fluorine bonds [fr

Forefront of PUREX system engineering. Chemistry and engineering of ruthenium, technetium and neptunium

International Nuclear Information System (INIS)

2004-07-01

The paper reports the activity of the research committee organized by the Atomic Energy Society of Japan on 'Ruthenium and Technetium Chemistry in the PUREX System', with focusing on basic behaviors of ruthenium, technetium and neptunium in the PUREX process, the principles of plant design, and behaviors during the final waste treatment. The scope of the work includes the following major topics: (1) basic solution and solid-state chemistry; (2) basic solution and solid-state chemistry of minor actinides in particular, Np; (3) partitioning chemistry in the PUREX system and environmental behavior of the components; (4) processes of recovery, purification, and utilization of rare metal fission products; (5) field data on plant design, operation, decontamination, and decommissioning; (6) numerical process simulations and process control technologies; (7) compilation of a data base for process chemistry and plant engineering. (S. Ohno)

Identity Styles and Conflict Resolution Styles: Associations in Mother-Adolescent Dyads

Science.gov (United States)

Missotten, Lies Christine; Luyckx, Koen; Branje, Susan; Vanhalst, Janne; Goossens, Luc

2011-01-01

Adolescent identity and parent-adolescent conflict have each attracted considerable research interest. However, few studies have examined the important link between the two constructs. The present study examined the associations between adolescent identity processing styles and adolescent conflict resolution styles in the mother-adolescent dyad.…

Study of methods for removing strontium, plutonium, and ruthenium from Savannah River Plant waste supernate

International Nuclear Information System (INIS)

Wiley, J.R.

1976-06-01

As a part of long-term waste management studies at the Savannah River Laboratory, tests were made to study removal of strontium, plutonium, and ruthenium from simulated and actual waste supernates. Plutonium was sorbed by Duolite ARC-359 ion exchange resin, the same resin that is used to remove cesium from waste supernate. Strontium was removed from supernate by sorption on a chelating resin Chelex 100, or by precipitation as Sr 3 (PO 4 ) 2 . Activities of 137 Cs, 90 Sr, and 238-241 Pu remaining in processed waste supernate should be 1-10 nanocuries of each element per gram of salt. Of the methods that were tested, none was adequate for plant-scale removal of ruthenium

Light induced intramolecular electron and energy transfer events in rigidly linked borondipyrromethene: Corrole Dyad

Energy Technology Data Exchange (ETDEWEB)

Giribabu, Lingamallu, E-mail: giribabu@iict.res.in [Inorganic & Physical Chemistry Division, CSIR-Indian Institute of Chemical Technology, Tarnaka, Hyderabad 500007, Telangana (India); Jain, Kanika [Department of Chemistry, School of Chemical Sciences & Pharmacy, Central University of Rajasthan, Kishangarh, Dist. Ajmer, Rajasthan 305817 (India); Sudhakar, Kolanu; Duvva, Naresh [Inorganic & Physical Chemistry Division, CSIR-Indian Institute of Chemical Technology, Tarnaka, Hyderabad 500007, Telangana (India); Chitta, Raghu, E-mail: raghuchitta@curaj.ac.in [Department of Chemistry, School of Chemical Sciences & Pharmacy, Central University of Rajasthan, Kishangarh, Dist. Ajmer, Rajasthan 305817 (India)

2016-09-15

We have designed and synthesized a photo-induced energy/electron donor–acceptor conjugate comprising of corrole linked to BODIPY at the 5-position via ester linkage. The dyad was characterized by elemental analysis, MALDI-MS, UV-Visible, {sup 1}H NMR fluorescence spectroscopy (steady-state and time-resolved) as well as electrochemical methods. A comparison of the UV–visible and {sup 1}H NMR spectra of the dyad with those of the corresponding individual model compounds (i.e., BODIPY-CO{sub 2}H and BPFC-OH) reveal that there exist minimum π–π interactions between BODIPY and corrole π-planes. Quenched emission of BODIPY and corrole part of the dyad has been observed in five different solvents. Excitation spectral data provided evidence for an intramolecular excitation energy transfer (EET) from the singlet BODIPY to the corrole and an intramolecular photoinduced electron transfer (PET) from singlet state of corrole to ground state of BODIPY. Detailed analysis of the data suggests that Forster's dipole–dipole mechanism does not adequately explain this energy transfer but, an electron exchange mediated mechanism can, in principle, contribute to the intramolecular EET.

Ruthenium(II) carbonyl compounds with the 4'-chloro-2,2':6',2''-terpyridine ligand.

Science.gov (United States)

Tatikonda, Rajendhraprasad; Haukka, Matti

2017-04-01

Two ruthenium carbonyl complexes with the 4'-chloro-2,2':6',2''-terpyridine ligand (tpy-Cl, C 15 H 10 ClN 3 ), i.e. [RuCl(tpy-Cl)(CO) 2 ][RuCl 3 (CO) 3 ] (I) [systematic name: cis -di-carbonyl-chlorido(4'-chloro-2,2':6',2''-terpyridine-κ 3 N )ruthenium(II) fac -tricarbonyltri-chlorido-ruthenate(II)], and [RuCl 2 (tpy-Cl)(CO) 2 ] (II) [ cis -dicarbonyl- trans -di-chlorido(4'-chloro-2,2':6',2''-terpyridine-κ 2 N 1 , N 1' )ruthenium(II)], were synthesized and characterized by single-crystal X-ray diffraction. The Ru II atoms in both centrosymmetric structures (I) and (II) display similar, slightly distorted octa-hedral coordination spheres. The coordination sphere in the complex cation in compound (I) is defined by three N atoms of the tridentate tpy-Cl ligand, two carbonyl carbon atoms and one chlorido ligand; the charge is balanced by an octa-hedral [Ru(CO) 3 Cl 3 ] - counter-anion. In the neutral compound (II), the tpy-Cl ligand coordinates to the metal only through two of its N atoms. The coordination sphere of the Ru II atom is completed by two carbonyl and two chlorido ligands. In the crystal structures of both (I) and (II), weak C-H⋯Cl inter-actions are observed.

Synthesis and Catalytic Applications of Ruthenium(0) Nanoparticles in Click Chemistry

Energy Technology Data Exchange (ETDEWEB)

Kumar, Avvaru Praveen; Baek, Minwook; Sridhar, Chirumarry; Kumar, Begari Prem; Lee, Yongill [Changwon National Univ., Changwon (Korea, Republic of)

2014-04-15

Here we report a facile synthesis of ruthenium (Ru) Nanoparticles (NPs) by chemical co-precipitation method. The calcination of ruthenium hydroxide samples at 500 .deg. C under hydrogen atmosphere lead to the formation of Ru{sup 0} NPs. The size and aggregation of Ru NPs depends on the pH of the medium, and type of surfactant and its concentration. The X-ray diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscope image (TEM) analyses of particles indicated the formation of Ru{sup 0} NPs, and have 10 to 20 nm sizes. As-synthesized Ru{sup 0} NPs are characterized and investigated their catalytic ability in click chemistry (azide-alkyne cycloaddition reactions), showing good results in terms of reactivity. Interestingly, small structural differences in triazines influence the catalytic activity of Ru{sup 0} nanocatalysts. Click chemistry has recently emerged to become one of the most powerful tools in drug discovery, chemical biology, proteomics, medical sciences and nanotechnology/nanomedicine. In addition, preliminary tests of recycling showed good results with neither loss of activity or significant precipitation.

Synthesis and catalytic activity of ruthenium complexes modified with chiral racemic per- and polyfluorooxaalkanoates

Czech Academy of Sciences Publication Activity Database

Lipovská, P.; Rathouská, L.; Šimůnek, O.; Hošek, J.; Kolaříková, V.; Rybáčková, M.; Cvačka, Josef; Svoboda, Martin; Kvíčala, J.

2016-01-01

Roč. 191, Nov (2016), s. 14-22 ISSN 0022-1139 Institutional support: RVO:61388963 Keywords : racemic * chiral * ruthenium complex * perfluorooxaalkanoate * polyfluorooxaalkanoate Subject RIV: CC - Organic Chemistry Impact factor: 2.101, year: 2016

Nitrile-functionalized ruthenium nanoparticles: charge delocalization through Ru − N ≡ C interface

Energy Technology Data Exchange (ETDEWEB)

Zhang, Fengqi; Huang, Lin; Zou, Jiasui [South China University of Technology, New Energy Research Institute, School of Environment and Energy, Guangzhou Higher Education Mega Centre (China); Yan, Jinwu; Zhu, Jiaying [South China University of Technology, School of Bioscience and Bioengineering, Guangzhou Higher Education Mega Centre (China); Kang, Xiongwu, E-mail: esxkang@scut.edu.cn; Chen, Shaowei, E-mail: shaowei@ucsc.edu [South China University of Technology, New Energy Research Institute, School of Environment and Energy, Guangzhou Higher Education Mega Centre (China)

2017-03-15

Ruthenium nanoparticles (2.06 ± 0.46 nm in diameter) were stabilized by the self-assembly of nitrile molecules onto the ruthenium colloid surface by virtue of the formation of Ru−N≡C interfacial bonding linkages. Thermogravimetric analysis showed that there were about 63 nitrile ligands per nanoparticle, corresponding to an average molecular footprint of 22.4 Å{sup 2}. Proton nuclear magnetic resonance (NMR) studies suggested an end-on configuration of the nitrile moiety on the metal core surface. Meanwhile, infrared measurements showed that the C≡N stretch red-shifted from 2246 to 1944 cm{sup −1} upon adsorption on the nanoparticle surfaces, as confirmed by {sup 15}N isotopic labeling. This apparent red-shift suggests extensive intraparticle charge delocalization, which was further manifested by photoluminescence measurements of 1-cyanopyrene-functionalized ruthenium nanoparticles that exhibited a red shift of 40 nm of the emission maximum, in comparison to that of free monomers. The results further highlight the significance of metal−organic contacts in the manipulation of the dynamics of intraparticle charge transfer and the nanoparticle optical and electronic properties.

Volatility of ruthenium during vitrification operations on fission products. part 1. nitric solutions distillation concentrates calcination. part 2. fixation on a steel tube. decomposition of the peroxide; Volatilite du ruthenium au cours des operations de vitrification des produits de fission. 1. partie distillation des solutions nitriques calcination des concentrats 2. partie fixation sur un tube d'acier decomposition du peroxyde

Energy Technology Data Exchange (ETDEWEB)

Ortins de Bettencourt, A.; Jouan, A. [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

1969-07-01

During vitrification of fission product solutions, a high percentage of the ruthenium initially present in these solutions in the form of nitrosyl-ruthenium nitrates is volatilized with the production of the peroxide which itself is decomposed to ruthenium dioxide. The aim of this work has been to study the volatility of the ruthenium during the vitrification processes. During the distillation of the nitric solutions, we have studied in particular the influence on the volatility of the temperature , of the chemical form in which the ruthenium is introduced, of the bubbling of a gas through the solution, of the nitric concentration and of the nitrate concentration. During the calcination, we have observed the influence of the temperature, of the time, of the flow rate and of the nature of the carrier gas, as well as of the action of the ruthenium bi-oxide and the iron oxide on the volatility of the ruthenium. Part 2. This report deals with the study of the thermal decomposition of ruthenium peroxide, RuO{sub 4}, and its deposition on steel tubing. After a brief bibliographic review of the various properties of this substance, a study is made, in the first part, of its deposition on a steel tube. In order to do this, we pass a gas current containing RuO{sub 4} marked with {sup 106}Ru through a stainless steel tube subjected to a temperature gradient which decreases in the direction of the gas flow. The temperature at which RuO{sub 4} is deposited or is fixed on the tube is determined and the influence of the flow rate on this deposit is studied. In the second part, an attempt has been made to study by a static method the kinetics of the decomposition reaction of ruthenium peroxide to give the dioxide: RuO{sub 4} {yields} RuO{sub 2} + O{sub 2}. To do this, we have tried to introduce gaseous RuO{sub 4} into a container placed in an electric oven, and to follow the reaction by {gamma} counting. (author) [French] Au cours de la vitrification des solutions de produits de

Volatility of ruthenium during vitrification operations on fission products. part 1. nitric solutions distillation concentrates calcination. part 2. fixation on a steel tube. decomposition of the peroxide; Volatilite du ruthenium au cours des operations de vitrification des produits de fission. 1. partie distillation des solutions nitriques calcination des concentrats 2. partie fixation sur un tube d'acier decomposition du peroxyde

Energy Technology Data Exchange (ETDEWEB)

Ortins de Bettencourt, A; Jouan, A [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

1969-07-01

During vitrification of fission product solutions, a high percentage of the ruthenium initially present in these solutions in the form of nitrosyl-ruthenium nitrates is volatilized with the production of the peroxide which itself is decomposed to ruthenium dioxide. The aim of this work has been to study the volatility of the ruthenium during the vitrification processes. During the distillation of the nitric solutions, we have studied in particular the influence on the volatility of the temperature , of the chemical form in which the ruthenium is introduced, of the bubbling of a gas through the solution, of the nitric concentration and of the nitrate concentration. During the calcination, we have observed the influence of the temperature, of the time, of the flow rate and of the nature of the carrier gas, as well as of the action of the ruthenium bi-oxide and the iron oxide on the volatility of the ruthenium. Part 2. This report deals with the study of the thermal decomposition of ruthenium peroxide, RuO{sub 4}, and its deposition on steel tubing. After a brief bibliographic review of the various properties of this substance, a study is made, in the first part, of its deposition on a steel tube. In order to do this, we pass a gas current containing RuO{sub 4} marked with {sup 106}Ru through a stainless steel tube subjected to a temperature gradient which decreases in the direction of the gas flow. The temperature at which RuO{sub 4} is deposited or is fixed on the tube is determined and the influence of the flow rate on this deposit is studied. In the second part, an attempt has been made to study by a static method the kinetics of the decomposition reaction of ruthenium peroxide to give the dioxide: RuO{sub 4} {yields} RuO{sub 2} + O{sub 2}. To do this, we have tried to introduce gaseous RuO{sub 4} into a container placed in an electric oven, and to follow the reaction by {gamma} counting. (author) [French] Au cours de la vitrification des solutions de produits de

Late side effects of Ruthenium 106 therapy for uveal melanomas

International Nuclear Information System (INIS)

Langmann, G.; Faulborn, J.; Poier, E.

1994-01-01

When effectiveness is evaluated in brachytherapy with Ruthenium 106 special emphasis has to be put on tumor destruction and late side effects responsible for the definite functional results. We evaluated the late side effects of 22 uveal melanomas, which had been treated with 106 Ruthenium plaques. The tumor prominences ranged from 3 to 10 mm, the diameter from 4 to 9 disc diameters. In 4 patients the tumor involved the posterior pole, 14 melanomas were located in the midperiphery of the fundus, 4 tumors were ciliary body melanomas. The total radiation dose of the apex ranged from 100 to 240 Gy with a corresponding dose to the sclera between 540 to 1000 Gy. Because of the short half life of the plaque we have been using different dose rates (1.6-11 Gy/h). In 17/22 eyes adequate regression could be achieved by Ruthenium therapy alone. In one case additional laser treatment of the macular part of the melanoma had to be performed, Gamma Knife therapy was necessary in another melanoma with 10 mm tumor prominence. 3 recurrences led to enucleation. The mean follow up was 4.8 years ranging from 1 to 7 years. In 2/22 patients opticopathy caused severe visual impairment, in another 2 patients radiation maculopathy and opticopathy was observed. 7/22 developed vasculopathy with neovascularization treated by photocoagulation. In one case of focal radiation maculopathy laser treatment could prevent further visual impairment. The following factors are responsible for a higher incidence of late side effects: 1. High dose rate of the plaques in combination with a high radiation dose to the sclera 2. Location of the tumor within a minimum distance of 2 disc diameters to the optic nerve or macula 3. Tumor location at the ciliary body Laser treatment in case of neovascularization and focal radiation maculopathy is the only effective treatment with regard to late side effects. Ischemic maculopathy and radiation opticopathy are responsible for late visual impairment. (authors)

TBP 20% diluent/H N O3/H2 O liquid-liquid extraction system: equilibrium data normalization of nitric acid, ruthenium and zirconium

International Nuclear Information System (INIS)

Oliveira, C.A.L.G. de; Araujo, B.F. de.

1991-11-01

The extraction behavior of nitric acid, nitrosyl ruthenium nitrate and zirconium hydroxide nitrate in the system tri-n-butyl phosphate (TBP) 20% -diluent was studied. The main purpose was to obtain enough data to elaborate process flowsheets for the treatment of irradiated uranium fuels. During the runs, the equilibrium diagrams of nitric acid, ruthenium and zirconium were settled. From the achieved data, the influence of nitric acid, ruthenium, zirconium and nitrate ions concentration in the aqueous phase was checked. Furthermore, the density and the surface tension of the aqueous and organic phases were determined, gathering the interfacial tension after the contact between the phases. (author)

A nanogravimmetric investigation of the charging processes on ruthenium oxide thin films and their effect on methanol oxidation

International Nuclear Information System (INIS)

Santos, M.C.; Cogo, L.; Tanimoto, S.T.; Calegaro, M.L.; Bulhoes, L.O.S

2006-01-01

The charging processes and methanol oxidation that occur during the oxidation-reduction cycles in a ruthenium oxide thin film electrode (deposited by the sol-gel method on Pt covered quartz crystals) were investigated by using cyclic voltammetry, chronoamperometry and electrochemical quartz crystal nanobalance techniques. The ruthenium oxide rutile phase structure was determined by X-ray diffraction analysis. The results obtained during the charging of rutile ruthenium oxide films indicate that in the anodic sweep the transition from Ru(II) to Ru(VI) occurs followed by proton de-intercalation. In the cathodic sweep, electron injection occurs followed by proton intercalation, leading to Ru(II). The proton intercalation/de-intercalation processes can be inferred from the mass/charge relationship which gives a slope close to 1 g mol -1 (multiplied by the Faraday constant) corresponding to the molar mass of hydrogen. From the chronoamperometric measurements, charge and mass saturation of the RuO 2 thin films was observed (440 ng cm -2 ) during the charging processes, which is related to the total number of active sites in these films. Using the electrochemical quartz crystal nanobalance technique to study the methanol oxidation reaction at these films was possible to demonstrate that bulk oxidation occurs without the formation of strongly adsorbed intermediates such as CO ads , demonstrating that Pt electrodes modified by ruthenium oxide particles can be promising catalysts for the methanol oxidation as already shown in the literature

In Situ FTIR and NMR Spectroscopic Investigations on Ruthenium-Based Catalysts for Alkene Hydroformylation.

Science.gov (United States)

Kubis, Christoph; Profir, Irina; Fleischer, Ivana; Baumann, Wolfgang; Selent, Detlef; Fischer, Christine; Spannenberg, Anke; Ludwig, Ralf; Hess, Dieter; Franke, Robert; Börner, Armin

2016-02-18

Homogeneous ruthenium complexes modified by imidazole-substituted monophosphines as catalysts for various highly efficient hydroformylation reactions were characterized by in situ IR spectroscopy under reaction conditions and NMR spectroscopy. A proper protocol for the preformation reaction from [Ru3 (CO)12] is decisive to prevent the formation of inactive ligand-modified polynuclear complexes. During catalysis, ligand-modified mononuclear ruthenium(0) carbonyls were detected as resting states. Changes in the ligand structure have a crucial impact on the coordination behavior of the ligand and consequently on the catalytic performance. The substitution of CO by a nitrogen atom of the imidazolyl moiety in the ligand is not a general feature, but it takes place when structural prerequisites of the ligand are fulfilled. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bioimaging of isosteric osmium and ruthenium anticancer agents by LA-ICP-MS.

Science.gov (United States)

Klose, Matthias H M; Theiner, Sarah; Kornauth, Christoph; Meier-Menches, Samuel M; Heffeter, Petra; Berger, Walter; Koellensperger, Gunda; Keppler, Bernhard K

2018-03-01

Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was used to study the spatial distribution of two metallodrugs with anticancer activities in vivo, namely the organoruthenium plecstatin-1 (1) and its isosteric osmium analogue (2), in liver, kidneys, muscles and tumours of treated mice bearing a CT-26 tumour after single-dose i.p. administration. To the best of our knowledge, this is the first time that the spatial distribution of an osmium drug candidate has been investigated using LA-ICP-MS in tissues. Independent measurements of the average ruthenium and osmium concentration via microwave digestion and ICP-MS in organs and tumours were in good agreement with the LA-ICP-MS results. Matrix-matched standards (MMS) ranging from 1 to 30 μg g -1 were prepared to quantify the spatial distributions of the metals and the average metal content of the MMS samples was additionally quantified by ICP-MS after microwave digestion. The recoveries for osmium and ruthenium in the MMS were 105% and 101% on average, respectively, validating the sample preparation procedure of the MMS. Preparation of MMS was carried out under an argon atmosphere to prevent oxidation of osmium-species to the volatile OsO 4 . The highest metal concentrations were found in the liver, followed by kidney, lung and tumour tissues, while muscles displayed only very low quantities of the respective metal. Both metallodrugs accumulated in the cortex of the kidneys more strongly compared to the medulla. Interestingly, osmium from 2 was largely located at the periphery and tissue edges, whereas ruthenium from 1 was observed to penetrate deeper into the organs and tumours.

Large-scale ruthenium- and enzyme-catalyzed dynamic kinetic resolution of (rac-1-phenylethanol

Directory of Open Access Journals (Sweden)

Bäckvall Jan-E

2007-12-01

Full Text Available Abstract The scale-up of the ruthenium- and enzyme-catalyzed dynamic kinetic resolution (DKR of (rac-1-phenylethanol (2 is addressed. The immobilized lipase Candida antarctica lipase B (CALB was employed for the resolution, which shows high enantioselectivity in the transesterification. The ruthenium catalyst used, (η 5-C5Ph5RuCl(CO2 1, was shown to possess very high reactivity in the "in situ" redox racemization of 1-phenylethanol (2 in the presence of the immobilized enzyme, and could be used in 0.05 mol% with high efficiency. Commercially available isopropenyl acetate was employed as acylating agent in the lipase-catalyzed transesterifications, which makes the purification of the product very easy. In a successful large-scale DKR of 2, with 0.05 mol% of 1, (R-1-phenylethanol acetate (3 was obtained in 159 g (97% yield in excellent enantiomeric excess (99.8% ee.

Electronic state of ruthenium deposited onto oxide supports: An XPS study taking into account the final state effects

International Nuclear Information System (INIS)

Larichev, Yurii V.; Moroz, Boris L.; Bukhtiyarov, Valerii I.

2011-01-01

The electronic state of ruthenium in the supported Ru/EO x (EO x = MgO, Al 2 O 3 or SiO 2 ) catalysts prepared by with the use of Ru(OH)Cl 3 or Ru(acac) 3 (acac = acetylacetonate) and reduced with H 2 at 723 K is characterized by X-ray photoelectron spectroscopy (XPS) in the Ru 3d, Cl 2p and O 1s regions. The influence of the final state effects (the differential charging and variation of the relaxation energy) on the binding energy (BE) of Ru 3d 5/2 core level measured for supported Ru nanoparticles is estimated by comparison of the Fermi levels and the modified Auger parameters determined for the Ru/EO x samples with the corresponding characteristics of the bulk Ru metal. It is found that the negative shift of the Ru 3d 5/2 peak which is observed in the spectrum of ruthenium deposited onto MgO (BE = 279.5-279.7 eV) with respect to that of Ru black (BE = 280.2 eV) or ruthenium supported on γ-Al 2 O 3 and SiO 2 (BE = 280.4 eV) is caused not by the transfer of electron density from basic sites of MgO, as considered earlier, but by the differential charging of the supported Ru particles compared with the support surface. Correction for the differential charging value reveals that the initial state energies of ruthenium in the Ru/EO x systems are almost identical (BE = 280.5 ± 0.1 eV) irrespectively of acid-base properties of the support, the mean size of supported Ru crystallites (within the range of 2-10 nm) and the surface Cl content. The results obtained suggest that the difference in ammonia synthesis activity between the Ru catalysts supported on MgO and on the acidic supports is accounted for by not different electronic state of ruthenium on the surface of these oxides but by some other reasons.

A simple and selective spectrophotometric flow injection determination of trace amounts of ruthenium by catalytic oxidation of safranin-O

Energy Technology Data Exchange (ETDEWEB)

Rezaei, Behzad [Department of Chemistry, Isfahan University of Technology, Isfahan 84156-84111 (Iran, Islamic Republic of)], E-mail: rezaei@cc.iut.ac.ir; Keyvanfard, Mohsen [Faculty of Science, Majlesi Campus, Islamic Azad University, Isfahan (Iran, Islamic Republic of)

2008-03-01

In this work, a simple, selective and rapid flow injection method has been developed for determination of ruthenium. The method is based on its catalytic effect on the oxidation of safranin-O by metaperiodate. The reaction was monitored spectrophotometrically by measuring safranin-O absorbance at {lambda}{sub max} = 521. The reagents and manifold variables, which have influences on the sensitivity, were investigated and the optimum conditions were established. The optimized conditions made it possible to determine ruthenium in the ranges of 0.4-20.0 ng/mL ({delta}A = 0.2819C{sub Ru} + 1.1840) and 20.0-100.0 ng/mL ({delta}A = 0.0984C{sub Ru} + 7.9391) with a detection limit of 0.095 ng/mL and a sample rate of 30 {+-} 5 samples/h. Relative standard deviation for the five replicate measurements was less than 1.84%. The proposed method has been successfully applied for analysis of ultra trace amounts of ruthenium in real samples.

A simple and selective spectrophotometric flow injection determination of trace amounts of ruthenium by catalytic oxidation of safranin-O

International Nuclear Information System (INIS)

Rezaei, Behzad; Keyvanfard, Mohsen

2008-01-01

In this work, a simple, selective and rapid flow injection method has been developed for determination of ruthenium. The method is based on its catalytic effect on the oxidation of safranin-O by metaperiodate. The reaction was monitored spectrophotometrically by measuring safranin-O absorbance at λ max = 521. The reagents and manifold variables, which have influences on the sensitivity, were investigated and the optimum conditions were established. The optimized conditions made it possible to determine ruthenium in the ranges of 0.4-20.0 ng/mL (ΔA = 0.2819C Ru + 1.1840) and 20.0-100.0 ng/mL (ΔA = 0.0984C Ru + 7.9391) with a detection limit of 0.095 ng/mL and a sample rate of 30 ± 5 samples/h. Relative standard deviation for the five replicate measurements was less than 1.84%. The proposed method has been successfully applied for analysis of ultra trace amounts of ruthenium in real samples

p-chloro- and p-bromo-benzoylacetoneoxime as the spectrophotometric reagents for palladium and ruthenium(III)

International Nuclear Information System (INIS)

Yeole, V.V.; Langade, A.D.; Shinde, V.M.

1980-01-01

A procedure is described for the extractive spectrophotometric determination of palladium or ruthenium(III) using p-chloro or p-bromobenzoylacetoneoxime as the reagent. The yellow palladium complexes which are extracted into chloroform from an aqueous solution of pH 3.5, absorb as 400 nm and conform to Beer's law in the range of 10 to 100 μg of Pd/10 ml of organic phase. The orange-red ruthenium complexes which are extracted into ethylacetate from an aqueous solution of pH 5.0, absorbs at 475 nm and conforms to Beer's law in the range of 20 to 200 μg of Ru/10 ml of organic phase. The molar absorptivities, Sandell's sensitivities and instability constants are reported. (author)

Influence of ruthenium ions on the precipitation of α-FeOOH, α-Fe2O3 and Fe3O4 in highly alkaline media

International Nuclear Information System (INIS)

Krehula, Stjepko; Music, Svetozar

2006-01-01

The influence of ruthenium ions on the precipitation of goethite (α-FeOOH), α-Fe 2 O 3 and Fe 3 O 4 in highly alkaline media was investigated by 57 Fe Moessbauer and FT-IR spectroscopies, thermal field emission scanning electron microscope (FE SEM) and EDS. The presence of Ru-dopant strongly affected the precipitation of α-FeOOH at highly alkaline pH, i.e. the formation of α-Fe 2 O 3 was also noticed. A decrease of hyperfine magnetic field (HMF) at RT from 35.1 T (undoped α-FeOOH) to 31.3 T for sample with [Ru]/([Ru] + [Fe]) = 0.0196 was assigned to the incorporation of ruthenium ions into the α-FeOOH structure. Moessbauer spectroscopy showed the formation of stoichiometric Fe 3 O 4 for [Ru]/([Ru] + [Fe]) = 0.0291-0.0909. α-Fe 2 O 3 and Fe 3 O 4 did not show a tendency to the formation of solid solutions with ruthenium ions. FE SEM observations of the samples showed that reference α-FeOOH sample contained acicular particles of good uniformity, which increased the length up to ∼5 times with increase of concentration of ruthenium ions. On the other hand, large octahedral Fe 3 O 4 crystals (particles) were associated with small particles of ruthenium (hydrous) oxide with a size in the range ∼100 nm or less. A possible catalytic action of ruthenium that created reduction conditions for Fe 3+ ions and formation of Fe 2+ ions for precipitation of Fe 3 O 4 was discussed

Dinuclear ruthenium sawhorse-type complexes containing carboxylato bridges and ferrocenyl substituents: Synthesis and electrochemistry

Czech Academy of Sciences Publication Activity Database

Auzias, M.; Süss-Fink, G.; Štěpnička, P.; Ludvík, Jiří

2007-01-01

Roč. 360, č. 6 (2007), s. 2023-2028 ISSN 0020-1693 Institutional research plan: CEZ:AV0Z40400503 Keywords : carboxylato bridges * dinuclear complexes * ruthenium * electrochemistry Subject RIV: CG - Electrochemistry Impact factor: 1.713, year: 2007

Tailoring the Selectivity for Electrocatalytic Oxygen Evolution on Ruthenium Oxides by Zinc Substitution

Czech Academy of Sciences Publication Activity Database

Petrykin, Valery; Macounová, Kateřina; Shlyakhtin, O. A.; Krtil, Petr

2010-01-01

Roč. 49, č. 28 (2010), s. 4813-4815 ISSN 1433-7851 R&D Projects: GA AV ČR IAA400400906 Institutional research plan: CEZ:AV0Z40400503 Keywords : electrocatalysis * ruthenium oxides * zinc substitution Subject RIV: CG - Electrochemistry Impact factor: 12.730, year: 2010

Self-assembled arene-ruthenium-based rectangles for the selective sensing of multi-carboxylate anions.

Science.gov (United States)

Vajpayee, Vaishali; Song, Young Ho; Lee, Min Hyung; Kim, Hyunuk; Wang, Ming; Stang, Peter J; Chi, Ki-Whan

2011-07-04

Novel arene-ruthenium [2+2] metalla-rectangles 4 and 5 have been synthesized by self-assembly using dipyridyl amide ligand 3 and arene-ruthenium acceptors (arene: benzoquinone (1), naphthacenedione (2)) and characterized by NMR spectroscopy and ESI-MS. The solid-state structure of 5 was determined by X-ray diffraction and shows encapsulated diethyl ether molecule in the rectangular cavity of 5. The luminescent 5 was further used for anion sensing with the amidic linkage serving as a hydrogen-bond donor site for anions and the ruthenium moiety serving as a signaling unit. A UV/Vis titration study demonstrated that although 5 interacts very weakly with common monoanions as well as with flexible dicarboxylate anions such as malonate and succinate, it displays significant binding affinity (K>10(3) in MeOH) for rigid multi-carboxylate anions such as oxalate, citrate, and tartrate, exhibiting a 1:1 stoichiometry. It has been suggested that 1:1 bidentate hydrogen bonding assisted by appropriate geometrical complementarity is mainly responsible for the increased affinity of 5 towards such anions. A fluorescence titration study revealed a large fluorescence enhancement of 5 upon binding to multi-carboxylate anions, which can be attributed to the blocking of the photoinduced electron-transfer process from the arene-Ru moiety to the amidic donor in 5 as a result of hydrogen bonding between the donor and the anion. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Disposable biosensor based on cathodic electrochemiluminescence of tris(2,2-bipyridine)ruthenium(II) for uric acid determination

International Nuclear Information System (INIS)

Ballesta-Claver, J.; Rodríguez-Gómez, R.; Capitán-Vallvey, L.F.

2013-01-01

Highlights: ► Cathodic ECL offers conventional and non-aggressive analysis conditions. ► The ECL hydrogen peroxide/ruthenium complex system for uric acid determination is novel. ► The ruthenium complex is electrochemically immobilized on graphite screen-printed electrodes. ► The quantification of the uric acid is based on a Stern–Volmer type equation. ► The use of the cathodic ECL working methodology reduces interferences during analysis. -- Abstract: A new method for uric acid (UA) determination based on the quenching of the cathodic ECL of the tris(2,2-bipyridine)ruthenium(II)–uricase system is described. The biosensor is based on a double-layer design containing first tris(2,2-bipyridine)ruthenium(II) (Ru(bpy) 3 2+ ) electrochemically immobilized on graphite screen-printed cells and uricase in chitosan as a second layer. The uric acid biosensing is based on the ECL quenching produced by uric acid over the cathodic ECL caused by immobilized Ru(bpy) 3 2+ in the presence of uricase. The use of a −1.1 V pulse for 1 s with a dwelling time of 10 s makes it possible to estimate the initial enzymatic rate, which is used as the analytical signal. The Stern–Volmer type calibration function shows a dynamic range from 1.0 × 10 −5 to 1.0 × 10 −3 M with a limit of detection of 3.1 × 10 −6 M and an accuracy of 13.6% (1.0 × 10 −4 M, n = 5) as relative standard deviation. Satisfactory results were obtained for urine samples, creating an affordable alternative for uric acid determination

Designing efficient photochromic dithienylethene dyads.

Science.gov (United States)

Fihey, Arnaud; Jacquemin, Denis

2015-06-01

Aiming at designing more efficient multiphotochromes, we investigate with the help of ab initio tools the impact of the substitution on a series of dimers constituted of two dithienylethene (DTE) moieties, strongly coupled to each other through an ethynyl linker. The electronic structure and the optical properties of a large panel of compounds, substituted on different positions by various types of electroactive groups, have been compared with the aim of designing a dyad in which the three possible isomers (open-open, closed-open, closed-closed) can be reached. We show that appending the reactive carbons atoms of the DTE core with electroactive groups on one of the two photochromes allows cyclisation to be induced on a specific moiety, which leads to the formation of the desired closed-open isomer. Substituting the lateral positions of the thiophene rings provides further control of the topology of the frontier molecular orbitals, so that the electronic transition inducing the second ring closure stands out in the spectrum of the intermediate isomer.

Ultrafast spectroscopic investigation of a fullerene poly(3-hexylthiophene) dyad

Science.gov (United States)

Banerji, Natalie; Seifter, Jason; Wang, Mingfeng; Vauthey, Eric; Wudl, Fred; Heeger, Alan J.

2011-08-01

We present the femtosecond spectroscopic investigation of a covalently linked dyad, PCB-P3HT, formed by a segment of the conjugated polymer P3HT (regioregular poly(3-hexylthiophene)) that is end capped with the fullerene derivative PCB ([6,6]-phenyl-C61-butyric acid ester), adapted from PCBM. The fluorescence of the P3HT segment in tetrahydrofuran (THF) solution is reduced by 64% in the dyad compared to a control compound without attached fullerene (P3HT-OH). Fluorescence upconversion measurements reveal that the partial fluorescence quenching of PCB-P3HT in THF is multiphasic and occurs on an average time scale of 100 ps, in parallel to excited-state relaxation processes. Judging from ultrafast transient absorption experiments, the origin of the quenching is excitation energy transfer from the P3HT donor to the PCB acceptor. Due to the much higher solubility of P3HT compared to PCB in THF, the PCB-P3HT dyad molecules self-assemble into micelles. When pure C60 is added to the solution, it is incorporated into the fullerene-rich center of the micelles. This dramatically increases the solubility of C60 but does not lead to significant additional quenching of the P3HT fluorescence by the C60 contained in the micelles. In PCB-P3HT thin films drop-cast from THF, the micelle structure is conserved. In contrast to solution, quantitative and ultrafast (microscopy images. Ultrafast charge separation occurs also for the fibrous morphology, but the transient absorption experiments show fast loss of part of the charge carriers due to intensity-induced recombination and annihilation processes and monomolecular interfacial trap-mediated or geminate recombination. The yield of the long-lived charge carriers in the highly organized fibers is however comparable to that obtained with annealed P3HT:PCBM blends. PCB-P3HT can therefore be considered as an active material in organic photovoltaic devices.

Dyads affected by chronic heart failure: a randomized study evaluating effects of education and psychosocial support to patients with heart failure and their partners.

Science.gov (United States)

Ågren, Susanna; Evangelista, Lorraine S; Hjelm, Carina; Strömberg, Anna

2012-05-01

Chronic heart failure (CHF) causes great suffering for both patients and their partners. The aim of this study was to evaluate the effects of an integrated dyad care program with education and psychosocial support to patients with CHF and their partners during a postdischarge period after acute deterioration of CHF. One hundred fifty-five patient-caregiver dyads were randomized to usual care (n = 71) or a psychoeducation intervention (n = 84) delivered in 3 modules through nurse-led face-to-face counseling, computer-based education, and other written teaching materials to assist dyads to develop problem-solving skills. Follow-up assessments were completed after 3 and 12 months to assess perceived control, perceived health, depressive symptoms, self-care, and caregiver burden. Baseline sociodemographic and clinical characteristics of dyads in the experimental and control groups were similar at baseline. Significant differences were observed in patients' perceived control over the cardiac condition after 3 (P effect was seen for the caregivers.No group differences were observed over time in dyads' health-related quality of life and depressive symptoms, patients' self-care behaviors, and partners' experiences of caregiver burden. Integrated dyad care focusing on skill-building and problem-solving education and psychosocial support was effective in initially enhancing patients' levels of perceived control. More frequent professional contact and ongoing skills training may be necessary to have a higher impact on dyad outcomes and warrants further research. Copyright © 2012 Elsevier Inc. All rights reserved.

Efficient oxygen reduction reaction using ruthenium tetrakis(diaquaplatinum)octacarboxyphthalocyanine catalyst supported on MWCNT platform

CSIR Research Space (South Africa)

Maxakato, NW

2011-02-01

Full Text Available -1 Electroanalysis 2011, 23, No. 2, 325 ? 329 Efficient Oxygen Reduction Reaction Using Ruthenium Tetrakis(diaquaplatinum)Octacarboxyphthalocyanine Catalyst Supported on MWCNT Platform Nobanathi W. Maxakato,a Solomon A. Mamuru,a Kenneth I. Ozoemena*a, b a...

Cellular responses of BRCA1-defective and triple-negative breast cancer cells and in vitro BRCA1 interactions induced by metallo-intercalator ruthenium(II) complexes containing chloro-substituted phenylazopyridine

International Nuclear Information System (INIS)

Nhukeaw, Tidarat; Temboot, Pornvichai; Hansongnern, Kanidtha; Ratanaphan, Adisorn

2014-01-01

Triple-negative breast cancer (TNBC) is defined by the absence of expression of estrogen receptor, progesterone receptor and human epidermal growth factor receptor 2. Breast cancers with a BRCA1 mutation are also frequently triple-negative. Currently, there is a lack of effective therapies and known specific molecular targets for this aggressive breast cancer subtype. To address this concern, we have explored the cellular responses of BRCA1-defective and triple-negative breast cancer cells, and in vitro BRCA1 interactions induced by the ruthenium(II) complexes containing the bidentate ligand, 5-chloro-2-(phenylazo)pyridine. Triple-negative MDA-MB-231, BRCA1-defective HCC1937 and BRCA1-competent MCF-7 breast cancer cell lines were treated with ruthenium(II) complexes. The cytoxoxicity of ruthenium-induced breast cancer cells was evaluated by a real time cellular analyzer (RTCA). Cellular uptake of ruthenium complexes was determined by ICP-MS. Cell cycle progression and apoptosis were assessed using propidium iodide and Annexin V flow cytometry. The N-terminal BRCA1 RING protein was used for conformational and functional studies using circular dichroism and in vitro ubiquitination. HCC1937 cells were significantly more sensitive to the ruthenium complexes than the MDA-MB-231 and MCF-7 cells. Treatment demonstrated a higher degree of cytotoxicity than cisplatin against all three cell lines. Most ruthenium atoms were retained in the nuclear compartment, particularly in HCC1937 cells, after 24 h of incubation, and produced a significant block at the G2/M phase. An increased induction of apoptotic cells as well as an upregulation of p53 mRNA was observed in all tested breast cancer cells. It was of interest that BRCA1 mRNA and replication of BRCA1-defective cells were downregulated. Changes in the conformation and binding constants of ruthenium-BRCA1 adducts were observed, causing inactivation of the RING heterodimer BRCA1/BARD1-mediated E3 ubiquitin ligase activity

Nanoengineering of Ruthenium and Platinum-based Nanocatalysts by Continuous-Flow Chemistry for Renewable Energy Applications

KAUST Repository

AlYami, Noktan Mohammed

2017-01-01

This thesis presents an integrated study of nanocatalysts for heterogenous catalytic and electrochemical processes using pure ruthenium (Ru) with mixed-phase and platinum-based nanomaterials synthesized by continuous-flow chemistry. There are three

Highly dispersed supported ruthenium oxide as an aerobic catalyst for acetic acid synthesis

DEFF Research Database (Denmark)

Laursen, Anders Bo; Gorbanev, Yury; Cavalca, Filippo

2012-01-01

The increasing need for shifting to renewable feedstocks in the chemical industry has driven research toward using green aerobic, selective oxidation reactions to produce bulk chemicals. Here, we report the use of a ruthenium mixed oxide/hydroxide (RuOx) on different support materials for the sel...

Fabrication of ruthenium metal nanosheets via topotactic metallization of exfoliated ruthenate nanosheets.

Science.gov (United States)

Fukuda, Katsutoshi; Sato, Jun; Saida, Takahiro; Sugimoto, Wataru; Ebina, Yasuo; Shibata, Tatsuo; Osada, Minoru; Sasaki, Takayoshi

2013-03-04

The metallization behavior of molecularly thin RuO2 nanosheets obtained from complete delamination of layered ruthenates was studied. Interestingly, the RuO2 nanosheets in a monolayer state topotactically transformed into a single layer of Ru atoms, i.e., ruthenium metal nanosheets, which can be regarded as a new family of nanosized metals.

Aerobic Oxidation of 5-(Hydroxymethyl)furfural in Ionic Liquids with Solid Ruthenium Hydroxide Catalysts

DEFF Research Database (Denmark)

Ståhlberg, Tim Johannes Bjarki; Eyjolfsdottir, Ester; Gorbanev, Yury

2012-01-01

The aerobic oxidation of 5-(hydroxymethyl)furfural was investigated over solid ruthenium hydroxide catalysts in ionic liquids at elevated temperatures and pressures. Several different catalyst supports were tested in combination with various ionic liquids. The best result was obtained in [EMIm...

Ruthenium(II)-catalysed remote C-H alkylations as a versatile platform to meta-decorated arenes

Science.gov (United States)

Li, Jie; Korvorapun, Korkit; de Sarkar, Suman; Rogge, Torben; Burns, David J.; Warratz, Svenja; Ackermann, Lutz

2017-06-01

The full control of positional selectivity is of prime importance in C-H activation technology. Chelation assistance served as the stimulus for the development of a plethora of ortho-selective arene functionalizations. In sharp contrast, meta-selective C-H functionalizations continue to be scarce, with all ruthenium-catalysed transformations currently requiring difficult to remove or modify nitrogen-containing heterocycles. Herein, we describe a unifying concept to access a wealth of meta-decorated arenes by a unique arene ligand effect in proximity-induced ruthenium(II) C-H activation catalysis. The transformative nature of our strategy is mirrored by providing a step-economical entry to a range of meta-substituted arenes, including ketones, acids, amines and phenols--key structural motifs in crop protection, material sciences, medicinal chemistry and pharmaceutical industries.

Ruthenium-catalysed decomposition of formic acid: Fuel cell and catalytic applications

KAUST Repository

Piola, Lorenzo

2017-08-08

The decomposition of formic acid into H2 and CO2 was successfully performed using a ruthenium hydride catalyst, without any concomitant CO evolution. The reaction mechanism is investigated by means of density functional theory calculations (DFT). The generated H2 was further exploited in a fuel cell to produce electricity. The catalytic hydrogenation of conjugated olefins, using this dihydrogen generation procedure, is also reported.

Ruthenium-catalysed decomposition of formic acid: Fuel cell and catalytic applications

KAUST Repository

Piola, Lorenzo; Ferná ndez-Salas, José A.; Nahra, Fady; Poater, Albert; Cavallo, Luigi; Nolan, Steven P.

2017-01-01

The decomposition of formic acid into H2 and CO2 was successfully performed using a ruthenium hydride catalyst, without any concomitant CO evolution. The reaction mechanism is investigated by means of density functional theory calculations (DFT). The generated H2 was further exploited in a fuel cell to produce electricity. The catalytic hydrogenation of conjugated olefins, using this dihydrogen generation procedure, is also reported.

Detection of pyrrolizidine alkaloids using flow analysis with both acidic potassium permanganate and tris(2,2'-bipyridyl)ruthenium(II) chemiluminescence

International Nuclear Information System (INIS)

Gorman, Bree A.; Barnett, Neil W.; Bos, Richard

2005-01-01

For the first time, analytically useful chemiluminescence was elicited from the reactions of the pyrrolizidine alkaloids. Heliotrine, retronecine, supinine, monocrotaline and echinatine N-oxide yielded chemiluminescence upon reaction with tris(2,2'-bipyridyl)ruthenium(II) whilst lasiocarpine, its N-oxide and supinine elicited light upon reaction with acidic potassium permanganate. Detection limits for heliotrine were 1.25 x 10 -7 M and 9 x 10 -9 M for tris(2,2'-bipyridyl)ruthenium(III) perchlorate with flow injection analysis (FIA) and the silica-immobilised reagent (4-[4-(dichloromethylsilanyl)-butyl]-4'-methyl-2,2'-bipyridine)bis (2,2'-bipyridyl)ruthenium(II) with sequential injection analysis (SIA), respectively. Lasiocarpine was detectable at 1.4 x 10 -7 M using acidic potassium permanganate with FIA. Additionally, the silica-immobilised reagent was optimised with respect to the oxidant (ammonium ceric nitrate) concentration and the aspiration times which afforded a detection limit for codeine of 5 x 10 -10 M using SIA

Acetic Acid Formation by Selective Aerobic Oxidation of Aqueous Ethanol over Heterogeneous Ruthenium Catalysts

DEFF Research Database (Denmark)

Gorbanev, Yury; Kegnæs, Søren; Hanning, Christopher William

2012-01-01

Heterogeneous catalyst systems comprising ruthenium hydroxide supported on different carrier materials, titania, alumina, ceria, and spinel (MgAl2O4), were applied in selective aerobic oxidation ethanol to form acetic acid, an important bulk chemical and food ingredient. The catalysts were...

Studies of dissolution solutions of ruthenium metal, oxide and mixed compounds in nitric acid

International Nuclear Information System (INIS)

Mousset, F.; Eysseric, C.; Bedioui, F.

2004-01-01

Ruthenium is one of the fission products generated by irradiated nuclear fuel. It is present throughout all the steps of nuclear fuel reprocessing-particularly during extraction-and requires special attention due to its complex chemistry and high βγ activity. An innovative electro-volatilization process is now being developed to take advantage of the volatility of RuO 4 in order to eliminate it at the head end of the Purex process and thus reduce the number of extraction cycles. Although the process operates successfully with synthetic nitrato-RuNO 3+ solutions, difficulties have been encountered in extrapolating it to real-like dissolution solutions. In order to better approximate the chemical forms of ruthenium found in fuel dissolution solutions, kinetic and speciation studies on dissolved species were undertaken with RuO 2 ,xH 2 O and Ru 0 in nitric acid media. (authors)

Investigation of the process for ruthenium fixation on stainless steel in concentrated nitric environment

International Nuclear Information System (INIS)

Massit, Hubert

1987-01-01

This research thesis reports the development of a process and the determination of the conditions for the fixation of insoluble ruthenium compounds on a Z2CN180 stainless steel in a concentrated nitric environment. The original characteristics and results of this research work are the use of a rotating disk to control the hydrodynamic conditions of suspension particle transport towards the collector surface, and the application of X ray spectrometry of solid deposits of ruthenium compounds fixed on this surface. Characterization techniques (granulometry, Auger electron spectroscopy or AES, electron spectroscopy for chemical analysis or ESCA) allowed the assessment of the influence of various parameters (size, surface chemical composition) on the studied process. Electrochemical techniques are used to show the role of particle-substrate Coulomb interactions, on the quantity of fixed particles and on fixation kinetics. The author evokes possible developments and applications, notably decontamination processes [fr

Disposable biosensor based on cathodic electrochemiluminescence of tris(2,2-bipyridine)ruthenium(II) for uric acid determination

Energy Technology Data Exchange (ETDEWEB)

Ballesta-Claver, J.; Rodríguez-Gómez, R. [ECsens, Department of Analytical Chemistry, Campus Fuentenueva, Faculty of Sciences, University of Granada, E-18071 Granada (Spain); Capitán-Vallvey, L.F., E-mail: lcapitan@ugr.es [ECsens, Department of Analytical Chemistry, Campus Fuentenueva, Faculty of Sciences, University of Granada, E-18071 Granada (Spain)

2013-04-03

Highlights: ► Cathodic ECL offers conventional and non-aggressive analysis conditions. ► The ECL hydrogen peroxide/ruthenium complex system for uric acid determination is novel. ► The ruthenium complex is electrochemically immobilized on graphite screen-printed electrodes. ► The quantification of the uric acid is based on a Stern–Volmer type equation. ► The use of the cathodic ECL working methodology reduces interferences during analysis. -- Abstract: A new method for uric acid (UA) determination based on the quenching of the cathodic ECL of the tris(2,2-bipyridine)ruthenium(II)–uricase system is described. The biosensor is based on a double-layer design containing first tris(2,2-bipyridine)ruthenium(II) (Ru(bpy){sub 3}{sup 2+}) electrochemically immobilized on graphite screen-printed cells and uricase in chitosan as a second layer. The uric acid biosensing is based on the ECL quenching produced by uric acid over the cathodic ECL caused by immobilized Ru(bpy){sub 3}{sup 2+} in the presence of uricase. The use of a −1.1 V pulse for 1 s with a dwelling time of 10 s makes it possible to estimate the initial enzymatic rate, which is used as the analytical signal. The Stern–Volmer type calibration function shows a dynamic range from 1.0 × 10{sup −5} to 1.0 × 10{sup −3} M with a limit of detection of 3.1 × 10{sup −6} M and an accuracy of 13.6% (1.0 × 10{sup −4} M, n = 5) as relative standard deviation. Satisfactory results were obtained for urine samples, creating an affordable alternative for uric acid determination.

Synthesis and characterisation of ruthenium(III) complexes with benzimidazole derivatives

International Nuclear Information System (INIS)

Vyas, P.C.; Kaur, N.; Goel, A.K.; Vyas, S.

1995-01-01

Complexes of ruthenium trichloride with biologically important benzimidazole derivatives, viz., 2-(hydroxy methyl) benzimidazole, 2-(l-hydroxy ethyl) benzimidazole, 2-(mercapto methyl) benzimidazole, 2-(l-mercapto ethyl) benzimidazole, and 2,2'-bis-benzimidazole have been synthesized by reacting the above metal chloride and ligands respectively in 1:3 molar ratio. These complexes are characterised on the basis of elemental analysis, molar conductance data, room temperature, magnetic moment values, electronic spectral and IR spectral studies. (author). 17 refs., 2 tabs

Absorption and emission spectroscopic characterisation of a pyrene-flavin dyad

International Nuclear Information System (INIS)

Shirdel, J.; Penzkofer, A.; Prochazka, R.; Shen, Z.; Strauss, J.; Daub, J.

2007-01-01

The pyrene-flavin (isoalloxazine) dyad, PFD {C 44 H 31 N 5 O 5 ; CA Index name: 1-pyrenepropanoic acid, α-[[4,10-dihydro-2,4-dioxo-10- phenylbenzo[g]pteridin-3(2H)-yl)acetyl]amino]-, phenylmethyl ester (αR)-(9Cl); CA Registry number: 618907-57-6}, dissolved in either dichloromethane or acetonitrile is characterized by absorption and emission spectroscopy. Absorption cross-section spectra, stimulated emission cross-section spectra, fluorescence quantum distributions, quantum yields, and degrees of fluorescence polarisation are determined. The fluorescence decay after femtosecond pulse excitation is determined by fluorescence up-conversion. The ground-state absorption recovery is determined by picosecond pump and probe transmission measurements. The dye photo-stability is investigated by observation of absorption spectral changes due to prolonged blue-light excitation. The absorption spectrum of PFD dyad resembles the superposition of the absorption of isoalloxazine (flavin) and 1-methylpyrene. Long-wavelength photo-excitation of the flavin moiety causes fluorescence quenching by ground-state electron transfer from pyrene to isoalloxazine. Short-wavelength photo-excitation of the pyrene moiety causes (i) excited-state electron transfer from pyrene to isoalloxazine, and (ii) Foerster-type energy transfer from pyrene to flavin followed by ground-state electron transfer from pyrene to flavin.

Photo-induced DNA cleavage and cytotoxicity of a ruthenium(II) arene anticancer complex

Czech Academy of Sciences Publication Activity Database

Brabec, Viktor; Prachařová, J.; Štěpánková, Jana; Sadler, P. J.; Kašpárková, Jana

2016-01-01

Roč. 160, JUL2016 (2016), s. 149-155 ISSN 0162-0134 R&D Projects: GA ČR(CZ) GA14-21053S; GA MŠk(CZ) LD14019 Institutional support: RVO:68081707 Keywords : Ruthenium anticancer complex * DNA cleavage * Phototoxicity Subject RIV: BO - Biophysics Impact factor: 3.348, year: 2016

Determination of microgramme amounts of osmium and ruthenium based on inhibition of the iodine-azide reaction by their complexes with 6-mercaptopurine

International Nuclear Information System (INIS)

Matusiewicz, H.; Kurzawa, Z.

1976-01-01

A new kinetic method of the determination of microamounts of osmium and ruthenium has been developed. The reaction between sodum azide and iodine induced by 6-mercaptopurine (6-MP) was used for this purpose. Under suitable experimental conditions the induction coefficient of 6-MP amounts to 1750+-40. The formed complexes of the metals are stable in the medium containing an excess of azide ions and do not induce the iodine-azide reaction. The method consists in the determination of the 6-MP not bound to the metal. The amount of osmium or ruthenium is then determined from linear relations. Before the determination osmium and ruthenium must be separated from other cations and from each other by distillation as volatile tetroxides. The iodine-azide method is simple, sensitive and does not require any apparatus. The range of the determination is 0.1-5.0 μg in 5 cm 3 of the solution of Os(8) and 0.5-5.0 μg for Ru(8). The error of the determination is +-6.4% and +- 6.1% for osmium and ruthenium, respectively. The time of the determination is 30 minutes not taking into account 2-hour waiting time necessary for the formation of the complexes. (author)

Contrasting intermolecular and intramolecular exciplex formation of a 1,4-dicyano-2-methylnaphthalene-N,N-dimethyl-p-toluidine dyad.

Science.gov (United States)

Imoto, Mitsutaka; Ikeda, Hiroshi; Fujii, Takayuki; Taniguchi, Hisaji; Tamaki, Akihiro; Takeda, Motonori; Mizuno, Kazuhiko

2010-05-07

An intramolecular exciplex is formed upon excitation of the cyclohexane solution of the 1,4-dicyano-2-methylnaphthalene-N,N-dimethyl-p-toluidine dyad, but little if any intramolecular CT complex exists in the ground state of this substance in solution. In contrast, in the crystalline state, the dyad forms an intermolecular mixed-stack CT complex in the ground state and an intermolecular exciplex when it is photoexcited.

New soluble functional polymers by free-radical copolymerization of methacrylates and bipyridine ruthenium complexes

NARCIS (Netherlands)

Holder, E.; Meier, M.A.R.; Marin, V.N.; Schubert, U.S.

2003-01-01

The luminescent complex [4-(3-hydroxypropyl)-4-methyl-2,2-bipyridine]-bis(2,2-bipyridine)-ruthenium(II)-bis(hexafluoroantimonate) and its methacrylate derivative were successfully synthesized and fully characterized by two-dimensional 1H and 13C{1H} NMR techniques [correlation spectroscopy (COSY)

Study of the ruthenium fission-product behavior in the containment, in the case of a nuclear reactor severe accident

International Nuclear Information System (INIS)

Mun, Ch.

2007-03-01

Ruthenium tetroxide is an extremely volatile and highly radio-toxic species. During a severe accident with air ingress in the reactor vessel, ruthenium oxides may reach the reactor containment building in significant quantities. Therefore, a better understanding of the RuO 4 (g) behaviour in the containment atmosphere is of primary importance for the assessment of radiological consequences, in the case of potential releases of this species into the environment. A RuO 4 (g) decomposition kinetic law was determined. Steam seems to play a catalytic role, as well as the presence of ruthenium dioxide deposits. The temperature is also a key parameter. The nature of the substrate, stainless steel or paint, did not exhibit any chemical affinities with RuO 4 (g). This absence of reactivity was confirmed by XPS analyses, which indicate the presence of the same species in the Ru deposits surface layer whatever the substrates considered. It has been concluded that RuO 4 (g) decomposition corresponds to a bulk gas phase decomposition. The ruthenium re-volatilization phenomenon under irradiation from Ru deposits was also highlighted. An oxidation kinetic law was determined. The increase of the temperature and the steam concentration promote significantly the oxidation reaction. The establishment of Ru behavioural laws allowed making a modelling of the Ru source term. The results of the reactor calculations indicate that the values obtained for 106 Ru source term are closed to the reference value considered currently by the IRSN, for 900 MWe PWR safety analysis. (author)

Improvements in iodine and ruthenium removal from advanced liquid processing system

Energy Technology Data Exchange (ETDEWEB)

Skibo, A. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

2017-09-27

SRNL has considerable experience in designing, engineering, and operating systems for removing iodine-129 (I-129) and ruthenium-106 (Ru-106) from waste streams that are directly analogous to the Advanced Liquid Processing System (ALPS) waste streams. SRNL proposes to provide the technical background and design and engineering support for an improved I-129 and Ru-106 removal system for application to ALPS on the Fukushima Daiichi Nuclear Power Station (NPS).

Contribution to the study of the fluorination of ruthenium and its dioxide

International Nuclear Information System (INIS)

Courtois, Charles.

1977-12-01

Compounds formed during fluorination of ruthenium and its dioxide are studied. By chemical analysis the constitution of these compounds is cleared up. RuF 5 is the main compound formed, but a secondary product is obtained which is RuF 8 . The vapor pressure of this product is given between 178 and 221 0 K, and its infrared spectrum is drawn [fr

Effect of Financial Incentives on Breastfeeding: A Cluster Randomized Clinical Trial.

Science.gov (United States)

Relton, Clare; Strong, Mark; Thomas, Kate J; Whelan, Barbara; Walters, Stephen J; Burrows, Julia; Scott, Elaine; Viksveen, Petter; Johnson, Maxine; Baston, Helen; Fox-Rushby, Julia; Anokye, Nana; Umney, Darren; Renfrew, Mary J

2018-02-05

Although breastfeeding has a positive effect on an infant's health and development, the prevalence is low in many communities. The effect of financial incentives to improve breastfeeding prevalence is unknown. To assess the effect of an area-level financial incentive for breastfeeding on breastfeeding prevalence at 6 to 8 weeks post partum. The Nourishing Start for Health (NOSH) trial, a cluster randomized trial with 6 to 8 weeks follow-up, was conducted between April 1, 2015, and March 31, 2016, in 92 electoral ward areas in England with baseline breastfeeding prevalence at 6 to 8 weeks post partum less than 40%. A total of 10 010 mother-infant dyads resident in the 92 study electoral ward areas where the infant's estimated or actual birth date fell between February 18, 2015, and February 17, 2016, were included. Areas were randomized to the incentive plus usual care (n = 46) (5398 mother-infant dyads) or to usual care alone (n = 46) (4612 mother-infant dyads). Usual care was delivered by clinicians (mainly midwives, health visitors) in a variety of maternity, neonatal, and infant feeding services, all of which were implementing the UNICEF UK Baby Friendly Initiative standards. Shopping vouchers worth £40 (US$50) were offered to mothers 5 times based on infant age (2 days, 10 days, 6-8 weeks, 3 months, 6 months), conditional on the infant receiving any breast milk. The primary outcome was electoral ward area-level 6- to 8-week breastfeeding period prevalence, as assessed by clinicians at the routine 6- to 8-week postnatal check visit. Secondary outcomes were area-level period prevalence for breastfeeding initiation and for exclusive breastfeeding at 6 to 8 weeks. In the intervention (5398 mother-infant dyads) and control (4612 mother-infant dyads) group, the median (interquartile range) percentage of women aged 16 to 44 years was 36.2% (3.0%) and 37.4% (3.6%) years, respectively. After adjusting for baseline breastfeeding prevalence and local government

Working in Dyads and Alone: Examining Process Variables in Solving Insight Problems

Science.gov (United States)

Tidikis, Viktoria; Ash, Ivan K.

2013-01-01

This study investigated the effects of working in dyads and their associated gender composition on performance (solution rate and time) and process variables (number of impasses, number of passed solutions, and number of problem solving suggestions and interactions) in a set of classic insight problem solving tasks. Two types of insight problems…

Detection of pyrrolizidine alkaloids using flow analysis with both acidic potassium permanganate and tris(2,2'-bipyridyl)ruthenium(II) chemiluminescence

Energy Technology Data Exchange (ETDEWEB)

Gorman, Bree A. [School of Biological and Chemical Sciences, Deakin University, Geelong, Vic. 3217 (Australia); Barnett, Neil W. [School of Biological and Chemical Sciences, Deakin University, Geelong, Vic. 3217 (Australia)]. E-mail: barnie@deakin.edu.au; Bos, Richard [School of Biological and Chemical Sciences, Deakin University, Geelong, Vic. 3217 (Australia)

2005-06-13

For the first time, analytically useful chemiluminescence was elicited from the reactions of the pyrrolizidine alkaloids. Heliotrine, retronecine, supinine, monocrotaline and echinatine N-oxide yielded chemiluminescence upon reaction with tris(2,2'-bipyridyl)ruthenium(II) whilst lasiocarpine, its N-oxide and supinine elicited light upon reaction with acidic potassium permanganate. Detection limits for heliotrine were 1.25 x 10{sup -7} M and 9 x 10{sup -9} M for tris(2,2'-bipyridyl)ruthenium(III) perchlorate with flow injection analysis (FIA) and the silica-immobilised reagent (4-[4-(dichloromethylsilanyl)-butyl]-4'-methyl-2,2'-bipyridine)bis (2,2'-bipyridyl)ruthenium(II) with sequential injection analysis (SIA), respectively. Lasiocarpine was detectable at 1.4 x 10{sup -7} M using acidic potassium permanganate with FIA. Additionally, the silica-immobilised reagent was optimised with respect to the oxidant (ammonium ceric nitrate) concentration and the aspiration times which afforded a detection limit for codeine of 5 x 10{sup -10} M using SIA.

New carboxy-functionalized terpyridines as precursors for zwitterionic ruthenium complexes for polymer-based solar cells

DEFF Research Database (Denmark)

Duprez, V.; Krebs, Frederik C

2006-01-01

New carboxy-terpyridines selectively functionalized at the 4-, 4'- and 4"-positions were prepared in a three-step procedure with good yields using, the Krohnke reaction followed by saponification. Their complexation with ruthenium led to symmetric and unsymmetric terpyridinyl zwitterionic complexes...

Ruthenium nanoparticles decorated curl-like porous carbons for high performance supercapacitors

Science.gov (United States)

Lou, Bih-Show; Veerakumar, Pitchaimani; Chen, Shen-Ming; Veeramani, Vediyappan; Madhu, Rajesh; Liu, Shang-Bin

2016-01-01

The synthesis of highly dispersed and stable ruthenium nanoparticles (RuNPs; ca. 2-3 nm) on porous activated carbons derived from Moringa Oleifera fruit shells (MOC) is reported and were exploited for supercapacitor applications. The Ru/MOC composites so fabricated using the biowaste carbon source and ruthenium acetylacetonate as the co-feeding metal precursors were activated at elevated temperatures (600-900 oC) in the presence of ZnCl2 as the pore generating and chemical activating agent. The as-prepared MOC carbonized at 900 oC was found to possess a high specific surface area (2522 m2 g-1) and co-existing micro- and mesoporosities. Upon incorporating RuNPs, the Ru/MOC nanocomposites loaded with modest amount of metallic Ru (1.0-1.5 wt%) exhibit remarkable electrochemical and capacitive properties, achiving a maximum capacitance of 291 F g-1 at a current density of 1 A g-1 in 1.0 M H2SO4 electrolyte. These highly stable and durable Ru/MOC electrodes, which can be facily fabricated by the eco-friendly and cost-effective route, should have great potentials for practical applications in energy storage, biosensing, and catalysis.

Correlations between electrochemical and spectrochemical parameters of ruthenium sulfoxides series with N-heterocyclic

International Nuclear Information System (INIS)

Oliveira, D. de; Toma, H.E.

1990-01-01

A systematic study of Ru Cl sub(2) (DMSO) sub(2) L sub(2) derivates, where L = N-heterocyclic base is described, contributing for a best understanding of chemical behaviour and electronic structure of the ruthenium sulfoxides. The correlations between the electrochemical and the spectroscopical parameters of the serie are presented with more emphasis. (author)

Ratiometric Fluorescent Detection of Pb2+ by FRET-Based Phthalocyanine-Porphyrin Dyads.

Science.gov (United States)

Zhang, Dongli; Zhu, Mengliang; Zhao, Luyang; Zhang, Jinghui; Wang, Kang; Qi, Dongdong; Zhou, Yang; Bian, Yongzhong; Jiang, Jianzhuang

2017-12-04

Sensitive and selective detection of Pb 2+ is a very worthwhile endeavor in terms of both human health and environmental protection, as the heavy metal is fairly ubiquitous and highly toxic. In this study, we designed phthalocyanine-porphyrin (Pc-Por) heterodyads, namely, H 2 Pc-α-ZnPor (1) and H 2 Pc-β-ZnPor (2), by connecting a zinc(II) porphyrin moiety to the nonperipheral (α) or peripheral (β) position of a metal-free phthalocyanine moiety. Upon excitation at the porphyrin Soret region (420 nm), both of the dyads exhibited not only a porphyrin emission (605 nm) but also a phthalocyanine emission (ca. 700 nm), indicating the occurrence of intramolecular fluorescence resonance energy transfer (FRET) processes from the porphyrin donor to the phthalocyanine acceptor. The dyads can selectively bind Pb 2+ in the phthalocyanine core leading to a red shift of the phthalocyanine absorption and thus a decrease of spectral overlap between the porphyrin emission and phthalocyanine absorption, which in turn suppresses the intramolecular FRET. In addition, the binding of Pb 2+ can highly quench the emission of phthalocyanine by heavy-metal ion effects. The synergistic coupled functions endow the dyads with remarkable ratiometric fluorescent responses at two distinct wavelengths (F 605 /F 703 for 1 and F 605 /F 700 for 2). The emission intensity ratio increased as a linear function to the concentration of Pb 2+ in the range of 0-4.0 μM, whereas the detection limits were determined to be 3.4 × 10 -9 and 2.2 × 10 -8 M for 1 and 2, respectively. Furthermore, by comparative study of 1 and 2, the effects of distance and relative orientation between Pc and ZnPor fluorophores on the FRET efficiency and sensing performance were highlighted, which is helpful for further optimizing such FRET systems.

Study of the ruthenium fission-product behavior in the containment, in the case of a nuclear reactor severe accident; Etude du comportement du produit de fission ruthenium dans l'enceinte de confinement d'un reacteur nucleaire, en cas d'accident grave

Energy Technology Data Exchange (ETDEWEB)

Mun, Ch

2007-03-15

Ruthenium tetroxide is an extremely volatile and highly radio-toxic species. During a severe accident with air ingress in the reactor vessel, ruthenium oxides may reach the reactor containment building in significant quantities. Therefore, a better understanding of the RuO{sub 4}(g) behaviour in the containment atmosphere is of primary importance for the assessment of radiological consequences, in the case of potential releases of this species into the environment. A RuO{sub 4}(g) decomposition kinetic law was determined. Steam seems to play a catalytic role, as well as the presence of ruthenium dioxide deposits. The temperature is also a key parameter. The nature of the substrate, stainless steel or paint, did not exhibit any chemical affinities with RuO{sub 4}(g). This absence of reactivity was confirmed by XPS analyses, which indicate the presence of the same species in the Ru deposits surface layer whatever the substrates considered. It has been concluded that RuO{sub 4}(g) decomposition corresponds to a bulk gas phase decomposition. The ruthenium re-volatilization phenomenon under irradiation from Ru deposits was also highlighted. An oxidation kinetic law was determined. The increase of the temperature and the steam concentration promote significantly the oxidation reaction. The establishment of Ru behavioural laws allowed making a modelling of the Ru source term. The results of the reactor calculations indicate that the values obtained for {sup 106}Ru source term are closed to the reference value considered currently by the IRSN, for 900 MWe PWR safety analysis. (author)

Tridimensional Acculturation and Adaptation among Jamaican Adolescent-Mother Dyads in the United States

Science.gov (United States)

Ferguson, Gail M.; Bornstein, Marc H.; Pottinger, Audrey M.

2012-01-01

A bidimensional acculturation framework cannot account for multiple destination cultures within contemporary settlement societies. A "tridimensional model" is proposed and tested among Jamaican adolescent-mother dyads in the United States compared to Jamaican Islander, European American, African American, and other Black and non-Black U.S.…

Mutual regulation between infant facial affect and maternal touch in depressed and nondepressed dyads

DEFF Research Database (Denmark)

Egmose, Ida; Cordes, Katharina; Smith-Nielsen, Johanne

2017-01-01

research suggests that touch is an important means through which parents regulate their infants’ affects. Also, previous research has shown that post-partum depressed (PPD) mothers and nonclinical mothers differ in their touching behaviors when interacting with their infants. We examined the affect......-regulating function of affectionate, caregiving and playful maternal touch in 24 PPD and 47 nonclinical mother-infant dyads when infants were four months old. In order to investigate the direction of effects and to account for repeated observations, the data were analysed using time-window sequential analysis......, only in the PPD dyads, were the mothers more likely to initiate affectionate touch when their infants were displaying negative facial affect. Our results also showed that mothers use specific touch types to regulate infants’ negative and positive affects; infants are more likely to initiate positive...

Magnetically Recoverable Supported Ruthenium Catalyst for Hydrogenation of Alkynes and Transfer Hydrogenation of Carbonyl Compounds

Science.gov (United States)

A ruthenium (Ru) catalyst supported on magnetic nanoparticles (NiFe2O4) has been successfully synthesized and used for hydrogenation of alkynes at room temperature as well as transfer hydrogenation of a number of carbonyl compounds under microwave irradiation conditions. The cata...

Inductively Coupled Plasma Mass Spectrometry: Sample Analysis of Zirconium and Ruthenium in Metal Organic Frameworks

Science.gov (United States)

2018-02-01

linear regression fits for the calibration curves. The goodness of the linear fits are summarized in Table 3 and Figure 1. Table 3. Concentration...and ruthenium at each calibration level. 11 REFERENCES 1. General Requirements for the Competence of Testing and Calibration Laboratories

Room temperature aerobic oxidation of amines by a nanocrystalline ruthenium oxide pyrochlore nafion composite catalyst.

Science.gov (United States)

Venkatesan, Shanmuganathan; Kumar, Annamalai Senthil; Lee, Jyh-Fu; Chan, Ting-Shan; Zen, Jyh-Myng

2012-05-14

The aerobic oxidation of primary amines to their respective nitriles has been carried out at room temperature using a highly reusable nanocrystalline ruthenium oxide pyrochlore Nafion composite catalyst (see figure). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Health Disparities Score Composite of Youth and Parent Dyads from an Obesity Prevention Intervention: iCook 4-H

Directory of Open Access Journals (Sweden)

Melissa D. Olfert

2018-05-01

Full Text Available iCook 4-H is a lifestyle intervention to improve diet, physical activity and mealtime behavior. Control and treatment dyads (adult primary meal preparer and a 9–10-year-old youth completed surveys at baseline and 4, 12, and 24 months. A Health Disparity (HD score composite was developed utilizing a series of 12 questions (maximum score = 12 with a higher score indicating a more severe health disparity. Questions came from the USDA short form U.S. Household Food Security Survey (5, participation in food assistance programs (1, food behavior (2, level of adult education completed (1, marital status (1, and race (1 adult and 1 child. There were 228 dyads (control n = 77; treatment n = 151 enrolled in the iCook 4-H study. Baseline HD scores were 3.00 ± 2.56 among control dyads and 2.97 ± 2.91 among treatment dyads, p = 0.6632. There was a significant decline in the HD score of the treatment group from baseline to 12 months (p = 0.0047 and baseline to 24 months (p = 0.0354. A treatment by 12-month time interaction was found (baseline mean 2.97 ± 2.91 vs. 12-month mean 1.78 ± 2.31; p = 0.0406. This study shows that behavioral change interventions for youth and adults can help improve factors that impact health equity; although, further research is needed to validate this HD score as a measure of health disparities across time.

Ruthenium(II) pincer complexes with oxazoline arms for efficient transfer hydrogenation reactions

KAUST Repository

Chen, Tao

2012-08-01

Well-defined P NN CN pincer ruthenium complexes bearing both strong phosphine and weak oxazoline donors were developed. These easily accessible complexes exhibit significantly better catalytic activity in transfer hydrogenation of ketones compared to their PN 3P analogs. These reactions proceed under mild and base-free conditions via protonation- deprotonation of the \\'NH\\' group in the aromatization-dearomatization process. © 2012 Elsevier Ltd. All rights reserved.

Synthesis of cationic diphosphine ruthenium complexes with nido-dicarbaundecaborate anions. Molecular structure of [RuCl(dppe)2]+[7,8-nido-C2B9H12]-

International Nuclear Information System (INIS)

Cheredilin, D.N.; Dolgushin, F.M.; Balagurova, E.V.; Godovikov, I.A.; Chizhevskij, I.T.

2004-01-01

Five new diphosphine ruthenium(II) complexes with nido-dicarbaundecaborate anions were synthesized. The composition and structure of the complexes were confirmed by data of 1 H, 31 P{ 1 H} NMR and elementary analysis. The crystal and molecular structure of solvated complex [RuCl(dppe) 2 + [7,8-nido-C 2 B 9 H 12 ] - ·CH 2 Cl 2 was ascertained by the method of X-ray diffraction analysis. It is shown that coordination sphere of ruthenium atom in the complex cation is a distorted trigonal bipyramid. The distances from ruthenium atom to phosphorus atoms are 2.398(1) and 2.391(1) A, while the angle P-Ru-P equals 175.85(5) Deg [ru

A technique for studying digestion by grasshoppers using a 103Ruthenium-labelled marker

International Nuclear Information System (INIS)

Gandar, M.V.

1981-01-01

103 Ru-labelled tris (I,10-phenanthroline) ruthenium (II) chloride has proved to be a convenient marker in investigating digestion in grasshoppers. Assimilation efficiencies and the retension time of the food in the gut were measured. It is surmised that the technique described in this paper will be applicable to studies of a variety of chewing herbivorous insects. (author)

Studies On An Aerobic Oxidation Of Dibenzothiophene And Related Compounds Using Ruthenium Catalyst

Directory of Open Access Journals (Sweden)

Morishita Y.

2015-06-01

Full Text Available An aerobic oxidation of dibenzothiophene and related compounds using a catalytic amount of ruthenium chloride in hydrocarbon solvents at 80°C for 20 h gave the corresponding sulfones in almost quantitative yields. The reaction might proceed via autoxidation of solvents to hydroperoxides and the reaction of sulfur compounds with the resulting hydroperoxides.

A new electrochemical sensor containing a film of chitosan-supported ruthenium: detection and quantification of sildenafil citrate and acetaminophen

International Nuclear Information System (INIS)

Delolo, Fabio Godoy; Rodrigues, Claudia; Silva, Monize Martins da; Batista, Alzir Azevedo; Dinelli, Luis Rogerio; Delling, Felix Nicolai; Zukerman-Schpector, Julio

2014-01-01

This work presents the construction of a novel electrochemical sensor for detection of organic analytes, using a glassy carbon electrode (GCE) modified with a chitosan-supported ruthenium film. The ruthenium-chitosan film was obtained starting from the mer-[RuCl 3 (dppb)(H 2 O)] complex as a [1,4-bis(diphenylphosphine)butane] (dppb) precursor, and chitosan (QT). The structure of the chitosan-supported ruthenium film on the surface of the glassy carbon electrode was characterized by UV-Vis spectroscopy, electron paramagnetic resonance (EPR), scanning electron microscopy (SEM), atomic force microscopy (AFM), powder X-ray diffraction (XRD) and atomic absorption spectroscopy (AAS) techniques. The glassy carbon electrode was modified with a film formed from the evaporation of 5 μL of a solution composed of 5 mg chitosan-supported ruthenium (RuQT) in 10 mL of 0.1 mol L -1 acetic acid. The modified electrode was tested as a sensor for sildenafil citrate (Viagra® 50 mg) and acetaminophen (Tylenol®) detection. The technique utilized for these analyses was differential pulse voltammetry (DPV) in 0.1 mol L -1 H 2 SO 4 (pH 1.0) and 0.1 mol L -1 CH 3 COOK (pH 6.5) as supporting electrolyte. All analyses were carried out during a month using the same electrode. The electrode was washed only with water in between the analyses, keeping it in the refrigerator when it was not in use. This electrode was stable during the period utilized showing no degradation and presenting a linear response over the evaluated concentration interval (1.25 × 10 -5 to 4.99 × 10 -4 mol L -1 ). (author)

Recent advances in the ruthenium-catalyzed hydroarylation of alkynes with aromatics: synthesis of trisubstituted alkenes.

Science.gov (United States)

Manikandan, Rajendran; Jeganmohan, Masilamani

2015-11-14

The hydroarylation of alkynes with substituted aromatics in the presence of a metal catalyst via chelation-assisted C-H bond activation is a powerful method to synthesize trisubstituted alkenes. Chelation-assisted C-H bond activation can be done by two ways: (a) an oxidative addition pathway and (b) a deprotonation pathway. Generally, a mixture of cis and trans stereoisomeric as well as regioisomeric trisubstituted alkenes was observed in an oxidative addition pathway. In the deprotonation pathway, the hydroarylation reaction can be done in a highly regio- and stereoselective manner, and enables preparation of the expected trisubstituted alkenes in a highly selective manner. Generally, ruthenium, rhodium and cobalt complexes are used as catalysts in the reaction. In this review, a ruthenium-catalyzed hydroarylation of alkynes with substituted aromatics is covered completely. The hydroarylation reaction of alkynes with amide, azole, carbamate, phosphine oxide, amine, acetyl, sulfoxide and sulphur directed aromatics is discussed.

Diagnostic electrocardiographic dyad criteria of emphysema in left ventricular hypertrophy.

Science.gov (United States)

Lanjewar, Swapnil S; Chhabra, Lovely; Chaubey, Vinod K; Joshi, Saurabh; Kulkarni, Ganesh; Kothagundla, Chandrasekhar; Kaul, Sudesh; Spodick, David H

2013-01-01

The electrocardiographic diagnostic dyad of emphysema, namely a combination of the frontal vertical P-vector and a narrow QRS duration, can serve as a quasidiagnostic marker for emphysema, with specificity close to 100%. We postulated that the presence of left ventricular hypertrophy in emphysema may affect the sensitivity of this electrocardiographic criterion given that left ventricular hypertrophy generates prominent left ventricular forces and may increase the QRS duration. We reviewed the electrocardiograms and echocardiograms for 73 patients with emphysema. The patients were divided into two groups based on the presence or absence of echocardiographic evidence of left ventricular hypertrophy. The P-vector, QRS duration, and forced expiratory volume in one second (FEV1) were computed and compared between the two subgroups. There was no statistically significant difference in qualitative lung function (FEV1) between the subgroups. There was no statistically significant difference in mean P-vector between the subgroups. The mean QRS duration was significantly longer in patients with left ventricular hypertrophy as compared with those without left ventricular hypertrophy. The presence of left ventricular hypertrophy may not affect the sensitivity of the P-vector verticalization when used as a lone criterion for diagnosing emphysema. However, the presence of left ventricular hypertrophy may significantly reduce the sensitivity of the electrocardiographic diagnostic dyad in emphysema, as it causes a widening of the QRS duration.

Radiation related complications after ruthenium plaque radiotherapy of uveal melanoma

Energy Technology Data Exchange (ETDEWEB)

Summanen, P.; Immonen, I.; Kivela, T.; Tommila, P.; Tarkkanen, A. [Helsinki Univ. Central Hospital (Finland). Meilahti Clinic; Heikkonen, J. [Helsinki Univ. (Finland). Dept of Radiotherapy and Oncology

1996-08-01

The aims were to analyse radiation related complications and secondary enucleation after irradiation of malignant uveal melanoma with ruthenium-106 plaques. A series of 100 consecutive eyes irradiated in 1981-91 was analysed using the life table method and the Cox proportional hazards model. The 3 and 5 year probabilities of being without radiation cataract were 73% and 63%, without neovascular glaucoma 91% and 81%, without vitreous haemorrhage 83% and 74%, without radiation maculopathy 85% and 70%, and without radiation optic neuropathy 90% and 88%, respectively. (Author).

Radiation related complications after ruthenium plaque radiotherapy of uveal melanoma

International Nuclear Information System (INIS)

Summanen, P.; Immonen, I.; Kivela, T.; Tommila, P.; Tarkkanen, A.; Heikkonen, J.

1996-01-01

The aims were to analyse radiation related complications and secondary enucleation after irradiation of malignant uveal melanoma with ruthenium-106 plaques. A series of 100 consecutive eyes irradiated in 1981-91 was analysed using the life table method and the Cox proportional hazards model. The 3 and 5 year probabilities of being without radiation cataract were 73% and 63%, without neovascular glaucoma 91% and 81%, without vitreous haemorrhage 83% and 74%, without radiation maculopathy 85% and 70%, and without radiation optic neuropathy 90% and 88%, respectively. (Author)

Spectroscopic and electrochemical study of the polynuclear clusters of ruthenium acetate

International Nuclear Information System (INIS)

Cipriano, C.

1989-01-01

The chemistry of the trinuclear clusters (Ru 3 O (C H 3 CO 2 ) 4 L 3 ) where L = imidazole, pyridine or pyrazine type of ligands, was investigated based on spectroscopic and electrochemical techniques. These complexes are of great interest from the point of view of their electronic and redox properties, providing multi site species for electron transfer processes. They were isolated in solid state, and characterized by means of elementary analyses and infrared spectra. The electrochemical behaviour in acetonitrile solution was typically reversible; the cyclic voltamograms exhibited a series of four or five mono electronic waves ascribed to the successive Ru I V Ru I I I Ru I I I / Ru I I I Ru I I I Ru I I I / ... Ru I I Ru I I Ru I I redox couples. The differences between the successive redox potentials were about 1 V, indicating strong metal-metal interaction in the trinuclear Ru 3 O centre. The E values were strongly sensitive to the nature of the N-heterocyclic ligand, increasing with the pi-acceptor properties of the pyridine and pyrazine derivatives, but in a much less pronounced way in the case of the imidazole derivatives. (author)

Ruthenium(ii)-catalyzed olefination via carbonyl reductive cross-coupling.

Science.gov (United States)

Wei, Wei; Dai, Xi-Jie; Wang, Haining; Li, Chenchen; Yang, Xiaobo; Li, Chao-Jun

2017-12-01

Natural availability of carbonyl groups offers reductive carbonyl coupling tremendous synthetic potential for efficient olefin synthesis, yet the catalytic carbonyl cross-coupling remains largely elusive. We report herein such a reaction, mediated by hydrazine under ruthenium(ii) catalysis. This method enables facile and selective cross-couplings of two unsymmetrical carbonyl compounds in either an intermolecular or intramolecular fashion. Moreover, this chemistry accommodates a variety of substrates, proceeds under mild reaction conditions with good functional group tolerance, and generates stoichiometric benign byproducts. Importantly, the coexistence of KO t Bu and bidentate phosphine dmpe is vital to this transformation.

Nano-scale islands of ruthenium oxide as an electrochemical sensor for iodate and periodate determination

International Nuclear Information System (INIS)

Chatraei, Fatemeh; Zare, Hamid R.

2013-01-01

In this study, a promising electrochemical sensor was fabricated by the electrodeposition of nano-scale islands of ruthenium oxide (ruthenium oxide nanoparticles, RuON) on a glassy carbon electrode (RuON–GCE). Then, the electrocatalytic oxidation of iodate and periodate was investigated on it, using cyclic voltammetry, chronoamperometry and amperometry as diagnostic techniques. The charge transfer coefficient, α, and the charge transfer rate constant, k s , for electron transfer between RuON and GCE were calculated as 0.5 ± 0.03 and 9.0 ± 0.7 s −1 respectively. A comparison of the data obtained from the electrocatalytic reduction of iodate and periodate at a bare GCE (BGCE) and RuON–GCE clearly shows that the unique electronic properties of nanoparticles definitely improve the characteristics of iodate and periodate electrocatalytic reduction. The kinetic parameters such as the electron transfer coefficient, α, and the heterogeneous electron transfer rate constant, k′, for the reduction of iodate and periodate at RuON–GCE surface were determined using cyclic voltammetry. Amperometry revealed a good linear relationship between the peak current and the concentration of iodate and periodate. The detection limits of 0.9 and 0.2 μM were calculated for iodate and periodate respectively. Highlights: ► Ruthenium oxide nanoparticles, RuON, were used for electrocatalytic reduction iodate and periodate. ► Formal potential, E 0 ′, of the surface redox couple of RuON is pH-dependent. ► The heterogeneous electron transfer rate constant values between both analytes and RuON were calculated.

Structural Features of Sibling Dyads and Attitudes toward Sibling Relationships in Young Adulthood

Science.gov (United States)

Riggio, Heidi R.

2006-01-01

This study examined sibling-dyad structural variables (sex composition, age difference, current coresidence, position adjacency, family size, respondent and/or sibling ordinal position) and attitudes toward adult sibling relationships. A sample of 1,053 young adults (M age = 22.1 years) described one sibling using the Lifespan Sibling Relationship…

Activity of iridium-ruthenium and iridium-rhodium adsorption catalysts in decomposition of hydrogen peroxide

Energy Technology Data Exchange (ETDEWEB)

Zubovich, I A; Mikhaylov, V A; Migulina, N N [Yaroslavskij Politekhnicheskij Inst. (USSR)

1976-06-01

Experimental data for the activities of iridium-ruthenium and iridium-rhodium adsorption catalysts in the decomposition of hydrogen peroxide are considered and the results of magnetic susceptibility measurements are presented. It is concluded that surface structures (complexes) may be formed and that micro-electronic feaures play a role in heterogeneous catalysis.

Synthesis and characterization of branched fcc/hcp ruthenium nanostructures and their catalytic activity in ammonia borane hydrolysis

KAUST Repository

AlYami, Noktan

2018-01-30

Several systems have shown the ability to stabilize uncommon crystal structures during the synthesis of metallic nanoparticles. By tailoring the nanoparticle crystal structure, the physical and chemical properties of the particles can also be controlled. Herein, we first synthesized branched nanoparticles of mixed hcp/fcc ruthenium, which were formed using tungsten carbonyl [W(CO)6] as both a reducing agent and a source of carbon monoxide. The branched particles were formed from multiple particulates off a central core. High-resolution transmission electron microscopy (HRTEM) clearly showed that the branched structures consisted of aligned hcp crystal domains, a mixture of fcc and hcp crystal domains with several defects and misalignments, and particles that contained multiple cores and branches. Branched particles were also formed with molybdenum carbonyl [Mo(CO)6], and faceted particles of hcp and fcc particles were formed with Re2(CO)10 as a carbon monoxide source. Without metal carbonyls, small particles of spherical hcp ruthenium were produced, and their size could be controlled by the selection of the precursor. The ruthenium nanoparticles were tested for ammonia borane hydrolysis; the branched nanoparticles were more reactive for catalytic hydrogen evolution than the faceted hcp/fcc nanoparticles or the spherical hcp nanoparticles. This work showcases the potential of crystal phase engineering of transition metal nanoparticles by different carbon monoxide precursors for tailoring their catalytic reactivity.

Atomic layer deposition of ruthenium on plasma-treated vertically aligned carbon nanotubes for high-performance ultracapacitors.

Science.gov (United States)

Kim, Jun Woo; Kim, Byungwoo; Park, Suk Won; Kim, Woong; Shim, Joon Hyung

2014-10-31

It is challenging to realize a conformal metal coating by atomic layer deposition (ALD) because of the high surface energy of metals. In this study, ALD of ruthenium (Ru) on vertically aligned carbon nanotubes (CNTs) was carried out. To activate the surface of CNTs that lack surface functional groups essential for ALD, oxygen plasma was applied ex situ before ALD. X-ray photoelectron spectroscopy and Raman spectroscopy confirmed surface activation of CNTs by the plasma pretreatment. Transmission electron microscopy analysis with energy-dispersive x-ray spectroscopy composition mapping showed that ALD Ru grew conformally along CNTs walls. ALD Ru/CNTs were electrochemically oxidized to ruthenium oxide (RuOx) that can be a potentially useful candidate for use in the electrodes of ultracapacitors. Electrode performance of RuOx/CNTs was evaluated using cyclic voltammetry and galvanostatic charge-discharge measurements.

Recent advances in the ruthenium(ii)-catalyzed chelation-assisted C-H olefination of substituted aromatics, alkenes and heteroaromatics with alkenes via the deprotonation pathway.

Science.gov (United States)

Manikandan, Rajendran; Jeganmohan, Masilamani

2017-08-08

The transition-metal-catalyzed chelation-assisted alkenylation at the inert C-H bond of aromatics with alkenes is one of the efficient methods to synthesize substituted vinylarenes in a highly regio- and stereoselective manner. Palladium, rhodium and ruthenium complexes are frequently used as catalysts for this type of transformation. The present review describes the recent advances in the ruthenium-catalyzed chelation-assisted alkenylation at the C-H bond of aromatics, alkenes and heteroaromatics with alkenes via the deprotonation pathway. Several directing groups including 2-pyridyl, carbonyl, amidine, amide, amine, imidate, sulphonic acid, triazole, cyano, oxazolidinone and hydontoin are widely used in the reaction. The scope, limitation and mechanistic investigation of the alkenylation reactions are discussed elaborately. This feature article includes all the reported ruthenium-catalyzed alkenylation reactions via the deprotonation pathway until the end of March 2017.

Interplay between singlet and triplet excited states in a conformationally locked donor–acceptor dyad

KAUST Repository

Filatov, Mikhail A.

2015-10-13

The synthesis and photophysical characterization of a palladium(II) porphyrin – anthracene dyad bridged via short and conformationally rigid bicyclo[2.2.2]octadiene spacer were achieved. A spectroscopic investigation of the prepared molecule in solution has been undertaken to study electronic energy transfer in excited singlet and triplet states between the anthracene and porphyrin units. By using steady-state and time-resolved photoluminescence spectroscopy it was shown that excitation of the singlet excited state of the anthracene leads to energy transfer to the lower-lying singlet state of porphyrin. Alternatively, excitation of the porphyrin followed by intersystem crossing to the triplet state leads to very fast energy transfer to the triplet state of anthracene. The rate of this energy transfer has been determined by transient absorption spectroscopy. Comparative studies of the dynamics of triplet excited states of the dyad and reference palladium octaethylporphyrin (PdOEP) have been performed.

Interplay between singlet and triplet excited states in a conformationally locked donor–acceptor dyad

KAUST Repository

Filatov, Mikhail A.; Etzold, Fabian; Gehrig, Dominik; Laquai, Fré dé ric; Busko, Dmitri; Landfester, Katharina; Baluschev, Stanislav

2015-01-01

The synthesis and photophysical characterization of a palladium(II) porphyrin – anthracene dyad bridged via short and conformationally rigid bicyclo[2.2.2]octadiene spacer were achieved. A spectroscopic investigation of the prepared molecule in solution has been undertaken to study electronic energy transfer in excited singlet and triplet states between the anthracene and porphyrin units. By using steady-state and time-resolved photoluminescence spectroscopy it was shown that excitation of the singlet excited state of the anthracene leads to energy transfer to the lower-lying singlet state of porphyrin. Alternatively, excitation of the porphyrin followed by intersystem crossing to the triplet state leads to very fast energy transfer to the triplet state of anthracene. The rate of this energy transfer has been determined by transient absorption spectroscopy. Comparative studies of the dynamics of triplet excited states of the dyad and reference palladium octaethylporphyrin (PdOEP) have been performed.

Half -sand wish ruthenium complexes of heterocyclic-dithio carboxylato ligands

International Nuclear Information System (INIS)

El-khateeb, M.; Al-Noaimi, M.; Harb, M.; Gorls, H.; Weigand, W.

2008-01-01

The heterocyclic-dithio carboxylato complexes Cp Ru(PPh 3 )(κ 2 S,S-S 2 C-h et) [h et= 2-C 4 H 3 O (1), 2-C 4 H 3 S (2), 1-C 4 H 8 N (3)] are obtained by the reaction of the ruthenium chloride, Cp Ru(PPh 3 ) 2 CI, with the anions, h et-CS 2 . The X-ray structure of Cp Ru(PPh 3 )(κ 2 S, S-S 2 C-1- C 4 H 8 N) (3) is determined by single crystal X-ray diffraction.

Progress in doping of ruthenium silicide (Ru2Si3)

International Nuclear Information System (INIS)

Vining, C.B.; Allevato, C.E.

1992-01-01

This paper reports that ruthenium silicide (Ru 2 Si 3 ) is currently under development as a promising thermoelectric material suitable for space power applications. Key to realizing the potentially high figure of merit values of this material is the development of appropriate doping techniques. In this study, manganese and iridium have been identified as useful p- and n-type dopants, respectively. Resistivity values have been reduced by more than 3 orders of magnitude. Anomalous Hall effect results, however, complicate interpretation of some of the results and further effort is required to achieve optimum doping levels

Elimination of ionic interference effects in the atomic absorption spectrometric determination of ruthenium

International Nuclear Information System (INIS)

El-Defrawy, M.M.M.; Posta, J.; Beck, M.T.

1978-01-01

In connection with work on the catalytic effect of ruthenium complexes, new compounds were prepared. Atomic absorption spectrometry (a.a.s.) was to be used for their analysis. The standard methods could not be applied to the complexes studied, therefore the effect of cyanide ions for elimination of interfering effects has been studied, because of the great stability of cyanide complexes. (Auth.)

Three-dimensional ruthenium-doped TiO ₂ sea urchins for enhanced visible-light-responsive H ₂ production

Energy Technology Data Exchange (ETDEWEB)

Nguyen-Phan, Thuy-Duong; Luo, Si; Vovchok, Dimitriy; Llorca, Jordi; Sallis, Shawn; Kattel, Shyam; Xu, Wenqian; Piper, Louis F. J.; Polyansky, Dmitry E.; Senanayake, Sanjaya D.; Stacchiola, Dario J.; Rodriguez, José A.

2016-01-01

Three-dimensional (3D) monodispersed sea urchin-like Ru-doped rutile TiO2 hierarchical architectures composed of radially aligned, densely-packed TiO2 nanorods have been successfully synthesized via an acid-hydrothermal method at low temperature without the assistance of any structure-directing agent and post annealing treatment. The addition of a minuscule concentration of ruthenium dopants remarkably catalyze the formation of the 3D urchin structure and drive the enhanced photocatalytic H2 production under visible light irradiation, not possible on undoped and bulk rutile TiO2. Increasing ruthenium doping dosage not only increases the surface area up to 166 m2 g-1 but also induces enhanced photo response in the regime of visible and near infrared light. The doping introduces defect impurity levels, i.e. oxygen vacancy and under-coordinated Ti3+, significantly below the conduction band of TiO2, and ruthenium species act as electron donors/acceptors that accelerate the photogenetated hole and electron transfer and efficiently suppress the rapid charge recombination, therefore improving the visible-light-driven activity.

Flow injection chemiluminescent determination of N-nitrosodimethylamine using photogenerated tris(2,2'-bipyridyl) ruthenium (III)

International Nuclear Information System (INIS)

Perez-Ruiz, Tomas; Martinez-Lozano, Carmen; Tomas, Virginia; Martin, Jesus

2005-01-01

A flow injection configuration was developed and evaluated for the chemiluminescent determination of N-nitrosodimethylamine. The method is based on the on-line cleavage of the N-NO bond of the nitrosamine by irradiation with ultraviolet light. The dimethylamine generated was subsequently reacted with tris(2,2'-bipyridyl) ruthenium (III), which was generated through the on-line photo-oxidation of tris(2,2'-bipyridyl) ruthenium (II) with peroxydisulfate. After selecting the best operating parameters, the emitted light showed a linear relationship with the concentration of N-nitrosodimethylamine between 1.5 and 148 ng ml -1 , with a detection limit of 0.29 ng ml -1 . The repeatability was 1.6% expressed as relative standard deviation (n = 10) and the reproducibility, studied on five consecutive days, was 3.2%. The sample throughput was 50 injections per hour. The method was applied to studying the recoveries of N-nitrosodimethylamine in water and different cured meat products

A new electrochemical sensor containing a film of chitosan-supported ruthenium: detection and quantification of sildenafil citrate and acetaminophen

Energy Technology Data Exchange (ETDEWEB)

Delolo, Fabio Godoy; Rodrigues, Claudia; Silva, Monize Martins da; Batista, Alzir Azevedo, E-mail: fabiodelolo@hotmail.com, E-mail: daab@power.ufscar.br [Universidade Federal de Sao Carlos (UFSCar), SP (Brazil). Departamento de Quimica. Lab. de Estrutura e Reatividade de Compostos Inorganicos; Dinelli, Luis Rogerio [Universidade Federal de Uberlandia (UFU), Ituiutaba, MG (Brazil). Faculdade de Ciencias Integradas do Pontal; Delling, Felix Nicolai; Zukerman-Schpector, Julio [Universidade Federal de Sao Carlos (UFSCar), SP (Brazil). Departamento de Quimica. Lab. de Cristalografia Estereodinamica e Modelagem Molecular

2014-03-15

This work presents the construction of a novel electrochemical sensor for detection of organic analytes, using a glassy carbon electrode (GCE) modified with a chitosan-supported ruthenium film. The ruthenium-chitosan film was obtained starting from the mer-[RuCl{sub 3}(dppb)(H{sub 2}O)] complex as a [1,4-bis(diphenylphosphine)butane] (dppb) precursor, and chitosan (QT). The structure of the chitosan-supported ruthenium film on the surface of the glassy carbon electrode was characterized by UV-Vis spectroscopy, electron paramagnetic resonance (EPR), scanning electron microscopy (SEM), atomic force microscopy (AFM), powder X-ray diffraction (XRD) and atomic absorption spectroscopy (AAS) techniques. The glassy carbon electrode was modified with a film formed from the evaporation of 5 μL of a solution composed of 5 mg chitosan-supported ruthenium (RuQT) in 10 mL of 0.1 mol L{sup -1} acetic acid. The modified electrode was tested as a sensor for sildenafil citrate (Viagra® 50 mg) and acetaminophen (Tylenol®) detection. The technique utilized for these analyses was differential pulse voltammetry (DPV) in 0.1 mol L{sup -1} H{sub 2}SO{sub 4} (pH 1.0) and 0.1 mol L{sup -1} CH{sub 3}COOK (pH 6.5) as supporting electrolyte. All analyses were carried out during a month using the same electrode. The electrode was washed only with water in between the analyses, keeping it in the refrigerator when it was not in use. This electrode was stable during the period utilized showing no degradation and presenting a linear response over the evaluated concentration interval (1.25 × 10{sup -5} to 4.99 × 10{sup -4} mol L{sup -1}). (author)

Influence of environmental health in the cow-calf dyad system

Directory of Open Access Journals (Sweden)

Thayná Barcelos Fernandes

2012-12-01

Full Text Available Health factors influence the cow-calf dyad system in the postpartum period until the first suckling. The use of maternity paddock is a recommended management to facilitate the monitoring of parturient cows and calves. However, side effects occur due to environmental health conditions of maternity paddock that can affect the behaviour of the cow and result in the separation of calf from the mother, undermining sucking and the formation of the cow-calf dyad. To improve the understanding of this complex and dynamic system we built a conceptual model using the technique of causal loop diagram, Figure 1. By hypothesis, the environmental variables that act in maternity paddock influence the variable "Sources of pathogens in maternity". Those sources present a positive effect (in the same direction in the infection process of the calf and cow. Thus, a recommended practice is exposing the parturient cow to pathogens in maternity for sufficient period to stimulate their immune system and build disease resistance. That process contributes to improve the quality of colostrum that will be consumed by the calf during the first hours postpartum which has the function of increasing calf immunity, minimizing the occurrence of infections. In the model, sanitary environmental factors work in two Balance feedback loops (B1 and B2. The B1 cycle refers to the production of a healthy cow with a low level of infection by means of the variables: “Vaccine”, "Stimulation of cow immune system" and "Health resistance" with delay. The variable "Cow infection" has a negative influence (in the opposite direction in the "Maternal behaviour", thus the more infected the cow, the less investment will occur in maternal behaviour. The B2 cycle refers to the calf’s health condition, which is positively influenced by “Calf infection” which, in turn, has positive influence, contributing to the increase of "Calf diseases". The increase in “Calf diseases” generates an

Production of ruthenium aluminide by reaction sintering of Ru and Al powder mix

International Nuclear Information System (INIS)

Povarova, K.B.; Kazanskaya, N.K.; Drozdov, A.A.; Skachkov, O.A.; Levin, V.P.

2002-01-01

The physicochemical processes, taking place by the RuAl alloy formation from the ruthenium and aluminium powder mixture within the temperature range of 250-1400 deg C in the vacuum from 10 -2 up to 10 -5 mm mercury column are studied on the alloys of the Ru 50 Al 50 stoichiometric and Ru 52 Al 48 hyperstoichiometric composition. The Ru + Al → RuAl interaction with the exothermal effect begins in the solid phase at the temperatures below the aluminium t melt . The Ru 2 Al 3 , RuAl 2 and RuAl traces rich in aluminium are formed already at 600 deg C; at 1000-1400 deg C the RuAl becomes the basic phase; the precipitates of the ruthenium-based solid solution are additionally present in the hyperstoichiometric Ru 52 Al 48 alloy. The Ru 52 Al 48 crystalline lattice period increases with the growth of the caking temperature from 0.29906 (660 deg C) up to 0.22955 nm (1400 deg C). The Al 2 O 3 inclusions up to 1 μm in diameter are identified in the caked alloys in vacuum after the reaction caking [ru

Electrophoretic deposition (EPD) of hydrous ruthenium oxides with PTFE and their supercapacitor performances

International Nuclear Information System (INIS)

Jang, Jong H.; Machida, Kenji; Kim, Yuri; Naoi, Katsuhiko

2006-01-01

The effect of PTFE addition was investigated for the electrophoretic deposition (EPD) of hydrous ruthenium oxide electrodes. Mechanical stability of electrode layers, together with deposition yield, was enhanced by using hydrous ruthenium oxide/PTFE dispersions. High supercapacitor performance was obtained for the electrodes prepared with 2% PTFE and 10% water. When PTFE content was higher, the rate capability became poor with low electronic conductivity; higher water content than 10% resulted in non-uniform depositions with poor cycleability and power capability. When electrodes were heat treated at 200 deg. C for 10 h, the specific energy was as high as 17.6 Wh/kg based on single electrode (at 200 W/kg); while utilizable energy was lower with heat treatment time of 1 and 50 h, due to the high resistance and gradual crystallization, respectively. With PTFE addition and heat treatment at 200 deg. C for 10 h, the specific capacitance was increased by 31% (460 → 599 F/g at ca. 0.6 mg/cm 2 ) at 10 mV/s, and the deposition weight was increased up to 1.7 mg/cm 2 with initial capacitance of 350 F/g

Behavior of ruthenium, cesium and antimony in high temperature processes for waste conditioning

International Nuclear Information System (INIS)

Klein, M.; Weyers, C.; Goossens, W.R.A.

1985-01-01

The fission products and the actinides of high level radioactive liquid wastes can be immobilized by incorporation into a glass matrix prior to disposal. The behaviour of so-called semi-volatile products during the vitrification process has been studied by the C.E.N./S.C.K. in Mol since 1979 in the framework of a contract with DWK of Germany in support to the HAW technological program PAMELA. The experiments were performed on laboratory and semi-pilot scale using simulated LEWC solutions tagged with radioisotopes of three suspected volatile fission products, namely ruthenium, cesium and antimony. The releases of these semi-volatile compounds to the off-gases have been investigated for a liquid fed melter as a function of the operational conditions. The study of a wet purification system, comprising in series of a dust scrubber, a condensor, an ejector venturi and an NOsub(x) column, has shown that cesium appears to be the reference isotope for the volatile elements released from the melter. Ruthenium seems not to be a problem from the point of view of gas purification although local radiation problems caused by deposits on metal surfaces cannot be excluded. (Auth.)

The effect of annealing temperature on the optical properties of a ruthenium complex thin film

Energy Technology Data Exchange (ETDEWEB)

Ocakoglu, Kasim, E-mail: kasim.ocakoglu@mersin.edu.tr [Advanced Technology Research & Application Center, Mersin University, TR-33343, Yenisehir, Mersin (Turkey); Department of Energy Systems Engineering, Faculty of Technology, Mersin University, TR-33480 Mersin (Turkey); Okur, Salih, E-mail: salih.okur@ikc.edu.tr [Department of Materials Science and Engineering, Faculty of Engineering and Architecture, Izmir Katip Celebi University, Izmir (Turkey); Aydin, Hasan [Izmir Institute of Technology, Department of Material Science and Engineering, Gulbahce Campus, 35430, Urla, Izmir (Turkey); Emen, Fatih Mehmet [Faculty of Arts and Sciences, Department of Chemistry, Mehmet Akif Ersoy University, TR-15030 Burdur (Turkey)

2016-08-01

The stability of the optical parameters of a ruthenium polypyridyl complex (Ru-PC K314) film under varying annealing temperatures between 278 K and 673 K was investigated. The ruthenium polypyridyl complex thin film was prepared on a quartz substrate by drop casting technique. The transmission of the film was recorded by using Ultraviolet/Visible/Near Infrared spectrophotometer and the optical band gap energy of the as-deposited film was determined around 2.20 eV. The optical parameters such as refractive index, extinction coefficient, and dielectric constant of the film were determined and the annealing effect on these parameters was investigated. The results show that Ru PC K314 film is quite stable up to 595 K, and the rate of the optical band gap energy change was found to be 5.23 × 10{sup −5} eV/K. Furthermore, the thermal analysis studies were carried out in the range 298–673 K. The Differential Thermal Analysis/Thermal Gravimmetry/Differantial Thermal Gravimmetry curves show that the decomposition is incomplete in the temperature range 298–673 K. Ru-PC K314 is thermally stable up to 387 K. The decomposition starts at 387 K with elimination of functional groups such as CO{sub 2}, CO molecules and SO{sub 3}H group was eliminated between 614 K and 666 K. - Highlights: • Optical parameters of a ruthenium polypyridyl complex film under varying annealing temperatures • The film is quite stable up to 573 K. • The rate of change of optical energy gap was obtained as 5.23 × 10{sup −5} eV/K.

The impact of a pilot cooking intervention for parent-child dyads on the consumption of foods prepared away from home.

Science.gov (United States)

Robson, Shannon M; Stough, Cathleen Odar; Stark, Lori J

2016-04-01

This pilot study investigated the impact of a parent-child dyad cooking intervention on reducing eating dinner away from home. Eating away from home often results in consumption of energy-dense, nutrient-poor foods that can contribute to excess energy consumption in children. A pre-post design to evaluate a 10-week cooking intervention on reducing eating dinner away from home, energy intake, and improving diet quality was implemented. The intervention was delivered at an instructional kitchen on a university campus and assessments were completed at a children's academic medical center. Subjects included six parent-child dyads whom reported eating dinner away from home ≥3 times/week and in which the parent was overweight based on their body mass index (BMI) of ≥25 kg/m(2). Parents were a mean age of 34.7 (SD = 3.9) years, and children were a mean age of 8.7 (SD = 2.0) years. Two-thirds of parents self-identified themselves and their children as White. Results showed the proportion of dinners consumed by parent-child dyads away from home significantly decreased (F (1,161) = 16.1, p cooking between baseline and post-treatment. A cooking intervention that involves parent-child dyads and incorporates behavior management strategies and nutrition education may be an innovative obesity prevention intervention. Copyright © 2016 Elsevier Ltd. All rights reserved.

Bifunctional amine-tethered ruthenium(II) arene complexes form monofunctional adducts on DNA

Czech Academy of Sciences Publication Activity Database

Melchart, M.; Habtemariam, A.; Nováková, Olga; Moggach, S.A.; Fabbiani, F.P.A.; Parsons, S.; Brabec, Viktor; Sadler, P.J.

2007-01-01

Roč. 46, č. 21 (2007), s. 8950-8962 ISSN 0020-1669 R&D Projects: GA ČR(CZ) GA305/05/2030; GA ČR(CZ) GA203/06/1239; GA AV ČR(CZ) 1QS500040581; GA AV ČR(CZ) KAN200200651 Institutional research plan: CEZ:AV0Z50040507; CEZ:AV0Z50040702 Keywords : DNA * ruthenium * cancer Subject RIV: BO - Biophysics Impact factor: 4.123, year: 2007

Ruthenium-catalyzed cyclization of N-carbamoyl indolines with alkynes: an efficient route to pyrroloquinolinones.

Science.gov (United States)

Manoharan, Ramasamy; Jeganmohan, Masilamani

2015-09-21

A regioselective synthesis of substituted pyrroloquinolinones via a ruthenium-catalyzed oxidative cyclization of substituted N-carbamoyl indolines with alkynes is described. The cyclization reaction was compatible with various symmetrical and unsymmetrical alkynes including substituted propiolates. Later, we performed the aromatization of pyrroloquinolinones into indole derivatives in the presence of 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ).

Electronic Interplay between TTF and Extended-TCNQ Electrophores along a Ruthenium Bis(acetylide) Linker.

Science.gov (United States)

Vacher, Antoine; Auffray, Morgan; Barrière, Frédéric; Roisnel, Thierry; Lorcy, Dominique

2017-11-17

A bis(TTF-butadiynyl) ruthenium D-D'-D complex, with intramolecular electronic interplay between the three electron-donating electrophores, was easily converted through a cycloaddition-retroelectrocyclization with TCNQ into a D-A-D'-A-D pentad complex, which exhibits an intense intramolecular charge transfer together with an electronic interplay between the two acceptors along the conjugated organometallic bridge.

Ruthenium-catalyzed direct C3 alkylation of indoles with α,β-unsaturated ketones.

Science.gov (United States)

Li, Shuai-Shuai; Lin, Hui; Zhang, Xiao-Mei; Dong, Lin

2015-01-28

In this paper, a simple and highly efficient ruthenium-catalyzed direct C3 alkylation of indoles with various α,β-unsaturated ketones without chelation assistance has been developed. This novel C-H activation methodology exhibits a broad substrate scope such as different substituted indoles, pyrroles, and other azoles. Further synthetic applications of the alkylation products can lead to more attractive 3,4-fused tricyclic indoles.

Selective Aerobic Oxidation of 5-Hydroxymethylfurfural in Water Over Solid Ruthenium Hydroxide Catalysts with Magnesium-Based Supports

DEFF Research Database (Denmark)

Gorbanev, Yury; Kegnæs, Søren; Riisager, Anders

2011-01-01

Solid catalyst systems comprised of ruthenium hydroxide supported on magnesium-based carrier materials (spinel, magnesium oxide and hydrotalcite) were investigated for the selective, aqueous aerobic oxidation of the biomass-derived chemical 5-hydroxymethylfurfural into 2,5-furandicarboxylic acid...

Interpersonal Attraction in Dyads and Groups: Effects of the Hearts of the Beholder and the Beheld.

Science.gov (United States)

Malloy, Thomas E

2018-04-01

Dyadic interpersonal attraction (IA) was studied within groups of very highly acquainted family members, friends and co-workers. IA was determined by the perceiver (i.e., the heart of the beholder), the target (i.e., the heart of the beheld), and in specific dyads, by the unique combination of the two. The consistency of one's attraction to others and others' attraction to the person across groups were addressed using the key person design . Attraction to a person in one group was independent of attraction to that person in another, although people predicted that members of different groups were similarly attracted to them. A new model (ARRMA) was specified to simultaneously study assumed reciprocity, actual reciprocity, and metaperception accuracy of attraction (i.e., accurate predictions of others' attraction to oneself). Assumed reciprocity of IA was substantial at the individual and dyadic levels. Reciprocity of attraction at the individual level, a heretofore unconfirmed "plausible hypothesis" (Newcomb, 1979), was supported; dyadic reciprocity was weak. Meta-accuracy of IA was observed among individuals but was weak in dyads. Perceived interpersonal similarity predicted IA among individuals and in specific dyads. Considering dyadic attraction within and between groups, and the use of componential analysis permitted the specification of new IA phenomena and resolved a long standing theoretical problem regarding the reciprocity of attraction.

Interactions between perceived uncertainty types in service dyads

DEFF Research Database (Denmark)

Kreye, Melanie

2018-01-01

to avoid business failure. A conceptual framework of four uncertainty types is investigated: environmental, technological, organisational, and relational uncertainty. We present insights from four empirical cases of service dyads collected via multiple sources of evidence including 54 semi-structured...... interviews, observations, and secondary data. The cases show seven interaction paths with direct knock-on effects between two uncertainty types and indirect knock-on effects between three or four uncertainty types. The findings suggest a causal chain from environmental, technological, organisational......, to relational uncertainty. This research contributes to the servitization literature by (i) con-firming the existence of uncertainty types, (ii) providing an in-depth characterisation of technological uncertainty, and (iii) showing the interaction paths between four uncertainty types in the form of a causal...

Synthesis and Catalytic Hydrogen Transfer Reaction of Ruthenium(II) Complex

Energy Technology Data Exchange (ETDEWEB)

Son, Jung Ik; Kim, Aram; Noh, Hui Bog; Lee, Hyun Ju; Shim, Yoon Bo; Park, Kang Hyun [Pusan National University, Busan (Korea, Republic of)

2012-01-15

The ruthenium(II) complex [Ru(bpy){sub 2}-(PhenTPy)] was synthesized, and used for the transfer hydrogenation of ketones and the desired products were obtained in good yield. Based on the presented results, transition-metal complexes can be used as catalysts for a wide range of organic transformations. The relationship between the electro-reduction current density and temperature are being examined in this laboratory. Attempts to improve the catalytic activity and determine the transfer hydrogenation mechanism are currently in progress. The catalytic hydrogenation of a ketone is a basic and critical process for making many types of alcohols used as the final products and precursors in the pharmaceutical, agrochemical, flavor, fragrance, materials, and fine chemicals industries. The catalytic hydrogenation process developed by Noyori is a very attractive process. Formic acid and 2-propanol have been used extensively as hydrogenation sources. The advantage of using 2-propanol as a hydrogen source is that the only side product will be acetone, which can be removed easily during the workup process. Hydrogen transfer (HT) catalysis, which generates alcohols through the reduction of ketones, is an attractive protocol that is used widely. Ruthenium(II) complexes are the most useful catalysts for the hydrogen transfer (HT) of ketones. In this method, a highly active catalytic system employs a transition metal as a catalyst to synthesize alcohols, and is a replacement for the hydrogen-using hydrogenation process. The most active system is based on Ru, Rh and Ir, which includes a nitrogen ligand that facilitates the formation of a catalytically active hydride and phosphorus.

Synthesis and Catalytic Hydrogen Transfer Reaction of Ruthenium(II) Complex

International Nuclear Information System (INIS)

Son, Jung Ik; Kim, Aram; Noh, Hui Bog; Lee, Hyun Ju; Shim, Yoon Bo; Park, Kang Hyun

2012-01-01

The ruthenium(II) complex [Ru(bpy) 2 -(PhenTPy)] was synthesized, and used for the transfer hydrogenation of ketones and the desired products were obtained in good yield. Based on the presented results, transition-metal complexes can be used as catalysts for a wide range of organic transformations. The relationship between the electro-reduction current density and temperature are being examined in this laboratory. Attempts to improve the catalytic activity and determine the transfer hydrogenation mechanism are currently in progress. The catalytic hydrogenation of a ketone is a basic and critical process for making many types of alcohols used as the final products and precursors in the pharmaceutical, agrochemical, flavor, fragrance, materials, and fine chemicals industries. The catalytic hydrogenation process developed by Noyori is a very attractive process. Formic acid and 2-propanol have been used extensively as hydrogenation sources. The advantage of using 2-propanol as a hydrogen source is that the only side product will be acetone, which can be removed easily during the workup process. Hydrogen transfer (HT) catalysis, which generates alcohols through the reduction of ketones, is an attractive protocol that is used widely. Ruthenium(II) complexes are the most useful catalysts for the hydrogen transfer (HT) of ketones. In this method, a highly active catalytic system employs a transition metal as a catalyst to synthesize alcohols, and is a replacement for the hydrogen-using hydrogenation process. The most active system is based on Ru, Rh and Ir, which includes a nitrogen ligand that facilitates the formation of a catalytically active hydride and phosphorus

Determination of ruthenium in photographic emulsions - Development and comparison of different sample treatments and mass spectrometric methods

NARCIS (Netherlands)

Krystek, Petra; Heumann, Klaus G.

1999-01-01

Different sample treatment procedures were combined with inductively coupled plasma mass spectrometry (ICP-MS) and negative thermal ionisation mass spectrometry (NTI-MS) for the determination of ruthenium traces in photographic emulsions. Dissolution of the samples in concentrated ammonia solution

Ion implantation to improve mechanical and electrical properties of resistive materials based on ruthenium dioxide

International Nuclear Information System (INIS)

Byeli, A.V.; Shykh, S.K.; Beresina, V.P.

1996-01-01

This paper reports the influence of ion implantation, using different chemical species, on the surface micromorphology, wear resistance, coefficient of friction and electrical resistivity, and its variation during friction for resistive materials based on ruthenium dioxide. It is demonstrated that nitrogen and hydrogen ions are the most effective for modifying surface properties. (Author)

Effect of Support in Heterogeneous Ruthenium Catalysts Used for the Selective Aerobic Oxidation of HMF in Water

DEFF Research Database (Denmark)

Gorbanev, Yury; Kegnæs, Søren; Riisager, Anders

2011-01-01

Heterogeneous ruthenium-based catalysts were applied in the selective, aerobic oxidation of 5-hydroxymethylfurfural, a versatile biomass-derived chemical, to form 2,5-furandicarboxylic acid. The oxidation reactions were performed in water with dioxygen as the oxidant at different pressures without...

Characterisation and application of new carboxylic acid-functionalised ruthenium complexes as dye-sensitisers for solar cells

DEFF Research Database (Denmark)

Duprez, Virginie; Biancardo, Matteo; Krebs, Frederik C

2007-01-01

A series of ruthenium complexes with and without TiO2, anchoring carboxylic acid groups have been synthesised and characterised using nuclear magnetic resonance (NMR), UV-vis and luminescence. These complexes were adsorbed on thin films of the wide band-gap semiconductor anatase and were tested a...

Caprolactone-based bipyridine macroligands for novel ruthenium polypyridyl complexes for applications in dye-sensitized solar cells

NARCIS (Netherlands)

Marin, V.N.; Holder, E.; Hoogenboom, R.; Schubert, U.S.

2004-01-01

In an attempt to reduce electrolyte loss in solar cells, the use of sold or quasi-solid state electrolytes is advantageous. The authors synthesized a metal contg. polymer via two synthetic pathways. In the first, a bipyridine-bisphenanthroline ruthenium metal complex with a hydroxy functionality was

What Happens When Parents and Children Go Grocery Shopping? An Observational Study of Latino Dyads in Southern California, USA.

Science.gov (United States)

Calderon, Joanna; Ayala, Guadalupe X; Elder, John P; Belch, George E; Castro, Iana A; Weibel, Nadir; Pickrel, Julie

2017-02-01

The objective of this study was to observe parent-child interactions in tiendas, limited assortment food stores catering to Latinos in the United States, and to examine the extent to which child involvement influenced these interactions and their purchase outcomes. Two confederates, one posing as a tienda employee and one posing as a customer, observed the entire shopping trip of 100 Latino parent-child (mean age = 8 years) dyads and coded the following: number and type of parent- and child-initiated request interactions, types of purchase influence attempts used by children and how parents responded, and whether the product was purchased. Level of child involvement was examined as a potential influencing factor on purchasing. The observations were relatively short (mean duration of 10 minutes), reflecting the "quick trip" nature of the observed shopping trips. From the 100 parent-child dyads, 144 request interactions were observed, and among dyads with at least 1 request interaction during the shopping trip, the average number of request interactions per dyad was 2. Children initiated most of the request interactions by asking for a product or simply placing it in the basket; parents initiated 24% of the request interactions. Child involvement in shopping and checkout were associated with spending and purchase outcomes. These results indicate that children and parents influence each other during grocery shopping, and children who are more involved have greater influence over purchases. Furthermore, this study identified a number of targets for future family/parent and consumer food environment interventions.

A Smart Europium-Ruthenium Complex as Anticancer Prodrug: Controllable Drug Release and Real-Time Monitoring under Different Light Excitations.

Science.gov (United States)

Li, Hongguang; Xie, Chen; Lan, Rongfeng; Zha, Shuai; Chan, Chi-Fai; Wong, Wing-Yan; Ho, Ka-Lok; Chan, Brandon Dow; Luo, Yuxia; Zhang, Jing-Xiang; Law, Ga-Lai; Tai, William C S; Bünzli, Jean-Claude G; Wong, Ka-Leung

2017-11-09

A unique, dual-function, photoactivatable anticancer prodrug, RuEuL, has been tailored that features a ruthenium(II) complex linked to a cyclen-europium chelate via a π-conjugated bridge. Under irradiation at 488 nm, the dark-inactive prodrug undergoes photodissociation, releasing the DNA-damaging ruthenium species. Under evaluation-window irradiation (λ irr = one-photon 350 nm or two-photon 700 nm), the drug delivery process can be quantitatively monitored in real-time because of the long-lived red europium emission. Linear relationships between released drug concentration and ESI-MS or luminescence responses are established. Finally, the efficiency of the new prodrug is demonstrated both in vitro RuEuL anticancer prodrug over some existing ones and open the way for decisive improvements in multipurpose prodrugs.

环戊二烯基钌配合物催化的高选择性苯乙炔二聚反应%HIGHLY SELECTIVE CATALYTIC DIMERIZATION OF PHENYLACETYLENE BY CYCLOPENTADIENYL RUTHENIUM COMPLEXES

Institute of Scientific and Technical Information of China (English)

金军挺; 黄吉玲; 陶晓春; 钱延龙

1999-01-01

@@ Transition metal vinylidene complexes (M=C=CHR) have attracted a great deal of attention in recent years as a new type of organometallic intermediates that may have unusual reactivity[1]. Their reactivity has been explored and their application to organic synthesis is developed[2]. Recent reports on the ruthenium-vinylidene complexes[3]suggest that the reaction of ruthenium-vinylidene complexes with a base generates the coordinatively unsaturated ruthenium acetylide species, which are involved in a number of catalytic and stoichiometric reactions of alkynes. For example,the coordinatively unsaturated ruthenium acetylide species C5Me5Ru(PPh3)-C≡CPh,formed from the reaction of the vinylidene complex C5Me5Ru(PPh3) (Cl)=C=CHPh with a base was reactive toward a variety of small molecules and active in catalytic dimerization of terminal alkynes[4]. The dimerization of terminal alkyne is an effective method of forming enynes, but its synthetic application in organic synthesis has been limited dueto low selectivity for dimeric products[5]. In this communication, we report that three ruthenium complexes were used as catalysts for the highly selective dimerization of phenylacetylene.

Effects of a Cooperative Learning Program on the Elaborations of Students Working in Dyads

NARCIS (Netherlands)

Krol, K.; Janssen, J.J.H.M.; Veenman, S.A.M.; Linden, A.A.M. van der

2004-01-01

In this study, the effects of a school improvement program on cooperative learning (CL) with respect to the elaborations of 6th-grade students working in mixed-ability and mixed-sex dyads on 2 cooperative tasks were examined. A posttest-only design with a control group was used to investigate the

Global analysis of the high temperature infrared emission spectrum of (12)CH4 in the dyad (ν2/ν4) region.

Science.gov (United States)

Amyay, Badr; Louviot, Maud; Pirali, Olivier; Georges, Robert; Vander Auwera, Jean; Boudon, Vincent

2016-01-14

We report new assignments of vibration-rotation line positions of methane ((12)CH4) in the so-called dyad (ν2/ν4) region (1100-1500 cm(-1)), and the resulting update of the vibration-rotation effective model of methane, previously reported by Nikitin et al. [Phys. Chem. Chem. Phys. 15, 10071 (2013)], up to and including the tetradecad. High resolution (0.01 cm(-1)) emission spectra of methane have been recorded up to about 1400 K using the high-enthalpy source developed at Institut de Physique de Rennes associated with the Fourier transform spectrometer of the SOLEIL synchrotron facility (AILES beamline). Analysis of these spectra allowed extending rotational assignments in the well-known cold band (dyad-ground state (GS)) and related hot bands in the pentad-dyad system (3000 cm(-1)) up to Jmax = 30 and 29, respectively. In addition, 8512 new transitions belonging to the octad-pentad (up to J = 28) and tetradecad-octad (up to J = 21) hot band systems were successfully identified. As a result, the MeCaSDa database of methane was significantly improved. The line positions assigned in this work, together with the information available in the literature, were fitted using 1096 effective parameters with a dimensionless standard deviation σ = 2.09. The root mean square deviations dRMS are 3.60 × 10(-3) cm(-1) for dyad-GS cold band, 4.47 ×10(-3) cm(-1) for the pentad-dyad, 5.43 × 10(-3) cm(-1) for the octad-pentad, and 4.70 × 10(-3) cm(-1) for the tetradecad-octad hot bands. The resulting new line list will contribute to improve opacity and radiative transfer models for hot atmospheres, such as those of hot-Jupiter type exoplanets.

Electrochemical DNA biosensor for detection of porcine oligonucleotides using ruthenium(II) complex as intercalator label redox

Energy Technology Data Exchange (ETDEWEB)

Halid, Nurul Izni Abdullah; Hasbullah, Siti Aishah; Heng, Lee Yook; Karim, Nurul Huda Abd [School of Chemical Sciences and Food Technology, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor Darul Ehsan (Malaysia); Ahmad, Haslina; Harun, Siti Norain [Chemistry Department, Faculty of Science, Universiti Putra Malaysia, 43400, Serdang, Selangor (Malaysia)

2014-09-03

A DNA biosensor detection of oligonucleotides via the interactions of porcine DNA with redox active complex based on the electrochemical transduction is described. A ruthenium(II) complex, [Ru(bpy){sub 2}(PIP)]{sup 2+}, (bpy = 2,2′bipyridine, PIP = 2-phenylimidazo[4,5-f[[1,10-phenanthroline]) as DNA label has been synthesized and characterized by 1H NMR and mass spectra. The study was carried out by covalent bonding immobilization of porcine aminated DNA probes sequences on screen printed electrode (SPE) modified with succinimide-acrylic microspheres and [Ru(bpy){sub 2}(PIP)]{sup 2+} was used as electrochemical redox intercalator label to detect DNA hybridization event. Electrochemical detection was performed by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) over the potential range where the ruthenium (II) complex was active. The results indicate that the interaction of [Ru(bpy){sub 2}(PIP)]{sup 2+} with hybridization complementary DNA has higher response compared to single-stranded and mismatch complementary DNA.

Ruthenium-platinum bimetallic catalysts supported on silica: characterization and study of benzene hydrogenation and CO methanation

Energy Technology Data Exchange (ETDEWEB)

Chakrabarty, D.K.; Rao, K.M.; Sundararaman, N.; Chandavar, K.

1986-12-15

Ru-Pt/SiO/sub 2/ bimetallic catalysts with varying Ru:Pt ratio have been prepared and studied with the aim to establish if they contain coclusters or isolated ruthenium and platinum particles. X-ray diffraction studies show that individual crystallites of ruthenium and platinum are present and no coclusters are formed. Metal dispersion has been determined by hydrogen chemisorption and surface composition of the catalysts has been obtained from XPS. It was found that preoxidation of the catalysts prior to reduction is essential for good platinum dispersion. The experimental turnover number (TN) for benzene hydrogenation on the bimetallic catalysts agrees very well with that of the weighted average on the individual metal catalysts and this may be taken as a kinetic evidence for the absence of coclusters. Carbon monoxide methanation activity of the bimetallic catalysts is quite similar to that of the supported platinum catalyst. 6 refs., 6 figs., 2 tabs.

Hydrogenation of esters catalyzed by ruthenium PN3-Pincer complexes containing an aminophosphine arm

KAUST Repository

Chen, Tao

2014-08-11

Hydrogenation of esters under mild conditions was achieved using air-stable ruthenium PN3-pincer complexes containing an aminophosphine arm. High efficiency was achieved even in the presence of water. DFT studies suggest a bimolecular proton shuttle mechanism which allows H2 to be activated by the relatively stable catalyst with a reasonably low transition state barrier. © 2014 American Chemical Society.

Separation of the noble metals ruthenium and palladium from nitric acid solution of the nuclear fuel reprocessing containing complexing agents

International Nuclear Information System (INIS)

Ghafourian, H.

1989-06-01

Two extraction chromatographic techniques have been developed. N'N diethylthiourea (DETU), which forms complexes with ruthenium that can be retained on an AG50W-X2 ion exchanger, has proved to be a suitable reagent. The structures of these complexes were elucidated by electrophoresis, ion exchange and IR spectroscopy. Under the same conditions Pd forms an insoluble DETU-complex of the formula [Pd(DETU) 4 ] 2+ , which allows the separation of this metal quantitatively. With regard to the application of the developed technique for recovery of the mentioned noble metals from dissolver residues of the nuclear fuel reprocessing, comparative studies were carried out for accompanying fission product nuclides and actinides such as Mo, Tc, Zr, Ce, U and Pu. It was found out that no complex between diethylthiourea and the fission products zirconium, molybdenum and cerium and the actinides uranium, plutonium and americium were formed. Technetium, which was originally present as pertechnetate, is reduced to Tc(IV) and retained on the cation exchanger together with ruthenium. Ruthenium was eluted with 6 M HNO 3 . The efficiency of the developed process has been demonstrated with simulated solutions. The achieved decontamination factors ranged from 10 2 to 10 6 depending on the nuclide. (orig./RB) [de

Enhanced intersystem crossing via a high energy charge transfer state in a perylenediimide-perylenemonoimide dyad

NARCIS (Netherlands)

Veldman, D.; Chopin-Cado, S.M.A; Meskers, S.C.J.; Janssen, R.A.J.

2008-01-01

The electronic relaxation processes of a photoexcited linear perylenediimide-perylenemonoimide (PDI-PMI) acceptor-donor dyad were studied. PDI-PMI serves as a model compound for donor-acceptor systems in photovoltaic devices and has been designed to have a high-energy PDI--PMI + charge transfer (CT)

Ruthenium-modified MCM-41 mesoporous molecular sieve and Y zeolite catalysts for selective hydrogenation of cinnamaldehyde

Czech Academy of Sciences Publication Activity Database

Hájek, J.; Kumar, N.; Mäki-Arvela, P.; Salmi, T.; Murzin, D. Z.; Paseka, Ivo; Heikkilä, T.; Laine, E.; Laukkanen, P.; Väyrynen, J.

2003-01-01

Roč. 251, č. 2 (2003), s. 385-396 ISSN 0926-860X R&D Projects: GA ČR GA104/03/0409 Institutional research plan: CEZ:AV0Z4032918 Keywords : mesoporous molecular sieve * zeolites * ruthenium Subject RIV: CA - Inorganic Chemistry Impact factor: 2.825, year: 2003

Flow-injection chemiluminescent determination of estrogen benzoate using the tris(1,10-phenanthroline) ruthenium(II)-permanganate system.

Science.gov (United States)

Ma, Yan; Cao, Wei; Qiao, Shuang; Liu, Wenwen; Yang, Jinghe

2011-01-01

Chemiluminescence (CL) detection for the determination of estrogen benzoate, using the reaction of tris(1,10-phenanthroline)ruthenium(II)-Na(2)SO(3)-permanganate, is described. This method is based on the CL reaction of estrogen benzoate (EB) with acidic potassium permanganate and tris(1,10-phenanthroline)ruthenium(II). The CL intensity is greatly enhanced when Na(2)SO(3) is added. After optimization of the different experimental parameters, a calibration graph for estrogen benzoate is linear in the range 0.05-10 µg/mL. The 3 s limit of detection is 0.024 µg/mL and the relative standard deviation was 1.3% for 1.0 µg/mL estrogen benzoate (n = 11). This proposed method was successfully applied to commercial injection samples and emulsion cosmetics. The mechanism of CL reaction was also studied. Copyright © 2011 John Wiley & Sons, Ltd.

Tunability of photoswitchable ruthenium sulfoxide compounds on the basis of ligand substitution

Energy Technology Data Exchange (ETDEWEB)

Eicke, Sebastian; Dieckmann, Volker; Springfeld, Kristin; Imlau, Mirco [Deparment of Physics, University of Osnabrueck (Germany)

2010-07-01

Photoswitchable ruthenium sulfoxide compounds provide a light-induced linkage isomerization in combination with pronounced changes in characteristic optical properties. As representative of the ruthenium sulfoxide group the molecular compound [Ru(bpy){sub 2}(R-OSO)]{sup +} (OSO: 2-methylsulfinylbenzoate) can be tuned in its optical properties by the substitution of the photoswitchable ligands (R=Bn, BnCl, BnMe). These modified sulfoxides were studied in respect to their photochromic properties and kinetics of the generation and relaxation of the light-induced isomers. The kinetics were determined by pump-probe technique and show in each case two reversible thermal decay processes following Arrhenius law. The two photo-excited states offer lifetimes in the magnitude of {tau}{sub 1}{approx}10{sup 3} s and {tau}{sub 2}{approx}10{sup 4} s at room temperature with activation energies about E{sub A,I}=0.72 eV to 0.92 eV and E{sub A,II}=0.8 eV to 1.00 eV. Another respresentative of the photoswitchable sulfoxides is the [Ru(bpy){sub 2}(pySO)]{sup 2+} compound. This molecule is the first sulfoxide which allows for reversible switching between the ground and metastable states by light exposure. With this compound the sulfoxides are highly qualified for optical data storage on a molecular scale.

16 CFR 23.7 - Misuse of the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium,” and “osmium.”

Science.gov (United States)

2010-01-01

... 16 Commercial Practices 1 2010-01-01 2010-01-01 false Misuse of the words âplatinum,â âiridium,â... § 23.7 Misuse of the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium,” and “osmium.” (a) It is unfair or deceptive to use the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium...

On the Role of Physical Interaction on Performance of Object Manipulation by Dyads

Directory of Open Access Journals (Sweden)

Keivan Mojtahedi

2017-11-01

Full Text Available Human physical interactions can be intrapersonal, e.g., manipulating an object bimanually, or interpersonal, e.g., transporting an object with another person. In both cases, one or two agents are required to coordinate their limbs to attain the task goal. We investigated the physical coordination of two hands during an object-balancing task performed either bimanually by one agent or jointly by two agents. The task consisted of a series of static (holding and dynamic (moving phases, initiated by auditory cues. We found that task performance of dyads was not affected by different pairings of dominant and non-dominant hands. However, the spatial configuration of the two agents (side-by-side vs. face-to-face appears to play an important role, such that dyads performed better side-by-side than face-to-face. Furthermore, we demonstrated that only individuals with worse solo performance can benefit from interpersonal coordination through physical couplings, whereas the better individuals do not. The present work extends ongoing investigations on human-human physical interactions by providing new insights about factors that influence dyadic performance. Our findings could potentially impact several areas, including robotic-assisted therapies, sensorimotor learning and human performance augmentation.

Broadband Two-Photon Absorption Characteristics of Highly Photostable Fluorenyl-Dicyanoethylenylated [60]Fullerene Dyads

Directory of Open Access Journals (Sweden)

Seaho Jeon

2016-05-01

Full Text Available We synthesized four C60-(light-harvesting antenna dyads C60 (>CPAF-Cn (n = 4, 9, 12, or 18 1-Cn for the investigation of their broadband nonlinear absorption effect. Since we have previously demonstrated their high function as two-photon absorption (2PA materials at 1000 nm, a different 2PA wavelength of 780 nm was applied in the study. The combined data taken at two different wavelength ranges substantiated the broadband characteristics of 1-Cn. We proposed that the observed broadband absorptions may be attributed by a partial π-conjugation between the C60 > cage and CPAF-Cn moieties, via endinitrile tautomeric resonance, giving a resonance state with enhanced molecular conjugation. This transient state could increase its 2PA and excited-state absorption at 800 nm. In addition, a trend of concentration-dependent 2PA cross-section (σ2 and excited-state absorption magnitude was detected showing a higher σ value at a lower concentration that was correlated to increasing molecular separation with less aggregation for dyads C60(>CPAF-C18 and C60(>CPAF-C9, as better 2PA and excited-state absorbers.

Branded into submission: Brand attributes and hierarchisation behavior in same-sex and mixed-sex dyads

NARCIS (Netherlands)

Fennis, B.M.

2008-01-01

In 2 experiments, the role of brand attributes in the process of nonconscious hierarchization in dyadic interactions was examined. Experiment 1 showed that in same-sex dyads, brands that are associated with an agent and that are rated high on the brand personality dimension of competence (Aaker,

Exciplex-like emission from a closely-spaced, orthogonally-sited anthracenyl-boron dipyrromethene (Bodipy) molecular dyad.

Science.gov (United States)

Benniston, Andrew C; Harriman, Anthony; Whittle, Victoria L; Zelzer, Mischa; Harrington, Ross W; Clegg, William

2010-07-30

A molecular dyad, , has been prepared that incorporates a boron dipyrromethene (Bodipy) group functionalized at the meso position with an anthracenyl unit. Emission from the dyad contains contributions from both localized fluorescence from the Bodipy unit and exciplex-like emission associated with an intramolecular charge-transfer state. The peak position, intensity and lifetime of this exciplex emission are solvent dependent and the shift in the emission maximum shows a linear relationship to the solvent polarity function (Deltaf). The calculated dipole moment for the exciplex is 22.5 +/- 2.2 D. The radiative rate constant (k(RAD)) for exciplex emission decreases progressively with increasing solvent polarity. In this latter case, k(RAD) shows an obvious dependence on the energy gap between the exciplex state and the first-excited singlet state resident on the Bodipy unit. The emission characteristics for dissolved in perfluorooctane are used to characterize the refractive index and dielectric constant of the solvent.

Ruthenium(II)-catalyzed direct addition of indole/pyrrole C2-H bonds to alkynes.

Science.gov (United States)

Liang, Libo; Fu, Shaomin; Lin, Dongen; Zhang, Xiao-Qi; Deng, Yuanfu; Jiang, Huanfeng; Zeng, Wei

2014-10-17

A ruthenium-catalyzed C2-hydroindolation of alkynes has been achieved. This protocol provides a rapid and concise access to kinds of 2-alkenyl-substituted N-(2-pyridyl)indoles in which the pyridyl moiety can be easily removed to afford free (N-H) indoles under mild conditions. Various arenes and alkynes, including electron-deficient and electron-rich internal alkynes and terminal alkynes, allow for this transformation.

Ruthenium(II)-Catalyzed C-H Activation of Imidamides and Divergent Couplings with Diazo Compounds: Substrate-Controlled Synthesis of Indoles and 3H-Indoles.

Science.gov (United States)

Li, Yunyun; Qi, Zisong; Wang, He; Yang, Xifa; Li, Xingwei

2016-09-19

Indoles are an important structural motif that is commonly found in biologically active molecules. In this work, conditions for divergent couplings between imidamides and acceptor-acceptor diazo compounds were developed that afforded NH indoles and 3H-indoles under ruthenium catalysis. The coupling of α-diazoketoesters afforded NH indoles by cleavage of the C(N2 )-C(acyl) bond whereas α-diazomalonates gave 3H-indoles by C-N bond cleavage. This reaction constitutes the first intermolecular coupling of diazo substrates with arenes by ruthenium-catalyzed C-H activation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ruthenium-catalyzed reactions--a treasure trove of atom-economic transformations.

Science.gov (United States)

Trost, Barry M; Frederiksen, Mathias U; Rudd, Michael T

2005-10-21

The demand for new chemicals spanning the fields of health care to materials science combined with the pressure to produce these substances in an environmentally benign fashion pose great challenges to the synthetic chemical community. The maximization of synthetic efficiency by the conversion of simple building blocks into complex targets remains a fundamental goal. In this context, ruthenium complexes catalyze a number of non-metathesis conversions and allow the rapid assembly of complex molecules with high selectivity and atom economy. These complexes often exhibit unusual reactivity. Careful consideration of the mechanistic underpinnings of the transformations can lead to the design of new reactions and the discovery of new reactivity.

Investigation of Ruthenium Dissolution in Advanced Membrane Electrode Assemblies for Direct Methanol Based Fuel Cells Stacks

Science.gov (United States)

Valdez, T. I.; Firdosy, S.; Koel, B. E.; Narayanan, S. R.

2005-01-01

This viewgraph presentation gives a detailed review of the Direct Methanol Based Fuel Cell (DMFC) stack and investigates the Ruthenium that was found at the exit of the stack. The topics include: 1) Motivation; 2) Pathways for Cell Degradation; 3) Cell Duration Testing; 4) Duration Testing, MEA Analysis; and 5) Stack Degradation Analysis.

Long-range electron transfer in zinc-phthalocyanine-oligo(phenylene-ethynylene)-based donor-bridge-acceptor dyads.

Science.gov (United States)

Göransson, Erik; Boixel, Julien; Fortage, Jérôme; Jacquemin, Denis; Becker, Hans-Christian; Blart, Errol; Hammarström, Leif; Odobel, Fabrice

2012-11-05

In the context of long-range electron transfer for solar energy conversion, we present the synthesis, photophysical, and computational characterization of two new zinc(II) phthalocyanine oligophenylene-ethynylene based donor-bride-acceptor dyads: ZnPc-OPE-AuP(+) and ZnPc-OPE-C(60). A gold(III) porphyrin and a fullerene has been used as electron accepting moieties, and the results have been compared to a previously reported dyad with a tin(IV) dichloride porphyrin as the electron acceptor (Fortage et al. Chem. Commun. 2007, 4629). The results for ZnPc-OPE-AuP(+) indicate a remarkably strong electronic coupling over a distance of more than 3 nm. The electronic coupling is manifested in both the absorption spectrum and an ultrafast rate for photoinduced electron transfer (k(PET) = 1.0 × 10(12) s(-1)). The charge-shifted state in ZnPc-OPE-AuP(+) recombines with a relatively low rate (k(BET) = 1.0 × 10(9) s(-1)). In contrast, the rate for charge transfer in the other dyad, ZnPc-OPE-C(60), is relatively slow (k(PET) = 1.1 × 10(9) s(-1)), while the recombination is very fast (k(BET) ≈ 5 × 10(10) s(-1)). TD-DFT calculations support the hypothesis that the long-lived charge-shifted state of ZnPc-OPE-AuP(+) is due to relaxation of the reduced gold porphyrin from a porphyrin ring based reduction to a gold centered reduction. This is in contrast to the faster recombination in the tin(IV) porphyrin based system (k(BET) = 1.2 × 10(10) s(-1)), where the excess electron is instead delocalized over the porphyrin ring.

Synthesis, Characterization and Shape-Dependent Catalytic CO Oxidation Performance of Ruthenium Oxide Nanomaterials: Influence of Polymer Surfactant

Directory of Open Access Journals (Sweden)

Antony Ananth

2015-08-01

Full Text Available Ruthenium oxide nano-catalysts supported on mesoporous γ-Al2O3 have been prepared by co-precipitation method and tested for CO oxidation. The effect of polyethylene glycol (PEG on the properties of the catalyst was studied. Addition of the PEG surfactant acted as a stabilizer and induced a change in the morphology of ruthenium oxide from spherical nanoparticles to one-dimensional nanorods. Total CO conversion was measured as a function of morphology at 175 °C and 200 °C with 1.0 wt.% loading for PEG-stabilized and un-stabilized catalysts, respectively. Conversion routinely increased with temperature but in each case, the PEG-stabilized catalyst exhibited a notably higher catalytic activity as compared to the un-stabilized equivalent. It can be assumed that the increase in the activity is due to the changes in porosity, shape and dispersion of the catalyst engendered by the use of PEG.

Electrochemical Sensing of Casein Based on the Interaction between Its Phosphate Groups and a Ruthenium(III) Complex.

Science.gov (United States)

Inaba, Iku; Kuramitz, Hideki; Sugawara, Kazuharu

2016-01-01

A reaction to casein, along with β-lactoglobulin, is a main cause of milk allergies, and also is a useful indicator of protein in allergic analyses. In the present study, a simple casein sensor was developed based on the interaction between a phosphate group of casein and electroactive [Ru(NH3)6](3+). We evaluated the voltammetric behavior of a casein-[Ru(NH3)6](3+) complex using a glassy carbon electrode. When the ruthenium(III) complex was combined with the phosphate groups of casein, the structure of the casein was changed. Since the hydrophobicity of casein was increased due to the binding, the casein was adsorbed onto the electrode. Furthermore, we modified an electrode with a ruthenium(III) ions/collagen film. When the sensor was applied to the detection of the casein contained in milk, the values coincided with those indicated by the manufacturer. Accordingly, this electrode could be a powerful sensor for the determination of casein in several foods.

Acceptability and Feasibility Results of a Strength-Based Skills Training Program for Dementia Caregiving Dyads

Science.gov (United States)

Judge, Katherine S.; Yarry, Sarah J.; Orsulic-Jeras, Silvia

2010-01-01

Purpose: The current article provides an in-depth description of a dyadic intervention for individuals with dementia and their family caregivers. Using a strength-based approach, caregiving dyads received skills training across 5 key areas: (a) education regarding dementia and memory loss, (b) effective communication, (c) managing memory loss, (d)…

Observed Sensitivity during Family Interactions and Cumulative Risk: A Study of Multiple Dyads per Family

Science.gov (United States)

Browne, Dillon T.; Leckie, George; Prime, Heather; Perlman, Michal; Jenkins, Jennifer M.

2016-01-01

The present study sought to investigate the family, individual, and dyad-specific contributions to observed cognitive sensitivity during family interactions. Moreover, the influence of cumulative risk on sensitivity at the aforementioned levels of the family was examined. Mothers and 2 children per family were observed interacting in a round robin…

Photoinduced electron transfer and photocurrent in multicomponent organic molecular films containing oriented porphyrin-fullerene dyad

NARCIS (Netherlands)

Kaunisto, Kimmo; Vuorinen, Tommi; Vahasalo, Heidi; Chukharev, Vladimir; Tkachenko, Nikolai V.; Efimov, Alexander; Tolkki, Antti; Lehtivuori, Heli; Lemmetyinen, Helge

2008-01-01

Layers of poly(3-hexylthiophene), PHT, phenyl vinyl thiophene, PVT3, poly(p-phenylene-2,3′-bis(3,2′-diphenyl)-quinoxaline-7-7′- diyl), PPQ, and covalently linked porphyrin-fullerene donor-acceptor dyad, P-F, were deposited as various multilayer films, which then were used to study photoinduced

Volatilization and trapping of ruthenium during calcination of nitric acid solutions

International Nuclear Information System (INIS)

Klein, M.; Weyers, C.; Goossens, W.R.A.; Smet, M. de; Trine, J.

1983-01-01

Solid radioactive aerosols and semi-volatile fission products e.g. Ru, Cs, Sb are generated during high level liquid waste calcination and vitrification processes. The retention of Ruthenium was studied because of its strong tendency to form volatile compounds in oxidative media. Since RuO 4 was the suspected form for high temperature processes, the study was carried out on the behaviour of RuO 4 and its retention on adsorbants and catalysts for various gas compositions. The behaviour of volatilized Ru species obtained by calcination of nitrosyl Ru compounds was then compared with the RuO 4 case

Evaluation of Ruthenium Capture Methods for Tritium Pretreatment Off-Gas Streams

Energy Technology Data Exchange (ETDEWEB)

Spencer, Barry B. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Jubin, Robert Thomas [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Bruffey, Stephanie H. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Strachan, Denis M. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

2017-07-01

In the reprocessing of used nuclear fuel, radioactive elements are released into various plant off-gas streams. While much research and development has focused on the abatement of the volatile nuclides ³H, ¹⁴C, ⁸⁵Kr, and ¹²⁹I, the potential release of semivolatile isotopes that could also report to the off-gas streams in a reprocessing facility has been examined. Ruthenium (as ¹⁰⁶Ru) has been identified as one of the semivolatile nuclides requiring the greatest degree of abatement prior to discharging the plant off-gas to the environment.

A water-soluble and retrievable ruthenium-based probe for colorimetric recognition of Hg(II) and Cys.

Science.gov (United States)

Cui, Yali; Hao, Yuanqiang; Zhang, Yintang; Liu, Baoxia; Zhu, Xu; Qu, Peng; Li, Deliang; Xu, Maotian

2016-08-05

A new ruthenium-based complex 1 [(bis(4,4'-dimethylphosphonic-2,2'-bipyridine) dithiocyanato ruthenium (II))] was developed as a colorimetric probe for the detection of Hg(II) and Cys (Cysteine). The obtained compound 1 can give interconversional color changes upon the alternating addition of Hg(II) and Cys in 100% aqueous solution. The specific coordination between NCS groups with Hg(II) can lead to the formation of 1-Hg(2+) complex, which can induce a remarkable spectral changes of probe 1. Afterwards the formed 1-Hg(2+) complex can act as effective colorimetric sensor for Cys. Owing to the stronger binding affinity of sulfhydryl group to Hg(2+), Cys can extract Hg(2+) from 1-Hg(2+) complex resulting in the release of 1 and the revival of absorption profile of the probe 1. By introducing the hydrophilic phosphonic acid groups, the proposed probe exhibited excellent water solubility. The limits of detection (LODs) of the assay for Hg(2+) and Cys are calculated to be 15nM and 200nM, respectively. Copyright © 2016. Published by Elsevier B.V.

A nanoporous ruthenium oxide framework for amperometric sensing of glucose and potentiometric sensing of pH

International Nuclear Information System (INIS)

Shim, J.H.; Kang, M.; Lee, Y.; Lee, C.

2012-01-01

Nanoporous ruthenium oxide frameworks (L 2 -eRuO) were electrodeposited on gold substrates by repetitive potential cycling in solutions of ruthenium(III) ions in the presence of reverse neutral micelles. The L 2 -eRuO was characterized in terms of direct oxidation of glucose and potentiometric response to pH values. The surface structures and morphologies of the L 2 -eRuO were characterized by scanning electron microscopy, energy dispersive X-ray spectroscopy, Raman spectroscopy, and high-resolution transmission electron microscopy. Their surface area was estimated via underpotential deposition of copper. L 2-eRuO-modified electrodes showed a 17-fold higher sensitivity (40 μA mM -1 cm -2 towards glucose in 0-4 mM concentration in solution of pH 7.4) than a RuO electrode prepared in the absence of reverse micelles. Potential interferents such as ascorbic acid, 4-acetamidophenol, uric acid and dopamine displayed no effect. The new electrode also revealed improved potentiometric response to pH changes compared to a platinum electrode of the same type. (author)

A ruthenium polypyridyl intercalator stalls DNA replication forks, radiosensitizes human cancer cells and is enhanced by Chk1 inhibition

Science.gov (United States)

Gill, Martin R.; Harun, Siti Norain; Halder, Swagata; Boghozian, Ramon A.; Ramadan, Kristijan; Ahmad, Haslina; Vallis, Katherine A.

2016-08-01

Ruthenium(II) polypyridyl complexes can intercalate DNA with high affinity and prevent cell proliferation; however, the direct impact of ruthenium-based intercalation on cellular DNA replication remains unknown. Here we show the multi-intercalator [Ru(dppz)2(PIP)]2+ (dppz = dipyridophenazine, PIP = 2-(phenyl)imidazo[4,5-f][1,10]phenanthroline) immediately stalls replication fork progression in HeLa human cervical cancer cells. In response to this replication blockade, the DNA damage response (DDR) cell signalling network is activated, with checkpoint kinase 1 (Chk1) activation indicating prolonged replication-associated DNA damage, and cell proliferation is inhibited by G1-S cell-cycle arrest. Co-incubation with a Chk1 inhibitor achieves synergistic apoptosis in cancer cells, with a significant increase in phospho(Ser139) histone H2AX (γ-H2AX) levels and foci indicating increased conversion of stalled replication forks to double-strand breaks (DSBs). Normal human epithelial cells remain unaffected by this concurrent treatment. Furthermore, pre-treatment of HeLa cells with [Ru(dppz)2(PIP)]2+ before external beam ionising radiation results in a supra-additive decrease in cell survival accompanied by increased γ-H2AX expression, indicating the compound functions as a radiosensitizer. Together, these results indicate ruthenium-based intercalation can block replication fork progression and demonstrate how these DNA-binding agents may be combined with DDR inhibitors or ionising radiation to achieve more efficient cancer cell killing.

Alkynes as Allylmetal Equivalents in Redox-Triggered C–C Couplings to Primary Alcohols: (Z)-Homoallylic Alcohols via Ruthenium-Catalyzed Propargyl C–H Oxidative Addition

Science.gov (United States)

2015-01-01

The cationic ruthenium catalyst generated upon the acid–base reaction of H2Ru(CO)(PPh3)3 and 2,4,6-(2-Pr)3PhSO3H promotes the redox-triggered C–C coupling of 2-alkynes and primary alcohols to form (Z)-homoallylic alcohols with good to complete control of olefin geometry. Deuterium labeling studies, which reveal roughly equal isotopic compositions at the allylic and distal vinylic positions, along with other data, corroborate a catalytic mechanism involving ruthenium(0)-mediated allene–aldehyde oxidative coupling to form a transient oxaruthenacycle, an event that ultimately defines (Z)-olefin stereochemistry. PMID:25075434

The influence of a new fabrication procedure on the catalytic activity of ruthenium-selenium catalysts

International Nuclear Information System (INIS)

Cheng, H.; Yuan, W.; Scott, K.

2006-01-01

A new procedure has been introduced to enhance catalytic activity of ruthenium-selenium electro-catalysts for oxygen reduction, in which materials are treated under hydrogen atmosphere at elevated temperatures. The characterisation using scanning electron microscopy, energy dispersive spectroscopy or energy dispersive X-ray spectroscopy exhibited that the treatment at 400 deg. C made catalysts denser while their porous nature remained, led to a good degree of crystallinity and an optimum Se:Ru ratio. The half cell test confirms feasibility of the new procedure; the catalyst treated at 400 deg. C gave the highest reduction current (55.9 mA cm -2 at -0.4 V) and a low methanol oxidation effect coefficient (3.8%). The direct methanol fuel cell with the RuSe 400 deg. C cathode catalyst (2 mg RuSe cm -2 ) generated a power density of 33.8 mW cm -2 using 2 M methanol and 2 bar oxygen at 90 deg. C. The new procedure produced the catalysts with low decay rates. The best sample was compared to the Pt and to the reported ruthenium-selenium catalyst. Possible reasons for the observations are discussed

Synthesis, characterization and dielectric properties of polynorbornadiene–clay nanocomposites by ROMP using intercalated Ruthenium catalyst

International Nuclear Information System (INIS)

Yalçınkaya, Esra Evrim; Balcan, Mehmet; Güler, Çetin

2013-01-01

Polynorbornadiene clay nanocomposites were prepared for the first time by the ring opening metathesis polymerization (ROMP) using modified montmorillonite and polynorbornadiene the latter of which is used commonly in electric–electronic industry. The Na–MMT clay was modified by a quaternary ammonium salt containing Ruthenium complex as a suitable catalyst and intercalant as well. The norbornadiene monomers were polymerized within the modified montmorillonite layers by in-situ polymerization method in different clay loading degrees. Intercalation ability of the Ru catalyst and partially exfoliated nanocomposite structure were proved by powder X-ray Diffraction (XRD) Spectroscopy and Transmission Electron Microscopy (TEM) methods. The nanocomposite materials with high thermal degradation temperature and low dielectric constant compared to the pure polynorbornadiene were obtained. The dielectric constants decreased with the increase of the clay content. - Highlights: • Polynorbornadiene–clay nanocomposites were prepared for the first time. • Ruthenium complex was assigned as both suitable catalyst and intercalant. • The norbornadiene was polymerized by in-situ polymerization method. • Exfoliation/intercalation structures were found to be related with loading degree. • PNBD–MMT nanocomposites had a higher thermal degradation temperature and lower dielectric constant

Similarities amid the difference: caregiving burden and adaptation outcomes in dyads of parents and their children with and without cerebral palsy.

Science.gov (United States)

Carona, C; Crespo, C; Canavarro, M C

2013-03-01

This study had two main objectives: first, to examine the direct and indirect effects, via social support, of caregiving burden on the adaptation outcomes of children/adolescents with cerebral palsy and their parents; and second, to assess the invariance of such models in clinical vs. healthy subsamples. Participants were 210 dyads of children/adolescents and one of their parents (total N=420), divided in 93 dyads of children/adolescents with cerebral palsy and 117 dyads of children/adolescents with no medical diagnosis. Data on caregiving burden, social support and adaptation outcomes were obtained through self-report questionnaires. Caregiving burden was linked to parents and their children's psychological maladjustment and quality of life both directly (except for children's quality of life) and indirectly through social support. Findings were invariant across clinical and healthy subsamples. Caregiving burden may influence adaptation outcomes of children/adolescents with CP and their parents both directly and via their social support perceptions. These patterns are similar to those observed in typically developing children/adolescents. Copyright © 2012 Elsevier Ltd. All rights reserved.

Intermolecular Dehydrative Coupling Reaction of Arylketones with Cyclic Alkenes Catalyzed by a Well-Defined Cationic Ruthenium-Hydride Complex: A Novel Ketone Olefination Method via Vinyl C–H Bond Activation

Science.gov (United States)

Yi, Chae S.; Lee, Do W.

2010-01-01

Summary The cationic ruthenium-hydride complex [(η6-C6H6)(PCy3)(CO)RuH]+BF4− was found to be a highly effective catalyst for the intermolecular olefination reaction of arylketones with cycloalkenes. The preliminary mechanistic analysis revealed that electrophilic ruthenium-vinyl complex is the key species for mediating both vinyl C–H bond activation and the dehydrative olefination steps of the coupling reaction. PMID:20567607

Study of the emission oxidative reactions of ruthenium (II) complex by cationic compounds in anionic micelles

International Nuclear Information System (INIS)

Bonilha, J.B.S.

1985-01-01

The oxidative quenching of the emission of the tetraanionic complex tris (4,4' dicarboxylate - 2,2' - bipyridine ruthenium (II) in aqueous solution, by both organic and inorganic compounds in presence of anionic detergents, above and below the critical micelle concentration is studied. The organic cations, the inorganic ion and detergents used are shown. (M.J.C.) [pt

Reactivity studies of eta sup (6)-p-cymene ruthenium(II) carboxylato complexes towards azide some neutral ligands

Digital Repository Service at National Institute of Oceanography (India)

Singh, K.S.; Kollipara, M.R.

sub (2)O sub (4)(7) or C sub (2)CH sub (2)O sub (4)(10)] have been prepared by the reaction of [(p-cymene)RuCl sub (2)]sub (2) with the corresponding sodium salts of the carboxylic acids. Treatment of (eta sup (6)-p-cymene) ruthenium(II) carboxylato...

Plasma-assisted synthesis of monodispersed and robust Ruthenium ultrafine nanocatalysts for organosilane oxidation and oxygen evolution reactions

NARCIS (Netherlands)

Gnanakumar, E.S.; Ng, W.; Filiz, B.C.; Rothenberg, G.; Wang, S.; Xu, H.; Pastor-Pérez, L.; Pastor-Blas, M.M.; Sepúlveda-Escribano, A.; Yan, N.; Shiju, N.R.

2017-01-01

We report a facile and general approach for preparing ultrafine ruthenium nanocatalysts by using a plasma-assisted synthesis at <100 °C. The resulting Ru nanoparticles are monodispersed (typical size 2 nm) and remain that way upon loading onto carbon and TiO2 supports. This gives robust catalysts

Modulation of ICT probability in bi(polyarene)-based O-BODIPYs: towards the development of low-cost bright arene-BODIPY dyads.

Science.gov (United States)

Gartzia-Rivero, Leire; Sánchez-Carnerero, Esther M; Jiménez, Josue; Bañuelos, Jorge; Moreno, Florencio; Maroto, Beatriz L; López-Arbeloa, Iñigo; de la Moya, Santiago

2017-09-12

We report the synthesis, and spectroscopic and electrochemical properties of a selected library of novel spiranic O-BODIPYs bearing a phenol-based bi(polyarene) unit tethered to the boron center through oxygen atoms. These dyes constitute an interesting family of arene-BODIPY dyads useful for the development of photonic applications due to their synthetic accessibility and tunable photonic properties. It is demonstrated that the electron-donor capability of the involved arene moiety switches on a non-emissive intramolecular charge transfer (ICT) state, which restricts the fluorescence efficiency of the dyad. Interestingly, the influence of this non-radiative deactivation channel can be efficiently modulated by the substitution pattern, either at the dipyrrin ligand or at the polyarene moiety. Thus, dyads featuring electron-rich dipyrrin and electron-poor polyarene show lower or almost negligible ICT probability, and hence display bright fluorescence upon dual excitation at far-away spectral regions. This synthetic approach has allowed the easy development of low-cost efficient ultraviolet-absorbing visible-emitting cassettes by selecting properly the substitution pattern of the involved key units, dipyrrin and bi(polyarene), to modulate not only absorption and emission wavelengths, but also fluorescence efficiencies.

Cyanuric acid hydrolase from Azorhizobium caulinodans ORS 571: crystal structure and insights into a new class of Ser-Lys dyad proteins.

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Seunghee Cho

Full Text Available Cyanuric acid hydrolase (CAH catalyzes the hydrolytic ring-opening of cyanuric acid (2,4,6-trihydroxy-1,3,5-triazine, an intermediate in s-triazine bacterial degradation and a by-product from disinfection with trichloroisocyanuric acid. In the present study, an X-ray crystal structure of the CAH-barbituric acid inhibitor complex from Azorhizobium caulinodans ORS 571 has been determined at 2.7 Å resolution. The CAH protein fold consists of three structurally homologous domains forming a β-barrel-like structure with external α-helices that result in a three-fold symmetry, a dominant feature of the structure and active site that mirrors the three-fold symmetrical shape of the substrate cyanuric acid. The active site structure of CAH is similar to that of the recently determined AtzD with three pairs of active site Ser-Lys dyads. In order to determine the role of each Ser-Lys dyad in catalysis, a mutational study using a highly sensitive, enzyme-coupled assay was conducted. The 10⁹-fold loss of activity by the S226A mutant was at least ten times lower than that of the S79A and S333A mutants. In addition, bioinformatics analysis revealed the Ser226/Lys156 dyad as the only absolutely conserved dyad in the CAH/barbiturase family. These data suggest that Lys156 activates the Ser226 nucleophile which can then attack the substrate carbonyl. Our combination of structural, mutational, and bioinformatics analyses differentiates this study and provides experimental data for mechanistic insights into this unique protein family.

Mediation in dyadic data at the level of the dyads: a Structural Equation Modeling approach.

Science.gov (United States)

Ledermann, Thomas; Macho, Siegfried

2009-10-01

An extended version of the Common Fate Model (CFM) is presented to estimate and test mediation in dyadic data. The model can be used for distinguishable dyad members (e.g., heterosexual couples) or indistinguishable dyad members (e.g., homosexual couples) if (a) the variables measure characteristics of the dyadic relationship or shared external influences that affect both partners; if (b) the causal associations between the variables should be analyzed at the dyadic level; and if (c) the measured variables are reliable indicators of the latent variables. To assess mediation using Structural Equation Modeling, a general three-step procedure is suggested. The first is a selection of a good fitting model, the second a test of the direct effects, and the third a test of the mediating effect by means of bootstrapping. The application of the model along with the procedure for assessing mediation is illustrated using data from 184 couples on marital problems, communication, and marital quality. Differences with the Actor-Partner Interdependence Model and the analysis of longitudinal mediation by using the CFM are discussed.

Estimating time-varying RSA to examine psychophysiological linkage of marital dyads.

Science.gov (United States)

Gates, Kathleen M; Gatzke-Kopp, Lisa M; Sandsten, Maria; Blandon, Alysia Y

2015-08-01

One of the primary tenets of polyvagal theory dictates that parasympathetic influence on heart rate, often estimated by respiratory sinus arrhythmia (RSA), shifts rapidly in response to changing environmental demands. The current standard analytic approach of aggregating RSA estimates across time to arrive at one value fails to capture this dynamic property within individuals. By utilizing recent methodological developments that enable precise RSA estimates at smaller time intervals, we demonstrate the utility of computing time-varying RSA for assessing psychophysiological linkage (or synchrony) in husband-wife dyads using time-locked data collected in a naturalistic setting. © 2015 Society for Psychophysiological Research.

Catalytic hydroprocessing of lignin β-O-4 ether bond model compound phenethyl phenyl ether over ruthenium catalysts

NARCIS (Netherlands)

Gomez-Monedero, B.; Faria, J.; Bimbela, F.; Ruiz, M.P.

2017-01-01

The catalytic hydroprocessing of phenethyl phenyl ether (PPE), a model compound of one of the most significant ether linkages within lignin structure, β-O-4, has been studied. Reactions were carried out using two ruthenium-based catalysts, supported on different materials: 3.8 wt.% Ru/C and 3.9 wt.%

Diagnostic electrocardiographic dyad criteria of emphysema in left ventricular hypertrophy

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Lanjewar SS

2013-11-01

Full Text Available Swapnil S Lanjewar,1 Lovely Chhabra,1 Vinod K Chaubey,1 Saurabh Joshi,1 Ganesh Kulkarni,1 Chandrasekhar Kothagundla,1 Sudesh Kaul,1 David H Spodick21Department of Internal Medicine, 2Department of Cardiovascular Medicine, Saint Vincent Hospital, University of Massachusetts Medical School, Worcester, MA, USABackground: The electrocardiographic diagnostic dyad of emphysema, namely a combination of the frontal vertical P-vector and a narrow QRS duration, can serve as a quasidiagnostic marker for emphysema, with specificity close to 100%. We postulated that the presence of left ventricular hypertrophy in emphysema may affect the sensitivity of this electrocardiographic criterion given that left ventricular hypertrophy generates prominent left ventricular forces and may increase the QRS duration.Methods: We reviewed the electrocardiograms and echocardiograms for 73 patients with emphysema. The patients were divided into two groups based on the presence or absence of echocardiographic evidence of left ventricular hypertrophy. The P-vector, QRS duration, and forced expiratory volume in one second (FEV1 were computed and compared between the two subgroups.Results: There was no statistically significant difference in qualitative lung function (FEV1 between the subgroups. There was no statistically significant difference in mean P-vector between the subgroups. The mean QRS duration was significantly longer in patients with left ventricular hypertrophy as compared with those without left ventricular hypertrophy.Conclusion: The presence of left ventricular hypertrophy may not affect the sensitivity of the P-vector verticalization when used as a lone criterion for diagnosing emphysema. However, the presence of left ventricular hypertrophy may significantly reduce the sensitivity of the electrocardiographic diagnostic dyad in emphysema, as it causes a widening of the QRS duration.Keywords: emphysema, electrocardiogram, left ventricular hypertrophy, chronic

The Biological Side of Water-Soluble Arene Ruthenium Assemblies

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Bruno Therrien

2014-01-01

Full Text Available This review article covers the synthetic strategies, structural aspects, and host-guest properties of ruthenium metalla-assemblies, with a special focus on their use as drug delivery vectors. The two-dimensional metalla-rectangles show interesting host-guest possibilities but seem less appropriate for being used as drug carriers. On the other hand, metalla-prisms allow encapsulation and possible targeted release of bioactive molecules and consequently show some potential as drug delivery vectors. The reactivity of these metalla-prisms can be fine-tuned to allow a fine control of the guest’s release. The larger metalla-cubes can be used to stabilize the formation of G-quadruplex DNA and can be used to encapsulate and release photoactive molecules such as porphins. These metalla-assemblies demonstrate great prospective in photodynamic therapy.

A trouble shared is a trouble halved: social context and status affect pain in mouse dyads.

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Laura Gioiosa

Full Text Available In mice behavioral response to pain is modulated by social status. Recently, social context also has been shown to affect pain sensitivity. In our study, we aimed to investigate the effects of interaction between status and social context in dyads of outbred CD-1 male mice in which the dominance/submission relationship was stable. Mice were assessed for pain response in a formalin (1% concentration test either alone (individually tested-IT, or in pairs of dominant and subordinate mice. In the latter condition, they could be either both injected (BI or only one injected (OI with formalin. We observed a remarkable influence of social context on behavioral response to painful stimuli regardless of the social status of the mice. In the absence of differences between OI and IT conditions, BI mice exhibited half as much Paw-licking behavior than OI group. As expected, subordinates were hypoalgesic in response to the early phase of the formalin effects compared to dominants. Clear cut-differences in coping strategies of dominants and subordinates appeared. The former were more active, whereas the latter were more passive. Finally, analysis of behavior of the non-injected subjects (the observers in the OI dyads revealed that dominant observers were more often involved in Self-grooming behavior upon observation of their subordinate partner in pain. This was not the case for subordinate mice observing the pain response of their dominant partner. In contrast, subordinate observers Stared at the dominant significantly more frequently compared to observer dominants in other dyads. The observation of a cagemate in pain significantly affected the observer's behavior. Additionally, the quality of observer's response was also modulated by the dominance/submission relationship.

Effects of Self-esteem, Optimism, and Perceived Control on Depressive Symptoms in Stroke Survivor-Spouse Dyads.

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Chung, Misook L; Bakas, Tamilyn; Plue, Laura D; Williams, Linda S

2016-01-01

Depressive symptoms are common in stroke survivors and their family caregivers. Given the interdependent relationship between the members of dyads in poststroke management, improving depressive symptoms in dyads may depend on their partner's characteristics. Self-esteem, optimism, and perceived control, all known to be associated with depressive symptoms in an individual, may also contribute to their partner's depressive symptoms. The purpose of this study is to examine actor and partner effects of self-esteem, optimism, and perceived control on depression in stroke survivors and their spousal caregivers. A total of 112 ischemic stroke survivors (78% white, 34% women; mean age, 62.5 ± 12.3 years) and their spouses (mean age, 60.6 ± 12.9 years) completed surveys in which depressive symptoms, self-esteem, optimism, and perceived control were assessed using the Patient Health Questionnaire, the Rosenberg Self-esteem Scale, the Revised Life Orientation Test, and the Sense of Control Scale. Multilevel modeling, actor-partner interdependence model regression was used to determine influences on depressive symptoms within the dyad. Individuals with lower self-esteem, optimism, and perceived control had higher levels of depressive symptoms. Stroke survivors whose spouses had lower levels of self-esteem (B = -0.338, P self-esteem (B = -0.047, P = .036) also had higher levels of depressive symptoms. We found significant partner effects of self-esteem on depression for both members and partner effect of optimism on patient's depressive symptoms. These findings suggest that further research is needed to determine if dyadic interventions may help to improve self-esteem, optimism, and depressive symptoms in both patients and their caregivers.

Study of physico-chemical release of uranium and plutonium oxides during the combustion of polycarbonate and of ruthenium during the combustion of solvents used in the reprocessing of nuclear fuel; Etude de la mise en suspension physico-chimique des oxydes de plutonium et d'uranium lors de la combustion de polycarbonate et de ruthenium lors de la combustion des solvants de retraitement du combustible irradie

Energy Technology Data Exchange (ETDEWEB)

Bouilloux, L

1998-07-01

The level of consequences concerning a fire in a nuclear facility is in part estimated by the quantities and the physico-chemical forms of radioactive compounds that may be emitted out of the facility. It is therefore necessary to study the contaminant release from the fire. Because of the multiplicity of the scenarios, two research subjects were retained. The first one concerns the study of the uranium or plutonium oxides chemical release during the combustion of the polycarbonate glove box sides. The second one is about the physico chemical characterisation of the ruthenium release during the combustion of an organic solvent mixture (tributyl phosphate-dodecane) used for the nuclear fuel reprocessing. Concerning the two research subjects, the chemical release, i.e. means the generation of contaminant compounds gaseous in the fire, was modelled using thermodynamical simulations. Experiments were done in order to determine the ruthenium release factor during solvent combustion. A cone calorimeter was used for small scale experiments. These results were then validated by large scale tests under conditions close to the industrial process. Thermodynamical simulations, for the two scenarios studied. Furthermore, the experiments on solvent combustion allowed the determination of a suitable ruthenium release factor. Finally, the mechanism responsible of the ruthenium release has been found. (author)

Synthesis and electrochemical performance of ruthenium oxide-coated carbon nanofibers as anode materials for lithium secondary batteries

Energy Technology Data Exchange (ETDEWEB)

Hyun, Yura; Choi, Jin-Yeong [Department of Chemistry, Keimyung University (Korea, Republic of); Park, Heai-Ku [Department of Chemical Engineering, Keimyung University (Korea, Republic of); Lee, Chang-Seop, E-mail: surfkm@kmu.ac.kr [Department of Chemistry, Keimyung University (Korea, Republic of)

2016-12-01

Highlights: • Ruthenium oxide (RuO{sub 2}) coated carbon nanofibers (CNFs) on Ni foam were synthesized by chemical vapor deposition method and applied as anode materials of Li secondary batteries. • When RuO{sub 2}/CNFs/Ni foam was used as the anode material, initial capacity was improved from 276 mAh/g to 494 mAh/g with retention rate of 47.4% after 30 cycles. - Abstract: In this study, ruthenium oxide (RuO{sub 2}) coated carbon nanofibers (CNFs) were synthesized and applied as anode materials of Li secondary batteries. The CNFs were grown on Ni foam via chemical vapor deposition (CVD) method after CNFs/Ni foam was put into the 0.01 M RuCl{sub 3} solution. The ruthenium oxide-coated CNFs/Ni foam was dried in a dryer at 80 °C. The morphologies, compositions, and crystal quality of RuO{sub 2}/CNFs/Ni foam were characterized by SEM, EDS, XRD, Raman spectroscopy, and XPS. The electrochemical characteristics of RuO{sub 2}/CNFs/Ni foam as anode of Li secondary batteries were investigated using three-electrode cell. The RuO{sub 2}/CNFs/Ni foam was directly employed as a working electrode without any binder, and lithium foil was used as the counter and reference electrodes. LiClO{sub 4} (1 M) was employed as electrolyte and dissolved in a mixture of propylene carbonate (PC): ethylene carbonate (EC) in a 1:1 volume ratio. The galvanostatic charge/discharge cycling and cyclic voltammetry measurements were carried out at room temperature by using a battery tester. In particular, synthesized RuO{sub 2}/CNFs/Ni foam showed the highest retention rate (47.4%). The initial capacity (494 mAh/g) was reduced to 234 mAh/g after 30 cycles.

Synthesis and electrochemical performance of ruthenium oxide-coated carbon nanofibers as anode materials for lithium secondary batteries

International Nuclear Information System (INIS)

Hyun, Yura; Choi, Jin-Yeong; Park, Heai-Ku; Lee, Chang-Seop

2016-01-01

Highlights: • Ruthenium oxide (RuO_2) coated carbon nanofibers (CNFs) on Ni foam were synthesized by chemical vapor deposition method and applied as anode materials of Li secondary batteries. • When RuO_2/CNFs/Ni foam was used as the anode material, initial capacity was improved from 276 mAh/g to 494 mAh/g with retention rate of 47.4% after 30 cycles. - Abstract: In this study, ruthenium oxide (RuO_2) coated carbon nanofibers (CNFs) were synthesized and applied as anode materials of Li secondary batteries. The CNFs were grown on Ni foam via chemical vapor deposition (CVD) method after CNFs/Ni foam was put into the 0.01 M RuCl_3 solution. The ruthenium oxide-coated CNFs/Ni foam was dried in a dryer at 80 °C. The morphologies, compositions, and crystal quality of RuO_2/CNFs/Ni foam were characterized by SEM, EDS, XRD, Raman spectroscopy, and XPS. The electrochemical characteristics of RuO_2/CNFs/Ni foam as anode of Li secondary batteries were investigated using three-electrode cell. The RuO_2/CNFs/Ni foam was directly employed as a working electrode without any binder, and lithium foil was used as the counter and reference electrodes. LiClO_4 (1 M) was employed as electrolyte and dissolved in a mixture of propylene carbonate (PC): ethylene carbonate (EC) in a 1:1 volume ratio. The galvanostatic charge/discharge cycling and cyclic voltammetry measurements were carried out at room temperature by using a battery tester. In particular, synthesized RuO_2/CNFs/Ni foam showed the highest retention rate (47.4%). The initial capacity (494 mAh/g) was reduced to 234 mAh/g after 30 cycles.

A feasible kinetic model for the hydrogen oxidation on ruthenium electrodes

International Nuclear Information System (INIS)

Rau, M.S.; Gennero de Chialvo, M.R.; Chialvo, A.C.

2010-01-01

The hydrogen oxidation reaction (hor) was studied on a polycrystalline ruthenium electrode in H 2 SO 4 solution at different rotation rates (ω). The experimental polarization curves recorded on steady state show the existence of a maximum current with a non-linear dependence of the current density on ω 1/2 . On the basis of the Tafel-Heyrovsky-Volmer kinetic mechanism, coupled with a process of inhibition of active sites by the reversible electroadsorption of hydroxyl species, it was possible to appropriately describe the origin of the maximum current. The corresponding set of kinetic parameters was also calculated from the correlation of the experimental results with the proposed kinetic model.

Multivariate Models of Parent-Late Adolescent Gender Dyads: The Importance of Parenting Processes in Predicting Adjustment

Science.gov (United States)

McKinney, Cliff; Renk, Kimberly

2008-01-01

Although parent-adolescent interactions have been examined, relevant variables have not been integrated into a multivariate model. As a result, this study examined a multivariate model of parent-late adolescent gender dyads in an attempt to capture important predictors in late adolescents' important and unique transition to adulthood. The sample…

Dihydrogen Phosphate Stabilized Ruthenium(0 Nanoparticles: Efficient Nanocatalyst for The Hydrolysis of Ammonia-Borane at Room Temperature

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Feyyaz Durap

2015-07-01

Full Text Available Intensive efforts have been devoted to the development of new materials for safe and efficient hydrogen storage. Among them, ammonia-borane appears to be a promising candidate due to its high gravimetric hydrogen storage capacity. Ammonia-borane can release hydrogen on hydrolysis in aqueous solution under mild conditions in the presence of a suitable catalyst. Herein, we report the synthesis of ruthenium(0 nanoparticles stabilized by dihydrogenphosphate anions with an average particle size of 2.9 ± 0.9 nm acting as a water-dispersible nanocatalyst in the hydrolysis of ammonia-borane. They provide an initial turnover frequency (TOF value of 80 min−1 in hydrogen generation from the hydrolysis of ammonia-borane at room temperature. Moreover, the high stability of these ruthenium(0 nanoparticles makes them long-lived and reusable nanocatalysts for the hydrolysis of ammonia-borane. They provide 56,800 total turnovers and retain ~80% of their initial activity even at the fifth catalytic run in the hydrolysis of ammonia-borane at room temperature.

Dihydrogen Phosphate Stabilized Ruthenium(0) Nanoparticles: Efficient Nanocatalyst for The Hydrolysis of Ammonia-Borane at Room Temperature

Science.gov (United States)

Durap, Feyyaz; Caliskan, Salim; Özkar, Saim; Karakas, Kadir; Zahmakiran, Mehmet

2015-01-01

Intensive efforts have been devoted to the development of new materials for safe and efficient hydrogen storage. Among them, ammonia-borane appears to be a promising candidate due to its high gravimetric hydrogen storage capacity. Ammonia-borane can release hydrogen on hydrolysis in aqueous solution under mild conditions in the presence of a suitable catalyst. Herein, we report the synthesis of ruthenium(0) nanoparticles stabilized by dihydrogenphosphate anions with an average particle size of 2.9 ± 0.9 nm acting as a water-dispersible nanocatalyst in the hydrolysis of ammonia-borane. They provide an initial turnover frequency (TOF) value of 80 min−1 in hydrogen generation from the hydrolysis of ammonia-borane at room temperature. Moreover, the high stability of these ruthenium(0) nanoparticles makes them long-lived and reusable nanocatalysts for the hydrolysis of ammonia-borane. They provide 56,800 total turnovers and retain ~80% of their initial activity even at the fifth catalytic run in the hydrolysis of ammonia-borane at room temperature. PMID:28793435

Study of physico-chemical release of uranium and plutonium oxides during the combustion of polycarbonate and of ruthenium during the combustion of solvents used in the reprocessing of nuclear fuel

International Nuclear Information System (INIS)

Bouilloux, L.

1998-01-01

The level of consequences concerning a fire in a nuclear facility is in part estimated by the quantities and the physico-chemical forms of radioactive compounds that may be emitted out of the facility. It is therefore necessary to study the contaminant release from the fire. Because of the multiplicity of the scenarios, two research subjects were retained. The first one concerns the study of the uranium or plutonium oxides chemical release during the combustion of the polycarbonate glove box sides. The second one is about the physico chemical characterisation of the ruthenium release during the combustion of an organic solvent mixture (tributyl phosphate-dodecane) used for the nuclear fuel reprocessing. Concerning the two research subjects, the chemical release, i.e. means the generation of contaminant compounds gaseous in the fire, was modelled using thermodynamical simulations. Experiments were done in order to determine the ruthenium release factor during solvent combustion. A cone calorimeter was used for small scale experiments. These results were then validated by large scale tests under conditions close to the industrial process. Thermodynamical simulations, for the two scenarios studied. Furthermore, the experiments on solvent combustion allowed the determination of a suitable ruthenium release factor. Finally, the mechanism responsible of the ruthenium release has been found. (author)

Ru-OSO coordination photogenerated at 100 K in tetraammineaqua(sulfur dioxide)ruthenium(II) (±)-camphorsulfonate.

Science.gov (United States)

Phillips, Anthony E; Cole, Jacqueline M; d'Almeida, Thierry; Low, Kian Sing

2012-02-06

The photoinduced O-bound coordination mode in RuSO(2) complexes, previously observed only at 13 K, has been generated at 100 K in tetraammineaqua(sulfur dioxide)ruthenium(II) (±)-camphorsulfonate. This coordination state, often denoted MS1, decays to the η(2)-bound MS2 state, with an estimated half-life of 3.4(8) h and a long-lived population of 2.9(4)% at 120 K.

Kinetics and Mechanistic Study of the Ruthenium(III Catalysed Oxidative Decarboxylation of L-Proline by Alkaline Heptavalent Manganese (Stopped flow technique

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R. S. Shettar

2005-01-01

Full Text Available The kinetics of ruthenium(III catalysed oxidation of L-Proline by permanganate in alkaline medium at a constant ionic strength has been studied spectrophotometrically using a rapid kinetic accessory. The reaction between permanganate and L-Proline in alkaline medium exhibits 2:1 stoichiometry (KMnO4: L-Proline. The reaction shows first order dependence on [permanganate] and [ruthenium(III] and apparent less than unit order dependence each in L-Proline and alkali concentrations. Reaction rate increases with increase in ionic strength and decrease in solvent polarity of the medium. Initial addition of reaction products did not affect the rate significantly. A mechanism involving the formation of a complex between catalyst and substrate has been proposed. The activation parameters were computed with respect to the slow step of the mechanism and discussed

Measuring child awareness for adult symptomatic HIV using a verbal assessment tool: concordance between adult-child dyads on adult HIV-associated symptoms and illnesses.

Science.gov (United States)

Becker, Elisabeth; Kuo, Caroline; Operario, Don; Moshabela, Mosa; Cluver, Lucie

2015-11-01

This study assessed children's awareness for adult HIV-associated symptoms and illnesses using a verbal assessment tool by analysing inter-rater reliability between adult-child dyads. This study also evaluated sociodemographic and household characteristics associated with child awareness of adult symptomatic HIV. A cross-sectional survey using a representative community sample of adult-child dyads (N=2477 dyads) was conducted in KwaZulu-Natal, South Africa. Analyses focused on a subsample (n=673 adult-child dyads) who completed verbal assessment interviews for symptomatic HIV. We used an existing validated verbal autopsy approach, originally designed to determine AIDS-related deaths by adult proxy reporters. We adapted this approach for use by child proxy reporters for reporting on HIV-associated symptoms and illnesses among living adults. Analyses assessed whether children could reliably report on adult HIV-associated symptoms and illnesses and adult provisional HIV status. Adult-child pairs concurred above the 65th percentile for 9 of the 10 HIV-associated symptoms and illnesses with sensitivities ranging from 10% to 100% and specificities ranging from 20% to 100%. Concordant reporting between adult-child dyads for the adult's provisional HIV status was 72% (sensitivity=68%, specificity=73%). Children were more likely to reliably match adult's reports of provisional HIV status when they lived in households with more household members, and households with more robust socioeconomic indicators including access to potable water, food security and television. Children demonstrate awareness of HIV-associated symptoms and illnesses experienced by adults in their household. Children in households with greater socioeconomic resources and more household members were more likely to reliably report on the adult's provisional HIV status. Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to http://group.bmj.com/group/rights-licensing/permissions.

Synergistic Interaction within Bifunctional Ruthenium Nanoparticle/SILP Catalysts for the Selective Hydrodeoxygenation of Phenols.

Science.gov (United States)

Luska, Kylie L; Migowski, Pedro; El Sayed, Sami; Leitner, Walter

2015-12-21

Ruthenium nanoparticles immobilized on acid-functionalized supported ionic liquid phases (Ru NPs@SILPs) act as efficient bifunctional catalysts in the hydrodeoxygenation of phenolic substrates under batch and continuous flow conditions. A synergistic interaction between the metal sites and acid groups within the bifunctional catalyst leads to enhanced catalytic activities for the overall transformation as compared to the individual steps catalyzed by the separate catalytic functionalities. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

General synthesis of (salen)ruthenium(III) complexes via N...N coupling of (salen)ruthenium(VI) nitrides.

Science.gov (United States)

Man, Wai-Lun; Kwong, Hoi-Ki; Lam, William W Y; Xiang, Jing; Wong, Tsz-Wing; Lam, Wing-Hong; Wong, Wing-Tak; Peng, Shie-Ming; Lau, Tai-Chu

2008-07-07

Reaction of [Ru (VI)(N)(L (1))(MeOH)] (+) (L (1) = N, N'-bis(salicylidene)- o-cyclohexylenediamine dianion) with excess pyridine in CH 3CN produces [Ru (III)(L (1))(py) 2] (+) and N 2. The proposed mechanism involves initial equilibrium formation of [Ru (VI)(N)(L (1))(py)] (+), which undergoes rapid N...N coupling to produce [(py)(L (1))Ru (III) N N-Ru (III)(L (1))(py)] (2+); this is followed by pyridine substituion to give the final product. This ligand-induced N...N coupling of Ru (VI)N is utilized in the preparation of a series of new ruthenium(III) salen complexes, [Ru (III)(L)(X) 2] (+/-) (L = salen ligand; X = H 2O, 1-MeIm, py, Me 2SO, PhNH 2, ( t )BuNH 2, Cl (-) or CN (-)). The structures of [Ru (III)(L (1))(NH 2Ph) 2](PF 6) ( 6), K[Ru (III)(L (1))(CN) 2] ( 9), [Ru (III)(L (2))(NCCH 3) 2][Au (I)(CN) 2] ( 11) (L (2) = N, N'-bis(salicylidene)- o-phenylenediamine dianion) and [N ( n )Bu 4][Ru (III)(L (3))Cl 2] ( 12) (L (3) = N, N'-bis(salicylidene)ethylenediamine dianion) have been determined by X-ray crystallography.

Commercial exchanges in B2B Dyads. A new model of decision-making in fast changing markets

NARCIS (Netherlands)

Moreno Bragado, Elisa

2003-01-01

This dissertation presents a Model of Commercial Exchanges in B2B Dyads. This model explains how buying and selling decisions are made in industrial markets that are subject to continuous change, particularly the market for telecommunication products and services.Buying and selling decision-making

Determination of gold osmium and ruthenium through iodine-azide reaction in presence of 2- or 6- mercaptopurine

International Nuclear Information System (INIS)

Matusiewicz, H.; Kurzawa, Z.

1978-01-01

The composition of osmium and ruthenium complexes with 6-mercaptopurine has been determined. The sensitivity of the method was enhanced due to a proper choice of the optimal time of the formation of these complexes and the time of equilibrium attainment in the presence of excess of azide. Also the gold complex with 2-mercaptopurine was investigated. (author)

Ruthenium supported on magnetic nanoparticles: An efficient and recoverable catalyst for hydrogenation of alkynes and transfer hydrogenation of carbonyl compounds

Science.gov (United States)

Ruthenium supported on surface modified magnetic nanoparticles (NiFe2O4) has been successfully synthesized and applied for hydrogenation of alkynes at room temperature as well as transfer hydrogenation of a number of carbonyl compounds under microwave irradiation conditions. The ...

Protege and Mentor Self-Disclosure: Levels and Outcomes within Formal Mentoring Dyads in a Corporate Context

Science.gov (United States)

Wanberg, Connie R.; Welsh, Elizabeth T.; Kammeyer-Mueller, John

2007-01-01

This study examined the role of self-disclosure within protege/mentor dyads in formal mentoring partnerships within a corporate context as a means of learning more about specific relationship processes that may enhance the positive outcomes of mentoring. While both proteges and mentors self-disclosed in their relationships, proteges disclosed at a…

Synthesis, structure, DNA binding and anticancer activity of mixed ligand ruthenium(II) complex

Science.gov (United States)

Gilewska, Agnieszka; Masternak, Joanna; Kazimierczuk, Katarzyna; Trynda, Justyna; Wietrzyk, Joanna; Barszcz, Barbara

2018-03-01

In order to obtain a potential chemotherapeutic which is not affected on the normal BALB/3T3 cell line, a new arene ruthenium(II) complex {[RuCl(L1)(η6-p-cymene)]PF6}2 · H2O has been synthesized by a direct reaction of precursor, [{(η6-p-cymene)Ru(μ-Cl)}2Cl2], with N,N-chelating ligand (L1 - 2,2‧-bis(4,5-dimethylimidazole). The compound has been fully characterized by elemental analysis, X-ray diffraction, IR, UV-Vis and 1H, 13C NMR spectroscopies. X-ray analysis have confirmed that the compound crystallized in the monoclinic group Cc as an inversion twin. The asymmetric unit contains two symmetrically independent cationic complexes [RuCl(L1)(η6-p-cymene)]+ whose charge is balanced by two PF6- counterions. The shape of each cationic coordination polyhedral can be described as a distorted dodecahedron and shows a typical piano-stool geometry. In addition, an analysis of the crystal structure and the Hirshfeld surface analysis were used to detect and visualize important hydrogen bonds and intermolecular interaction. Moreover, the antiproliferative behavior of the obtained complex was assayed against three human cells: MV-4-11, LoVo, MCF-7 and BALB/3T3 - normal mice fibroblast cells. To predict a binding mode, a potential interaction of ruthenium complex with calf thymus DNA (CT-DNA) has been explored using UV absorption and circular dichroism (CD).

Raman spectra of ruthenium and tantalum trimers in argon matrices

Science.gov (United States)

Fang, Li; Shen, Xiaole; Chen, Xiaoyu; Lombardi, John R.

2000-12-01

The resonance Raman spectra of ruthenium trimers (Ru 3) in argon matrices have been obtained. Three resonance Raman transitions were observed between 570 and 590 nm. Two of them (303.4 and 603.7 cm -1) are assigned to the totally symmetric vibrational progression, giving k e=1.86 mdyne/ Å. The line at 581.5 cm-1 is assigned as the origin of a low-lying electronic state. We also report on the observation of a resonance Raman spectrum of tantalum trimers (Ta 3). Observed lines include 251.2 and 501.9 cm-1 which we assign to the fundamental and the first overtone of the symmetric stretch in Ta 3. This gives k e=2.25 mdyne/ Å.

Evidence for Dynamic Chemical Kinetics at Individual Molecular Ruthenium Catalysts.

Science.gov (United States)

Easter, Quinn T; Blum, Suzanne A

2018-02-05

Catalytic cycles are typically depicted as possessing time-invariant steps with fixed rates. Yet the true behavior of individual catalysts with respect to time is unknown, hidden by the ensemble averaging inherent to bulk measurements. Evidence is presented for variable chemical kinetics at individual catalysts, with a focus on ring-opening metathesis polymerization catalyzed by the second-generation Grubbs' ruthenium catalyst. Fluorescence microscopy is used to probe the chemical kinetics of the reaction because the technique possesses sufficient sensitivity for the detection of single chemical reactions. Insertion reactions in submicron regions likely occur at groups of many (not single) catalysts, yet not so many that their unique kinetic behavior is ensemble averaged. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrogenation of fast pyrolyis oil and model compounds in a two-phase aqueous organic system using homogeneous ruthenium catalysts

NARCIS (Netherlands)

Mahfud, F. H.; Ghijsen, F.; Heeres, H. J.

2007-01-01

The use of homogeneous ruthenium catalysts to hydrogenate the water-soluble fraction of pyrolysis oil is reported. Pyrolysis oil, which is obtained by fast pyrolysis of lignocellulosic biomass at 450-600 degrees C, contains significant amounts of aldehydes and ketones (e.g. 1-hydroxy-2-propanone (1)

The dyad palindromic glutathione transferase P enhancer binds multiple factors including AP1.

OpenAIRE

Diccianni, M B; Imagawa, M; Muramatsu, M

1992-01-01

Glutathione Transferase P (GST-P) gene expression is dominantly regulated by an upstream enhancer (GPEI) consisting of a dyad of palindromically oriented imperfect TPA (12-O-tetradecanoyl-phorbol-13-acetate)-responsive elements (TRE). GPEI is active in AP1-lacking F9 cells as well in AP1-containing HeLa cells. Despite GPEI's similarity to a TRE, c-jun co-transfection has only a minimal effect on transactivation. Antisense c-jun and c-fos co-transfection experiments further demonstrate the lac...

Mitochondria are the primary target in the induction of apoptosis by chiral ruthenium(II) polypyridyl complexes in cancer cells.

Science.gov (United States)

Wang, Jin-Quan; Zhang, Ping-Yu; Qian, Chen; Hou, Xiao-Juan; Ji, Liang-Nian; Chao, Hui

2014-03-01

A series of novel chiral ruthenium(II) polypyridyl complexes (Δ-Ru1, Λ-Ru1, Δ-Ru2, Λ-Ru2, Δ-Ru3, Λ-Ru3) were synthesized and evaluated to determine their antiproliferative activities. Colocalization, inductively coupled plasma mass spectrometry, and 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay studies showed that these ruthenium(II) complexes accumulated preferentially in the mitochondria and exhibited cytotoxicity against various cancer cells in vitro. The complex Δ-Ru1 is of particular interest because it was found to have half-maximal inhibitory concentrations comparable to those of cisplatin and better activity than cisplatin against a cisplatin-resistant cell line, A549-CP/R. Δ-Ru1 induced alterations in the mitochondrial membrane potential and triggered intrinsic mitochondria-mediated apoptosis in HeLa cells, which involved the regulation of Bcl-2 family members and the activation of caspases. Taken together, these data suggest that Δ-Ru1 may be a novel mitochondria-targeting anticancer agent.

An alternative pathway for production of acetonitrile: ruthenium catalysed aerobic dehydrogenation of ethylamine

DEFF Research Database (Denmark)

Corker, Emily; Mentzel, Uffe Vie; Mielby, Jerrik Jørgen

2013-01-01

The oxidative synthesis of acetonitrile from ethylamine was studied using a supported ruthenium catalyst. The reaction was conducted in both batch and flow processes and high conversions (over 85%) were achieved in both cases. Selectivity of both reactions was improved by optimisation of reaction...... conditions, achieving over 90% selectivity in the batch process and 80% selectivity in the continuous flow process. The use of a selective solid catalyst that utilises a feedstock that can be derived from biomass, dioxygen as the oxidant and water as the solvent represents a new, green route...

Mono and dinuclear iridium, rhodium and ruthenium complexes containing chelating carboxylato pyrazine ligands: Synthesis, molecular structure and electrochemistry

Czech Academy of Sciences Publication Activity Database

Govindaswamy, P.; Therrien, B.; Süss-Fink, G.; Štěpnička, P.; Ludvík, Jiří

2007-01-01

Roč. 692, č. 8 (2007), s. 1661-1671 ISSN 0022-328X R&D Projects: GA MŠk LC510; GA MŠk(CZ) LC06070 Institutional research plan: CEZ:AV0Z40400503 Keywords : dinuclear complexes * iridium * rhodium * ruthenium * electrochemistry Subject RIV: CG - Electrochemistry Impact factor: 2.168, year: 2007

Emotional reactions of mothers facing premature births: study of 100 mother-infant dyads 32 gestational weeks.

Science.gov (United States)

Eutrope, Julien; Thierry, Aurore; Lempp, Franziska; Aupetit, Laurence; Saad, Stéphanie; Dodane, Catherine; Bednarek, Nathalie; De Mare, Laurence; Sibertin-Blanc, Daniel; Nezelof, Sylvie; Rolland, Anne-Catherine

2014-01-01

This current study has been conducted to clarify the relationship between the mother's post-traumatic reaction triggered by premature birth and the mother-infant interactions. In this article, the precocious maternal feelings are described. A multicenter prospective study was performed in three French hospitals. 100 dyads with 100 very premature infants and their mothers were recruited. Mothers completed, at two different times self-questionnaires of depression/anxiety, trauma and social support. The quality of interactions in the dyads was evaluated. Thirty-nine percent of the mothers obtained a score at HADS suggesting a high risk of depression at the first visit and approximately one-third at visit two. Seventy-five percent of the mothers were at risk of suffering from an anxiety disorder at visit one and half remained so at visit two. A "depressed" score at visits one and two correlated with a hospitalization for a threatened premature labor. We noted a high risk of trauma for 35% of the mothers and high interactional synchrony was observed for approximately two-thirds of the dyads. The mothers' psychological reactions such as depression and anxiety or postnatal depression correlate strongly with the presence of an initial trauma. At visit one and visit two, a high score of satisfaction concerning social support correlates negatively with presence of a trauma. A maternal risk of trauma is more frequent with a C-section delivery. Mothers' psychological reactions such as depression and anxiety correlate greatly with the presence of an initial trauma. The maternal traumatic reaction linked to premature birth does not correlate with the term at birth, but rather with the weight of the baby. Social support perceived by the mother is correlated with the absence of maternal trauma before returning home, and also seems to inhibit from depressive symptoms from the time of the infant's premature birth.

Emotional reactions of mothers facing premature births: study of 100 mother-infant dyads 32 gestational weeks.

Directory of Open Access Journals (Sweden)

Julien Eutrope

Full Text Available OBJECTIVES: This current study has been conducted to clarify the relationship between the mother's post-traumatic reaction triggered by premature birth and the mother-infant interactions. In this article, the precocious maternal feelings are described. METHODS: A multicenter prospective study was performed in three French hospitals. 100 dyads with 100 very premature infants and their mothers were recruited. Mothers completed, at two different times self-questionnaires of depression/anxiety, trauma and social support. The quality of interactions in the dyads was evaluated. RESULTS: Thirty-nine percent of the mothers obtained a score at HADS suggesting a high risk of depression at the first visit and approximately one-third at visit two. Seventy-five percent of the mothers were at risk of suffering from an anxiety disorder at visit one and half remained so at visit two. A "depressed" score at visits one and two correlated with a hospitalization for a threatened premature labor. We noted a high risk of trauma for 35% of the mothers and high interactional synchrony was observed for approximately two-thirds of the dyads. The mothers' psychological reactions such as depression and anxiety or postnatal depression correlate strongly with the presence of an initial trauma. At visit one and visit two, a high score of satisfaction concerning social support correlates negatively with presence of a trauma. A maternal risk of trauma is more frequent with a C-section delivery. CONCLUSIONS: Mothers' psychological reactions such as depression and anxiety correlate greatly with the presence of an initial trauma. The maternal traumatic reaction linked to premature birth does not correlate with the term at birth, but rather with the weight of the baby. Social support perceived by the mother is correlated with the absence of maternal trauma before returning home, and also seems to inhibit from depressive symptoms from the time of the infant's premature birth.

Modification of Ammonia Decomposition Activity of Ruthenium Nanoparticles by N-Doping of CNT Supports

OpenAIRE

Bell, Tamsin; Zhan, G; Wu, Kejun; Torrente Murciano, Laura

2017-01-01

The use of ammonia as a hydrogen vector has the potential to unlock the hydrogen economy. In this context, this paper presents novel insights into improving the ammonia decomposition activity of ruthenium nanoparticles supported on carbon nanotubes (CNT) by nitrogen doping. Our results can be applied to develop more active systems capable of delivering hydrogen on demand, with a view to move towards the low temperature target of less than 150 °C. Herein we demonstrate that nitrogen doping of ...

Highly efficient quenching of tris(2,2'-bipyridyl)ruthenium(II) electrochemiluminescence by ozone using formaldehyde, methylglyoxal, and glyoxalate as co-reactants and its application to ozone sensing.

Science.gov (United States)

Gao, Ying; Liu, Xiaoyun; Qi, Wenjing; Gao, Wenyue; Li, Yunhui; Xu, Guobao

2015-06-21

Most electrochemiluminescence (ECL) systems require high concentrations of quencher to totally quench ECL. In this study, we found that ozone can quench tris(2,2'-bipyridyl)ruthenium(II) ECL using formaldehyde, methylglyoxal, or glyoxalate as co-reactants at a glassy carbon electrode with remarkable efficiencies even when the concentration of ozone is merely 0.25% of that of the co-reactant. The strongest quenching is observed with the tris(2,2'-bipyridyl)ruthenium(II)/formaldehyde ECL system. The tris(2,2'-bipyridyl)ruthenium(II)/formaldehyde ECL intensities decrease linearly with the ozone concentration over the range of 0.025-25 μM (r = 0.9947) with a limit of detection of 8 nM. The method is more sensitive and faster than most methods. It shows high selectivity in the presence of other ROS or oxidants and some metal ions, such as H2O2, ClO(-), Mg(2+), Ni(2+), etc. The method exhibits high recoveries for the detection of ozone in a ventilated photocopy room.

Theoretical characterization of the surface composition of ruthenium nanoparticles in equilibrium with syngas

Science.gov (United States)

Cusinato, Lucy; Martínez-Prieto, Luis M.; Chaudret, Bruno; Del Rosal, Iker; Poteau, Romuald

2016-05-01

A deeper understanding of the relationship between experimental reaction conditions and the surface composition of nanoparticles is crucial in order to elucidate mechanisms involved in nanocatalysis. In the framework of the Fischer-Tropsch synthesis, a resolution of this complex puzzle requires a detailed understanding of the interaction of CO and H with the surface of the catalyst. In this context, the single- and co-adsorption of CO and H to the surface of a 1 nm ruthenium nanoparticle has been investigated with density functional theory. Using several indexes (d-band center, crystal overlap Hamilton population, density of states), a systematic analysis of the bond properties and of the electronic states has also been done, in order to bring an understanding of structure/property relationships at the nanoscale. The H : CO surface composition of this ruthenium nanoparticle exposed to syngas has been evaluated according to a thermodynamic model fed with DFT energies. Such ab initio thermodynamic calculations give access to the optimal H : CO coverage values under a wide range of experimental conditions, through the construction of free energy phase diagrams. Surprisingly, under the Fischer-Tropsch synthesis experimental conditions, and in agreement with new experiments, only CO species are adsorbed at the surface of the nanoparticle. These findings shed new light on the possible reaction pathways underlying the Fischer-Tropsch synthesis, and specifically the initiation of the reaction. It is finally shown that the joint knowledge of the surface composition and energy descriptors can help to identify possible reaction intermediates.A deeper understanding of the relationship between experimental reaction conditions and the surface composition of nanoparticles is crucial in order to elucidate mechanisms involved in nanocatalysis. In the framework of the Fischer-Tropsch synthesis, a resolution of this complex puzzle requires a detailed understanding of the interaction

Elution behavior of N-heterocyclic derivatives of mixed ruthenium(II)-sulfoxide complexes in reversed-phase high-performance liquid chromatography

International Nuclear Information System (INIS)

Toma, H.E.; Silva, D.O.

1991-01-01

The elution behaviour of a series of dichlorobis-(dimethylsulfoxide)bis(N-heterocyclic) ruthenium(II) complexes has been investigated using reversed-phase HPLC. Similar trends as those displayed by the free N-heterocyclic bases have been observed for the complexes, essentially reflecting the hydrophobic properties of the aromatic ligands. (orig.)

Partitioning of rhodium and ruthenium between Pd–Rh–Ru and (Ru,Rh)O{sub 2} solid solutions in high-level radioactive waste glass

Energy Technology Data Exchange (ETDEWEB)

Sugawara, Toru, E-mail: toru@gipc.akita-u.ac.jp [Center for Engineering Science, Akita University, 1-1, Tegatagakuenmachi, Akita City, Akita 010-8502 (Japan); Ohira, Toshiaki [Center for Engineering Science, Akita University, 1-1, Tegatagakuenmachi, Akita City, Akita 010-8502 (Japan); Komamine, Satoshi; Ochi, Eiji [Research and Development Department, Reprocessing Business Division, Japan Nuclear Fuel Limited, 4-108, Okitsuke, Obuchi, Rokkasho-mura, Aomori 039-3212 (Japan)

2015-10-15

The partitioning of rhodium and ruthenium between Pd–Rh–Ru alloy with a face-centered cubic (FCC) structure and (Ru,Rh)O{sub 2} solid solution has been investigated between 1273 and 1573 K at atmospheric oxygen fugacity. The rhodium and ruthenium contents in FCC increase, while the RhO{sub 2} content in (Ru,Rh)O{sub 2} decreases with increasing temperature due to progressive reduction of the system. Based on the experimental results and previously reported thermodynamic data, the thermodynamic mixing properties of FCC phase and (Ru,Rh)O{sub 2} have been calibrated in an internally consistent manner. Phase equilibrium of platinum grope metals in an HLW glass was calculated by using the obtained thermodynamic parameters.

Effect of ozone on ruthenium species in alkaline medium. Pt. II. Oxidation of pentahydroxo nitrosyl ruthenate(II) ion RuNO(OH)52-

International Nuclear Information System (INIS)

Floquet, S.; Eysseric, C.

2006-01-01

Oxidation of the nitrosyl ruthenium complex RuNO(OH) 5 2- has been carried out in sodium hydroxide solutions in contact with a gas flow containing ozone. The RuNO(OH) 5 2- complex is converted successively into ruthenate and perruthenate ions. An empirical kinetic rate law for the first step has been determined and was shown to depend on concentrations of (i) the ruthenium complex, (ii) the hydroxide ions and (iii) ozone concentration in the gas flow. The second step of the reaction, corresponding to the perruthenate ion formation, shows a complex mechanism and four competing reactions have been proposed to represent it. The influences on the second step kinetics of several parameters such as ozone or hydroxide concentrations or the conditions of the gas-liquid exchange area are also qualitatively discussed. (orig.)

Molecular mass spectrometry in metallodrug development: A case of mapping transferrin-mediated transformations for a ruthenium(III) anticancer drug

Energy Technology Data Exchange (ETDEWEB)

Jarosz, Maciej [Chair of Analytical Chemistry, Faculty of Chemistry, Warsaw University of Technology, Noakowskiego St. 3, 00-664 Warsaw (Poland); Matczuk, Magdalena, E-mail: mmatczuk@ch.pw.edu.pl [Chair of Analytical Chemistry, Faculty of Chemistry, Warsaw University of Technology, Noakowskiego St. 3, 00-664 Warsaw (Poland); Pawlak, Katarzyna [Chair of Analytical Chemistry, Faculty of Chemistry, Warsaw University of Technology, Noakowskiego St. 3, 00-664 Warsaw (Poland); Timerbaev, Andrei R. [Vernadsky Institute of Geochemistry and Analytical Chemistry, Russian Academy of Sciences, Kosygin St. 19, 119991 Moscow (Russian Federation)

2014-12-03

Highlights: • Extra- and intra-cellular interactions of Ru(III) anticancer drug candidate. • ESI-TOF-MS mapping of the ruthenium species bound to transferring. • ESI-QqQ-MS identification of released Ru species under cytosol simulated conditions. - Abstract: Electrospray ionization mass spectrometry (ESI-MS) techniques have been used to characterize the speciation of a Ru(III) anticancer drug, indazolium trans-[tetrachloridobis(1H-indazole) ruthenate(III)], upon its binding to transferrin and the impact of cellular reducing components on drug–transferrin adducts. Using time-of-flight ESI-MS, the polymorphism of apo- (iron-free) and holo-form (iron-saturated) of the protein was confirmed. While the ruthenium moieties bound to each of five isoforms under simulated extracellular conditions are essentially identical in numbers for apo- and holo-transferrin, distinct differences were found in the composition of Ru(III) species attached to either of the protein forms, which are dominated by differently coordinated aquated complexes. On the other hand, at least one of the Ru-N bonds in metal-organic framework remains intact even after prolonged interaction with the protein. Triple quadrupole tandem ESI-MS measurements demonstrated that the ruthenium species released from drug adducts with holo-transferrin in simulated cancer cytosol are underwent strong ligand exchange (as compared to the protein-bound forms) but most strikingly, they contain the metal center in the reduced Ru(II) state. In vitro probing the extra- and intracellular interactions of promising Ru(III) drug candidate performed by ESI-MS is thought to shed light on the transportation to tumor cells by transferrin and on the activation to more reactive species by the reducing environment of solid tumors.

Nickel-foam-supported ruthenium oxide/graphene sandwich composite constructed via one-step electrodeposition route for high-performance aqueous supercapacitors

Science.gov (United States)

Li, Meng; He, Hanwei

2018-05-01

A high-performance supercapacitor both considered high power and high energy density is needed for its applications such as portable electronics and electric vehicles. Herein, we construct a high-performance ruthenium oxide/graphene (RuO2-ERG) composite directly grown on Ni foam through cyclic voltammetric deposition process. The RuO2-ERG composite with sandwich structure is achieved effectively from a mixed solution of graphene oxide and ruthenium trichloride in the -1.4 V to 1.0 V potential range at a scan rate of 5 mV s-1. The electrochemical performance is optimized by tuning the concentration of the ruthenium trichloride. This integrative RuO2-ERG composite electrode can effectively maintains the accessible surface for redox reaction and stable channels for electrolyte penetration, leading to an improved electrochemical performance. Symmetrical aqueous supercapacitors based on RuO2-ERG electrodes exhibit a wider operational voltage window of 1.5 V. The optimized RuO2-ERG electrode displays a superior specific capacitance with 89% capacitance retention upon increasing the current density by 50 times. A high energy density of 43.8 W h kg-1 at a power density of 0.75 kW kg-1 is also obtained, and as high as 39.1 W h kg-1 can be retained at a power density of 37.5 kW kg-1. In addition, the capacitance retention is still maintained at 92.8% even after 10,000 cycles. The excellent electrochemical performance, long-term cycle stability, and the ease of preparation demonstrate that this typical RuO2-ERG electrode has great potentialities to develop high-performance supercapacitors.