Exploiting Natural Products to Build Metalla-Assemblies: The Anticancer Activity of Embelin-Derived Rh(III and Ir(III Metalla-Rectangles

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Gajendra Gupta

2014-05-01

Full Text Available Six new pentamethylcyclopentadienyl Rh(III and Ir(III metalla-rectangles ([3](CF3SO34–[8](CF3SO34 have been prepared by a self-assembly strategy using the embelin-derived metalla-clips (η5-C5Me52M2(μ4-C6HRO4-κOCl2 (M = Rh, 1; M = Ir, 2; R = (CH210CH3 and the linear ditopic ligands, pyrazine, 4,4'-bipyridine and 1,2-bis (4-pyridylethylene. These new metalla-rectangles have been obtained in high yield and isolated as their triflate salts. The complexes have been fully characterized by standard spectroscopic techniques and the antiproliferative activity of these tetranuclear complexes was evaluated in vitro on cancerous (DU-145, A-549, HeLa and noncancerous (HEK-293 cell lines. The biological study has showed a better activity for the rhodium derivatives over the iridium analogs and for all complexes a very good selectivity for cancerous over noncancerous cells. The presence of lipophilic side chains coupled with the positive charge of the tetranuclear complexes suggested a cytotoxic activity involving the mitochondrial machinery, as demonstrated by multiple biological experiments.

Synthesis, Molecular Structure and Cytotoxicity of Molecular Materials Based on Water Soluble Half-Sandwich Rh(III) and Ir(III) Tetranuclear Metalla-Cycles

Science.gov (United States)

Gupta, Gajendra; Murray, Benjamin S.; Dyson, Paul J.; Therrien, Bruno

2013-01-01

The neutral dinuclear complexes [(η5-C5Me5)2Rh2(μ-dhnq)Cl2] (1) and [(η5-C5Me5)2Ir2(μ-dhnq)Cl2] (2) (dhnqH2 = 5,8-dihydroxy-1,4-naphthoquinone) were obtained from the reaction of [(η5-C5Me5)M(μ-Cl)Cl]2 (M = Rh, Ir) with dhnqH2 in the presence of CH3COONa. Treatment of 1 or 2 in methanol with linear ditopic ligands L (L = pyrazine, 4,4′-bipyridine or 1,2-bis(4-pyridyl)ethylene), in the presence of AgCF3SO3, affords the corresponding tetranuclear metalla-rectangles [(η5-C5Me5)4M4(μ-dhnq)2(μ-L)2]4+ (L = pyrazine, M = Rh, 3; M = Ir, 4; L = 4,4′-bipyridine, M = Rh, 5; M = Ir, 6; L = 1,2-bis(4-pyridyl)ethylene, M = Rh, 7; M = Ir, 8). All complexes were isolated as their triflate salts and were fully characterized by infrared, 1H and 13C NMR spectroscopy, and some representative complexes by single-crystal X-ray structure analysis. The X-ray structures of 3, 5 and 6 confirm the formation of the tetranuclear metalla-cycles, and suggest that complexes 5 and 6 possess a cavity of sufficient size to encapsulate small guest molecules. In addition, the antiproliferative activity of the metalla-cycles 3–8 was evaluated against the human ovarian A2780 (cisplatin sensitive) and A2780cisR (cisplatin resistant) cancer cell lines and on non-tumorigenic human embryonic kidney HEK293 cells. All cationic tetranuclear metalla-rectangles were found to be highly cytotoxic, with IC50 values in the low micromolar range. PMID:28788394

Synthesis, Molecular Structure and Cytotoxicity of Molecular Materials Based on Water Soluble Half-Sandwich Rh(III and Ir(III Tetranuclear Metalla-Cycles

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Gajendra Gupta

2013-11-01

Full Text Available The neutral dinuclear complexes [(η5-C5Me52Rh2(μ-dhnqCl2] (1 and [(η5-C5Me52Ir2(μ-dhnqCl2] (2 (dhnqH2 = 5,8-dihydroxy-1,4-naphthoquinone were obtained from the reaction of [(η5-C5Me5M(μ-ClCl]2 (M = Rh, Ir with dhnqH2 in the presence of CH3COONa. Treatment of 1 or 2 in methanol with linear ditopic ligands L (L = pyrazine, 4,4′-bipyridine or 1,2-bis(4-pyridylethylene, in the presence of AgCF3SO3, affords the corresponding tetranuclear metalla-rectangles [(η5-C5Me54M4(μ-dhnq2(μ-L2]4+ (L = pyrazine, M = Rh, 3; M = Ir, 4; L = 4,4′-bipyridine, M = Rh, 5; M = Ir, 6; L = 1,2-bis(4-pyridylethylene, M = Rh, 7; M = Ir, 8. All complexes were isolated as their triflate salts and were fully characterized by infrared, 1H and 13C NMR spectroscopy, and some representative complexes by single-crystal X-ray structure analysis. The X-ray structures of 3, 5 and 6 confirm the formation of the tetranuclear metalla-cycles, and suggest that complexes 5 and 6 possess a cavity of sufficient size to encapsulate small guest molecules. In addition, the antiproliferative activity of the metalla-cycles 3–8 was evaluated against the human ovarian A2780 (cisplatin sensitive and A2780cisR (cisplatin resistant cancer cell lines and on non-tumorigenic human embryonic kidney HEK293 cells. All cationic tetranuclear metalla-rectangles were found to be highly cytotoxic, with IC50 values in the low micromolar range.

Uranium metalla-allenes with carbene imido R_2C=U"I"V=NR' units (R=Ph_2PNSiMe_3; R'=CPh_3): alkali-metal-mediated push-pull effects with an amido auxiliary

International Nuclear Information System (INIS)

Lu, Erli; Tuna, Floriana; Kaltsoyannis, Nikolas; Liddle, Stephen T.; Lewis, William

2016-01-01

We report uranium(IV)-carbene-imido-amide metalla-allene complexes [U(BIPM"T"M"S)(NCPh_3)(NHCPh_3)(M)] (BIPM"T"M"S=C(PPh_2NSiMe_3)_2; M=Li or K) that can be described as R_2C=U=NR' push-pull metalla-allene units, as organometallic counterparts of the well-known push-pull organic allenes. The solid-state structures reveal that the R_2C=U=NR' units adopt highly unusual cis-arrangements, which are also reproduced by gas-phase theoretical studies conducted without the alkali metals to remove their potential structure-directing roles. Computational studies confirm the double-bond nature of the U=NR' and U=CR_2 interactions, the latter increasingly attenuated by potassium then lithium when compared to the hypothetical alkali-metal-free anion. Combined experimental and theoretical data show that the push-pull effect induced by the alkali metal cations and amide auxiliary gives a fundamental and tunable structural influence over the C=U"I"V=N units. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Uranium metalla-allenes with carbene imido R{sub 2}C=U{sup IV}=NR' units (R=Ph{sub 2}PNSiMe{sub 3}; R'=CPh{sub 3}): alkali-metal-mediated push-pull effects with an amido auxiliary

Energy Technology Data Exchange (ETDEWEB)

Lu, Erli; Tuna, Floriana; Kaltsoyannis, Nikolas; Liddle, Stephen T. [School of Chemistry, The University of Manchester (United Kingdom); Lewis, William [School of Chemistry, The University of Nottingham (United Kingdom)

2016-08-08

We report uranium(IV)-carbene-imido-amide metalla-allene complexes [U(BIPM{sup TMS})(NCPh{sub 3})(NHCPh{sub 3})(M)] (BIPM{sup TMS}=C(PPh{sub 2}NSiMe{sub 3}){sub 2}; M=Li or K) that can be described as R{sub 2}C=U=NR' push-pull metalla-allene units, as organometallic counterparts of the well-known push-pull organic allenes. The solid-state structures reveal that the R{sub 2}C=U=NR' units adopt highly unusual cis-arrangements, which are also reproduced by gas-phase theoretical studies conducted without the alkali metals to remove their potential structure-directing roles. Computational studies confirm the double-bond nature of the U=NR' and U=CR{sub 2} interactions, the latter increasingly attenuated by potassium then lithium when compared to the hypothetical alkali-metal-free anion. Combined experimental and theoretical data show that the push-pull effect induced by the alkali metal cations and amide auxiliary gives a fundamental and tunable structural influence over the C=U{sup IV}=N units. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

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.

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...

A computational study of the addition of ReO3L (L = Cl(-), CH3, OCH3 and Cp) to ethenone.

Science.gov (United States)

Aniagyei, Albert; Tia, Richard; Adei, Evans

2016-01-01

The periselectivity and chemoselectivity of the addition of transition metal oxides of the type ReO3L (L = Cl, CH3, OCH3 and Cp) to ethenone have been explored at the MO6 and B3LYP/LACVP* levels of theory. The activation barriers and reaction energies for the stepwise and concerted addition pathways involving multiple spin states have been computed. In the reaction of ReO3L (L = Cl(-), OCH3, CH3 and Cp) with ethenone, the concerted [2 + 2] addition of the metal oxide across the C=C and C=O double bond to form either metalla-2-oxetane-3-one or metalla-2,4-dioxolane is the most kinetically favored over the formation of metalla-2,5-dioxolane-3-one from the direct [3 + 2] addition pathway. The trends in activation and reaction energies for the formation of metalla-2-oxetane-3-one and metalla-2,4-dioxolane are Cp Cp Cp Cp Cp. The direct [2 + 2] addition pathways leading to the formations of metalla-2-oxetane-3-one and metalla-2,4-dioxolane is thermodynamically the most favored for the ligands L = OCH3 and Cl(-). The difference between the calculated [2 + 2] activation barriers for the addition of the metal oxide LReO3 across the C=C and C=O functionalities of ethenone are small except for the case of L = Cl(-) and OCH3. The rearrangement of the metalla-2-oxetane-3-one-metalla-2,5-dioxolane-3-one even though feasible, are unfavorable due to high activation energies of their rate-determining steps. For the rearrangement of the metalla-2-oxetane-3-one to metalla-2,5-dioxolane-3-one, the trends in activation barriers is found to follow the order OCH3 Cp. The trends in the activation energies for the most favorable [2 + 2] addition pathways for the LReO3-ethenone system is CH3 > CH3O(-) > Cl(-) > Cp. For the analogous ethylene-LReO3 system, the trends in activation and reaction energies for the most favorable [3 + 2] addition pathway is CH3 > CH3O(-) > Cl(-) > Cp [10]. Even though the most favored pathway in the ethylene-LReO3 system is

Dichlorido[N-(N,N-dimethylcarbamimidoyl-N′,N′,4-trimethylbenzohydrazonamide]platinum(II nitromethane hemisolvate

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Dmitrii S. Bolotin

2014-04-01

Full Text Available In the title compound, [PtCl2(C13H21N5]·0.5CH3NO2, the PtII atom is coordinated in a slightly distorted square-planar geometry by two Cl atoms and two N atoms of the bidentate ligand. The (1,3,5-triazapentadienePtII metalla ring is slightly bent and does not conjugate with the aromatic ring. In the crystal, N—H...Cl hydrogen bonds link the complex molecules, forming chains along [001]. The nitromethane solvent molecule shows half-occupancy and is disordered over two sets of sites about an inversion centre.

The traces of roman metallurgy in Eastern Serbia

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Petković Sofija

2009-01-01

Full Text Available The archaeological traces of the Roman mining and metallurgy in eastern Serbia are rather frequent but insufficiently studied and published. Three mining-metallurgical regions abounding in gold, silver, copper, iron and lead could be distinguished there: 1. the upper course of the Pek river, metalla Pincensia, 2. the area between Bor, Zlot, Crna Reka and Rgotina and 3. the area in the river basin of Beli Timok, two latter ones had been organized as territoria metallorum. The archeometallurgical sites confirmed by investigations are: Kraku lu Jordan at the confluence of the Brodica river and the Pek river, Rudna Glava, Tilva Roš in Bor, Gamzigrad - Romuliana, Rgotina near Zaječar and Timacum Minus in the village Ravna near Knjaževac. Roman mining-metallurgical activities in eastern Serbia flourished from the end of the 3rd century, were interrupted by the invasion of Huns in AD 441. and restored in the time of emperors Anastasius and Justin I, in the end of the 5th - beginning of the 6th centuries. The Roman mining-metallurgical centers functioned in the 6th century until the Slav invasion in the beginning of the 7th century.

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.

Double-Sampling Method for Carrying Out Quality Control of a Fabrication Process; Methode du Double Echantillonnage pour le Controle de la Qualite d'un Procede de Fabrication; Metod dvukh obraztsov dlya osushchestvleniya kontrolya za kachestvom v protsesse izgotovleniya; Metodo de Muestreo Doble para el Control de Calidad de un Proceso de Fabricacion

Energy Technology Data Exchange (ETDEWEB)

Cerrolaza, J. A.; Lago, A.; Montojo, Rosa M. [Junta de Energia Nuclear, Madrid (Spain)

1966-02-15

' malyj procent defektnyh detalej, i ochen' vysokaja stoimost' kazhdogo iz komponentov. Po jetim soobrazhenijam v hode izgotovlenija neobhodimo tshhatel'no priderzhivat'sja krivoj proizvodstvennyh operacij, i pri sobljudenii jetogo uslovija chislo detalej, razrushaemyh pri kazhdoj proverke, dolzhno byt' minimal'nym. Obychnye metody, osnovannye na opredelenii oshibki pervogo roda, ne mogut byt' ispol'zovany, tak kak oni voobshhe nedostatochno jeffektivny. Kave razrabotal metod, pri kotorom razmer obrazcov i predely kontrolja javljajutsja funkciej oshibok pervogo i vtorogo roda. Jetot metod, hotja on i primenim, nevozmozhno ispol'zovat' dlja proverki komponentov reaktora, poskol'ku pri jetom nuzhny slishkom bol'shie obrazcy. Daetsja opisanie metoda, analogichnogo metodu Kave, no osnovannogo na ispol'zovanii dvuh obrazcov, blagodarja chemu znachitel'no umen'shaetsja srednij razmer obrazca. (author)

Diffusion, recrystallization and phase transformations; Diffusion, recristallisation et changements de phase; Diffuziya, rekristallizatsiya i fazovye prevrashcheniya; Difusion, recristalizacion y cambios de fase

Energy Technology Data Exchange (ETDEWEB)

Bokshtejn, S Z; Gubareva, M A; Kishkin, S T; Moroz, L M

1962-01-15

estructura del metal sufre modificaciones importantes despues de la recristalizacion, asi como despues de la transformacion polimorfica {alpha} {r_reversible} {gamma}, los atomos situados en los limites de los granulos iniciales no experimentan desplazamientos considerables. De manera analoga, los atomos de un aditivo (carbono radiactivo) situados en los limites de los granulos iniciales no migran a traves de los limites de los nuevos granulos del metal recristalizado. En cambio, la deformacion plastica va acompanada de migraciones considerables de los atomos situados en los limites de los granulos. Los datos obtenidos demuestran que la migracion de los limites de los granulos durante la recristalizacion y subsiguiente formacion de los granulos esta relacionada con un mecanismo especifico distinto del habitual mecanismo de difusion. Los autores han demostrado que las transformaciones estructurales que ocurren en las aleaciones a temperaturas elevadas pueden modificar la velocidad de los proceseos de autodifusion y heterodifusion. Basandose en el estudio de los procesos de difusion en el titanio y sus aleaciones en relacion con el estado polimorfico, los autores han comprobado que la velocidad de los procesos difiere notablemente en las distintas variedades cristalinas del titanio. Con ello desaparece la contradicion que existia entre el elevado punto de fusion del titanio y la energia de activacion del proceso de difusion en este elemente, que es relativamente baja. (author) [Russian] Razrabotana metodika, pozvolyayushchaya s pomoshch'yu radioaktivnykh izotopov issledovat' povedenie granits zeren v protsesse plasticheskoj deformatsii i posleduyushchej rekristallizatsii. Pokazano, chto rekristallizatsiya zheleza pri sravnitel'no malykh (15%) i bol'shikh (50-70%) stepenyakh deformatsii ne privodit k sushchestvennomu izmeneniyu mestopolozheniya atomov osnovnogo metalla, nakhodyashchikhsya na granitse iskhodnykh zeren. Pri znachitel'nom izmenenii struktury metalla posle

Crucible-Free Synthesis of Silicides and Borides; Synthese de siliciures et de borures sans creuset; Bestigel'nyj sintez silitsidov i boridov; Sintesis de siliciuros y boruros sin crisol

Energy Technology Data Exchange (ETDEWEB)

Ban, Z.; Sikirica, M. [Rudjer Boskovic Institute, Zagreb, Yugoslavia (Croatia)

1963-11-15

The laboratory method for preparing pure silicides and borides, reducing the corresponding oxides of metals, has been developed. Synthesis of silicides was carried out in the floating zone of molten silicon. The floating zone was obtained by means of electron bombardment. Synthesis of borides is similar but reactions are generally of the solid-solid type. Initial heating of the reaction mixture was also obtained by means of the electron beam but further heating was produced by the ionized gaseous products of the reaction. (author) [French] On a mis au point une methode pour la preparation en laboratoire de siliciures et de borures purs, par reduction des oxydes des metaux correspondants. La synthese des siliciures a pu etre faite dans la ''zone flottante'' du silicium fondu. Cette zone flottante a ete obtenue par bombardement electronique. La synthese des borures est analogue, mais les reactions ont lieu generalement a Tetat solide. Le chauffage initial du melange reactionnel a egalement ete obtenu pai bombardement electronique, mais le chauffage ulterieur etait assure par les electrons diffuses des produits ionises gazeux de la reaction. (author) [Spanish] Los autores idearon un metodo de laboratorio para preparar siliciuros y boruros puros por reduccion de los respectivos oxidos metalicos. La sintesis de los siliciuros se llevo a cabo en la zona flotante del silicio fundido. Esa zona se obtuvo por bombardeo electronico. La sintesis de los boruros se llevo a cabo de manera similar, pero generalmente las reacciones son del tipo solido-solido. El calentamiento inicial de la mezcla se efectuo tambien mediante un haz electronico, pero el calentamiento ulterior es producido por la dispersion electronica en los productos de reaccion ionizados en estado gaseoso. (author) [Russian] Razrabotan laboratornyj metod prigotovleniya chistykh silitsidov i boridov putem vosstanovleniya sootvetstvennykh okislov metalla. Sintez, silitsidov provodili v plavayushchej zone

Study of inclusions and segregation in metals by autoradiography; Etude autoradiographic des inclusions et de la segregation dans les metaux; Izuchenie primesej i usadki metalla s pomoshch'yu avtoradiografii; Estudio autoradiografico de las inclusiones y de la segregacion en los metales

Energy Technology Data Exchange (ETDEWEB)

Makin, S M [Wantage Research Laboratory, Wantage, Berks (United Kingdom)

1962-01-15

Three applications of radioisotope techniques to metallurgy are described. During the course of this work, new autoradiographic techniques are developed. These include the irradiation and autoradiography of extraction replicas, similar to those used in electron microscopy, and a two-colour dye-transfer process in which colour prints of autoradiographs are shown with the corresponding micrographs superposed. These methods are applied to the study of inclusions in steel and uranium and to an investigation of the segregation of sulphur and phosphorus in welds in stainless steel. (author) [French] Le memoire decrit trois applications des radioisotopes en metallurgie. Au cours de ces travaux, l'auteur a mis au point de nouvelles techniques d'autoradiographie. Celles-ci comportent l'irradiation d'empreintes pour autoradiographie et d'empreintes d'extraction, semblables a celles qui sont employees dans la microscopie electronique, et font appel a un procede de transfert en deux couleurs dans lequel on superpose des autoradiographies en couleur et les microphotographies correspondantes. Ces methodes sont appliquees a l'etude des inclusions dans l'acier et l'uranium ainsi qu'aux recherches sur la segregation du soufre et du phosphore dans les pieces soudees en acier inoxydable. (author) [Spanish] Se describen tres aplicaciones de las tecnicas de los radioisotopes en la metalurgia. En el curso de los experimentos se han perfeccionado nuevas tecnicas autorradiograficas, que comprenden la irradiacion de replicas de autorradiografia y extraccion, analogas a las utilizadas en la microscopia electronica y un procedimiento de impresion a dos colores que permite obtener autorradiografias superpuestas a las correspondientes micrografias. Estos metodos se aplican al estudio de inclusiones en el acero y el uranio y a una investigacion de la segregacion del azufre y del fosforo en soldaduras hechas en acero inoxidable. (author) [Russian] Daetsya opisanie trekh sposobov primeneniya radioizotopov v metallurgii. V khode ehtoj raboty byli sozdany novye avtoradiograficheskie metody. Oni vklyuchayut obluchenie i avtoradiografiyu ehkstraktsionnykh modelej, podobno ispol'zuemym v ehlektronnoj mikroskopii, i protsess dvukhtsvetnogo perekhoda, pri kotorom tsvetnye kopii chertezhej avtoradiografa pokazyvayutsya s sootvetstvuyushchimi nalozhennymi dannymi mikrografov. EHti metody ispol'zuyutsya pri izuchenii primesej v stali i urane i pri issledovanii segregatsii sery i fosfora pri svarke v nerzhaveyushchej stali. (author)

Measurement of the wear rate of cast grinding balls using radioactive tracers; Evaluation de l'usure des boulets pour concasseurs, au moyen des indicateurs radioactifs; Izmerenie skorosti iznosa litykh drobil'nykh sharov pri pomoshchi mechenykh atomov; Medicion de la velocidad de desgaste de bolas trituradoras de acero colado con ayuda de indicadores radiactivos

Energy Technology Data Exchange (ETDEWEB)

Keys, J D; Eichholz, G G [Department of Mines and Technical Surveys, Ottawa, ON (Canada)

1962-01-15

The wear rate of grinding balls used in ball mills is usually hard to determine under operational conditions and little is known-about the factors determining ball life. Radioactive tracers have been used successfully to mark cast steel balls to obtain information on their life under various operating conditions for comparison with balls of different type or composition. A batch of marked steel balls has been followed through a milling operation over several weeks and statistics on wear and loss of weight have been obtained. In the test runs cobalt-60 was added to the molten metal before casting and the balls were then observed in use at an iron mine. The radioactive batch was added to a ball mill with a normal charge of about 75 tons and the mill charge was sampled at weekly intervals to pick out active balls. These balls were inspected and weighed, and the wear rate has been calculated. This procedure has proved to be a practical way of investigating wear properties under plant operating conditions. (author) [French] Il est en general difficile de determiner le taux d'usure des boulets de broyeurs dans des conditions normales d'utilisation et l'on ne sait pas grand-chose des facteurs qui determinent la longevite des boulets. Les auteurs ont employe avec succes des indicateurs radioactifs pour marquer des boulets d'acier moule, en vue d'obtenir des indications sur leur duree dans diverses conditions de. fonctionnement et de faire une comparaison entre des boulets de type different ou de. composition differente. Ils ont suivi un lot de boulets, d'acier ainsi marques pendant une operation de broyage qui a dirre plusieurs semaines, ce qui a permis de recueillir des donnees statistiques sur leur usure et leur perte de poids. Au cours des essais, du cobalt-60 a ete ajoute au metal fondu avant le moulage des boulets. Ceux-ci ont ete ensuite maintenus en observation pendant leur emploi dans une mine de fer et une mine d'or. Le lot radioactif a ete introduit danfe un broyeur ayant une charge normale d'environ 75 tonnes et des echantillons ont ete preleves a des intervalles d'une semaine pour la recuperation des boulets radioactifs. Ces boulets etaient alors inspectes et peses, apres quoi on a pu calculer leur taux d'usure. Cette methode s'est revelee tres pratique. pour l'etude de la resistance des boulets a l'usure dans les conditions habituelles d'utilisation. (author) [Spanish] La velocidad de desgaste de las bolas trituradoras empleadas en los molinos suele ser dificil de determinar durante el funcionamiento de la maquina, y solo se poseen escasos conocimientos acerca de los factores que determinan su vida util. Los autores utilizaron con exito indicadores radiactivos para marcar bolas de acero colado, con miras a obtener informacion sobre su vida util en diversas condiciones de empleo y compararlas con otras bolas de composicion o tipo distintos. Tomaron un juego de bolas de acero marcadas, y observaron su comportamiento a lo largo de varias semanas de empleo en el molino, obteniendo asi datos estadisticos sobre el desgaste y la perdida de peso sufridos. En las pruebas experimentales anadieron {sup 60}Co al metal fundido antes de colarlas bolas y observaron su comportamiento utilizandolas en una mina de hierro y en otra de oro. Emplearon las bolas marcadas en un molino cuya carga normal es de 75 toneladas aproximadamente, y extrajeron semanalmente muestras del contenido de la maquina para separar bolas activas. Examinaron estas y las pesaron, calculando asi su velocidad de desgaste. Este procedimiento se ha revelado como un metodo practico para el estudio de la resistencia al desgaste de las bolas en condiciones industriales. (author) [Russian] Skorost' iznosa drobil'nykh sharov, ispol'zuemykh v sharovykh drobilkakh, obychno trudno poddaetsya opredeleniyu v rabochikh usloviyakh; k tomu zhe malo chto izvestno otnositel'no faktorov, opredelyayushchikh srok sluzhby drobil'nykh sharov. Dlya polucheniya svedenij o sroke sluzhby drobil'nykh sharov v razlichnykh rabochikh usloviyakh i dlya sopostavleniya rezul'tatov, poluchaemykh s sharami raznykh tipov ili raznogo sostava, byli uspeshno ispol'zovany mechenye atomy. Na protyazhenii neskol'kikh nedel' bylo provedeno nablyudenie za partiej mechenykh stal'nykh sharov v drobil'noj rabote i byli sobrany statisticheskie dannye otnositel'no iznosa i poteri vesa. V khode opytnykh tsiklov do otlivki sharov k rasplavlennomu metallu byl dobavlen kobal't-60 i posle ehtogo bylo provedeno nablyudenie nad litymi sharami v ikh rabote na razrabotkakh zheleznoj rudy. Partiya mechenykh radioizotopami sharov byla dobavlena k drobil'nym sharam drobilki s normal'noj emkost'yu zagruzki priblizitel'no v 75 tonn, H cherez kazhduyu nedelyu iz drobilki vybiralis' obraztsy zagruzki dlya iz{sup y}atiya mechenykh sharov. EHti shary proveryalis' i vzveshivalis' i podschityvalas' skorost' ikh iznosa. EHtot metod okazalsya praktichnym sposobom issledovaniya svojstv iznosa v rabochikh usloviyakh na ustanovke. (author)

The use of radiotracer techniques to study lubrication and wear in large diesel engines; Emploi des indicateurs radioactifs pour l'etude de la lubrification et de l'usure dans les moteurs diesel de grande puissance; Ispol'zovanie metodov radioaktivnykh indikatorov dlya izucheniya smazki i iznosa bol'shikh dizel'nykh motorov; Aplicacion de los indicadores radiactivos al estudio de la lubricacion y desgaste de los motores diesel de gran potencia

Energy Technology Data Exchange (ETDEWEB)

Howes, Jr, J E; Braun, W J; Sunderman, D N [Battelle Memorial Institute, Columbus, OH (United States)

1962-01-15

iznosa bol'shikh dizel'nykh motorov v masshtabe, kotoryj do sikh por schitalsya prakticheski neosushchestvimym. Kak potreblenie smazochnogo masla, tak i iznos rubashki tsilindra opredelyalis' v funktsii ot rabochikh uslovij dizelya moshchnost'yu okolo 1000 tormoznykh loshadinykh sil. Byl vyrabotan metod mecheniya 200 gallonov smazochnogo masla 60 millikyuri tsinka-65 i opredeleniya potrebleniya masla pri pomoshchi vzyatiya obraztsov gazov vykhlopa pri rabote motora v raznoobraznykh usloviyakh. Izmerenie potrebleniya smazochnogo masla moglo byt' proizvedeno za 10 minut vremeni, vmesto 24 ili 48 chasov, trebovavshikhsya ran'she. Byl vyrabotan metod aktivatsii nejtronami nizshej chasti tsilindra dlinoyu v 48 dyujmov i diametrom rubashki v 8 dyujmov. Nadlezhashchee ehkranirovanie teplovykh nej- tronov dalo vozmozhnost' poluchit' marganets-54 s 300-dnevnym periodom poluraspada; issledovanie iznosa privelo k udlineniyu poleznogo sroka sluzhby rubashki v 6-8 raz po sravneniyu s analogichnoj rubashkoj, aktivirovannoj termicheski dlya proizvodstva zheleza-59. To obstoyatel'stvo, chto issledovaniya s takimi bol'shimi kolichestvami radioaktivnogo materiala mogut vypolnyat'sya v oblasti dizelej na normal'noj issledovatel'skoj ustanovke, otkryvaet sovershenno novuyu oblast' primeneniya indikatorov. Izbiratel'naya aktivatsiya i tselesoobraznoe ispol'zovanie ehkranirovaniya teplovykh nejtronov uvelichivayut raznoobrazie vozmozhnostej ispol'zovaniya metodov indikatorov; izmereniya sosredotochivayutsya na interesuyushchem meste, i tem samym sokrashchaetsya obshchee kolichestvo trebuemogo dlya izucheniya iznosa krupnykh detalej radioaktivnogo materiala; vmeste s tem odnovremenno oblegchaetsya izmerenie iznosa detalej motora iz materialov s odinakovym khimicheskim sostavom. (author)

Some solvent extraction studies of trivalent metal halides; Quelques etudes sur l'extraction par solvant d'halogenures de metaux trivalents; Izuchenie ehkstraktsii nekotorykh rastvoritelej iz trekhvalentnykh metallicheskikh galoidov; Algunos estudios de la extraccion mediante disolventes de haluros de metales trivalentes

Energy Technology Data Exchange (ETDEWEB)

Dietz, Jr, R J; Mendez, J; Irvine, Jr, J W [Department of Chemistry and Laboratory for Nuclear Science, Massachusetts Institute of Technology, Cambridge, MA (United States)

1962-03-15

el orden de magnitud del coeficiente varia en un intervalo de 10{sup 5}. Los autores explican los datos obtenidos sobre la base de la ionizacion del acido complejo HMX{sub 4} en estos disolventes, cuyas constantes dielectricas son relativamente elevadas. Empleando un metodo ideado por Poskanzer, han calculado la constante de ionizacion del electrolito soporte, HCl o HBr, en la fase no acuosa a partir de las variaciones que el coeficiente de extraccion experimenta en funcion de las concentraciones del metal. Las variaciones del coeficiente de extraccion con la concentracion de HX han servido para calcular las constantes de estabilidad de las especies complejas MX{sub 3} y MX{sub 4}{sup -}. Como se trata de reacciones en fase acuosa, las constantes son independientes del disolvente organico que se emplee. Para el sistema In (III)-HCl los autores obtuvieron resultados perfectamente concordantes tanto al emplear eter bis (2-cloroetilico) como nitrobenceno. Los autores no consiguieron evaluar las constantes de los complejos de cloruro y bromuro de galio porque dichos compuestos solo se forman en un intervalo de concentraciones de acido muy estrecho. Los valores del cociente (GaCl{sub 4}{sup -})/{Sigma} Ga (III) en funcion de la concentracion de HCl, calculados a partir de los datos de extraccion, concuerdan con los datos que Kraus y Nelson obtuvieron por mediciones del intercambio ionico. (author) [Russian] Metod mechenykh atomov pozvolil provesti izuchenie fiziko-khimicheskogo raspredeleniya Ga (III) i In (III) mezhdu vodnymi rastvorami HCl i HBr i organicheskimi rastvoritelyami, dvojnym ehfirom (2-khloroehtil) i nitrobenzolom. Na osnove izmerenij koehffitsientov ehkstraktsii pri kontsentratsii metalla vyshe 10{sup 10} i pri kolebanii dannogo koehffitsienta v predelakh 10{sup 5} tshchatel'no bylo razrabotano ehmpiricheskoe povedenie dannykh sistem. Rezul'taty vyrazhalis' v stepeni ionizatsii slozhnoj kisloty, HMX{sub 4}, izvestnoj v kachestve rastvoritelya s otnositel

Design of the Small Rods Forming the Fuel Element of the First Charge of the EL4 Reactor. Cladding Problems; Etude des crayons constituant l'element combustible du premier jeu d'EL4 - probleme de la gaine; Problema pokrytiya nebol'shikh steeknej, obrazushchikh toplivnyj ehlement pervoj zagruzki reaktora EL.4; Estudio de las barras que constituyen los elementos combustibles de la primera carga del reactor EL4 - el problema de las vainas

Energy Technology Data Exchange (ETDEWEB)

Bailly, H.; Ringot, C.; Weisz, M. [Centre d' Etudes Nucleaires de Saclay (France)

1963-11-15

) [Spanish] Las vainas de los elementos combustibles de la primera carga del reactor EL-4 son de acero inoxidable. La eleccion del grado del acero y del espesor de la vaina depende de la resistencia a la corrosion y de la resistencia mecanica que se deseen. Las tensiones y las temperaturas de funcionamiento no permiten concebir una vaina que resista durante toda la vida util del elemento combustible si no se uti liza un grado de acero muy resistente y un espesor,superior a 0,5 mm. Se admite que la vaina se adhiera al combustible por fluencia: la deformacion por juego en sentido diametral puede producir una ovalizacion y un pliegue; el juego longitudinal puede dar lugar a flexiones de la vaina. Se han realizado muchos ensayos con vainas de 0,3 a 0,4 mm de espesor para estudiar el modo de deformacion en funcion de los juegos. Para estar seguros de que no se produciran ovaliza ciones con los espesores previstos, y para mantener lo mas baja posible la temperatura en el interior de la barra es preciso eliminar completamente el juego durante la fabricacion. (author) [Russian] Dlya pervoj nagruzki toplivnogo ehlementa reaktora EL.4 ispol'zuetsya pokrytie iz nerzhaveyushchej stali. Vybor splava i tolshchiny pokrytiya svyazan s korrozionnymi i mekhanicheskimi svojstvami metalla. Rabochie napryakheniya i temperatury ne dast vozmokhnosti sproektirovat' pokrytie, stojkoe v techenie vsego sroka sluzhby toplivnogo ehlementa; dlya dostikheniya takoj tseli neobkhodimo bylo by ispol'zovat' ochen' stojkoe pokrytie tolshchinoj bolee 0,5 mm. Dopuskaetsya, chto pokrytie v protsesse spekaniya soedinyaetsya s toplivom. Diametral'noe izmenenie toplivnykh ehlementov mokhet privesti k obrazovaniyu oval'noj formy i nerovnostej; prodol'noe izmenenie sistemy toplivnykh ehlementov mokhet privesti k prodol'nomu izgibu pokrytiya. Byli provedeny mnogochislennye opyty v otnoshenii tolshchiny pokrytiya v predelakh' 0,3 - 0,4 mm s tem, chtoby vyyasnit' kharakter izmeneniya toplivnykh ehlementov v zavisimosti

Separation of Impurities in the Zinc Rectification Process by Radioactive Isotopes; Separation des Impuretes, a l'Aide de Radioisotopes, dans l'Affinage du Zinc par Voie Seche; ОТДЕЛЕНИЕ ПРИМЕСЕЙ В ПРОЦЕССЕ РЕКТИФИКАЦИИ ЦИНКА С ПРИМЕНЕНИЕМ РАДИОАКТИВНЫХ РАДИОИЗОТОПОВ; Estudio Mediante Radioisotopos de la Separacion de Impurezas en el Proceso de Purificacion del Cinc

Energy Technology Data Exchange (ETDEWEB)

Akerman, K.; Brafman, M.; Fik, H.; Kitala, J.; Nowak, M.; Poczynajlo, A. [Institute of Nuclear Research, Polish Academy of Sciences, Warsaw (Poland)

1963-03-15

. Privedeny takte prakticheskie vyvody, kotorye javljajutsja rezul'tatom matematicheskogo issledovanija processa rektifikacii s tochki zrenija jetoj teorii. V rabote opisany opyty po issledovaniju processa rektifikacii cinka, v kotoryh byli primeneny radioaktivnye izotopy. Issledovalos' otdelenie primesej, obladajushhih vysokoj i nizkoj temperaturoj kipenija, a takzhe povedenie osnovnoj sostavljajushhej, to-est' cinka, vo vremja normal'noj raboty kolonny. V opytah byli primeneny sledujushhie radioaktivnye izotopy: Cu{sup 64}, Fe{sup 98} (vysokokipjashhie primesi), Cd{sup 115} (primes' s nizkoj temperaturoj kipenija) i Zneem (osnovnaja sostavljajushhaja). Rezul'taty provedennyh issledovanij javljajutsja opytnym podtverzhdeniem teorii A. Krupkovskogo. Poluchennye dannye ukazyvajut na celesoobraznost' izmenenija parametrov kondensacii parov cinka i kadmija v kadmievoj kolonne dlja togo, chtoby uvelichit' izvlechenie kadmija iz ishodnogo metalla i povysit' kachestvo cinka, poluchaemogo v rezul'tate rektifikacii. (author)