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Sample records for f-elements osobennosti kompleksoobrazovaniya

  1. Cyanide metallocenes of trivalent f-elements

    International Nuclear Information System (INIS)

    Maynadie, J.; Berthet, J.C.; Thuery, P.; Ephritikhine, M.

    2007-01-01

    Addition of N n Bu 4 CN to (C 5 Me 5 ) 2 UI(py), (C 5 Me 5 ) 2 CeI, or (C 5 Me 5 ) 2 M(OTf) (M = U, Ce) in acetonitrile led to the precipitation of the neutral mono-cyanide species [(C 5 Me 5 ) 2 M(μ-CN)] n [M = U (1), Ce (2)], which likely have an oligomeric structure, as shown by the tri-meric cyanide-bridged complex [(C 5 Me 5 ) 2 Ce(μ-CN)(CN t Bu)] 3 (3) obtained by addition of excess t BuNC into a suspension of 2 in acetonitrile. The structure of the U(III,IV) mixed valence compound [{(C 5 Me 5 ) 2 U} 2 (μ-CN){(μ-CN) 2 Na(thf)} 2 ] ∞ (4), which crystallized from a thf solution of (C 5 Me 5 ) 2 UI(py) in the presence of excess NaCN, reveals a unique example of an f-element-(μ-CN)-M interaction (M = main group or d transition metal). The anionic poly-cyanides [(C 5 Me 5 ) 2 M(CN) 3 ][N n Bu 4 ] 2 [M = U (5), Ce (6)] were synthesized by treatment of 1 and 2 with 2 equiv or an excess of N n Bu 4 CN in acetonitrile; they were also prepared in a one-pot procedure by stepwise addition of 1 equiv of KCN and 2 equiv of N n Bu 4 CN to the parent iodides in acetonitrile. The bent metallocenes 5 and 6 are unique low-valent molecular poly-cyanide compounds of an f-element that have been structurally identified, while 5 is the first fully characterized actinide(III) cyanide. Comparison of the crystal structures of 5 and 6 shows that the M-C(C 5 Me 5 ) and M-C(CN) distances are 0.02-0.03 Angstroms shorter for M = U than for M Ce, while the ionic radius of uranium(III) is 0.02 Angstroms larger than that of cerium(III). (authors)

  2. High-pressure on f-element materials

    International Nuclear Information System (INIS)

    Haire, R.G.

    1991-01-01

    540Studies of the f-elements under pressure provide important insights into their solid state chemistry and physics. From such studies of the elements and their alloys, it has been established that the normally localized f-electrons of several of these elements can become involved in bonding under pressure. The electronic behavior of f-element compounds under pressure tend to be more difficult to interpret, due to the variety and the nature of electronic orbitals that are present. The 4f-elements and some 60% of the 5f-elements have been studied under pressure. The systematic comparisons that have been established for these materials are discussed. 76 refs., 3 figs

  3. Organometallic chemistry of the f-elements: toward new development: cyanide ligand of f-elements

    International Nuclear Information System (INIS)

    Herve, Alexandre

    2014-01-01

    The cyanide ligand is one of the most widely used ligands in coordination chemistry of d-transition metals. The low number of cyanide complexes of lanthanides and actinides incited us to develop this field for reactivity and theoretical aspects, and also for their potentially interesting physicochemical properties. In this Ph.D., we investigated the reactivity of [An(Cot) 2 ] (An = Th, U ; Cot = C 8 H 8 2- ) and [M f (N*) 3 ] q+ (q = 0, 1; M f = Ce, U ; N* = -N(SiMe 3 ) 2 ) precursors toward the cyanide ion. The first chapter is dedicated to the synthesis and characterization of trivalent f-elements cyanide complexes [M f (N*) 3 (CN)][M], [M f (N*) 3 (CN) 2 ][M] 2 et [M f (N*) 2 (CN) 3 ][M] 2 and the cyanido-bridged binuclear compounds [{M f (N*) 3 } 2 (μ-CN)][M] (M = NR 4 , K(18-C-6)). Crystals of the bis(cyanido) uranium and cerium complexes are not isostructural since the data revealed distinct coordination modes of the CN group, through the C or N atom to the U 3+ or Ce 3+ metal center, respectively. In chapter 2, the novel silyl-amide uranium(IV) precursor [U(N*) 3 ][BPh 4 ] has been isolated, and proved to be useful for the synthesis of the cationic species [{U(N*) 3 } 2 (μ-CN)][BPh 4 ] and the neutral monocyanide [M f (N*) 3 (CN)] and anionic bis(cyanide) [M f (N*) 3 (CN) 2 ][M] derivatives. Here again, the X-ray data reveal the uncommon N coordination mode of the CN group to the U(IV) center. This global differentiation has been analyzed using density functional theory calculations. The observed preferential coordination of the cyanide ion in Ce(III)-NC, U(III)-CN and U(IV)-NC is corroborated by energetic considerations and by the comparison of DFT optimized geometries with the true crystal structures. Finally, the recent discovery of the first bent 'uranocene' species, eg [U(Cot) 2 (CN)] - , led us to compare the reactivity of the actinocenes [An(Cot) 2 ] (Th, U) in order to understand the effect of the metal electron configuration

  4. The application of f-elements in ecological research

    International Nuclear Information System (INIS)

    Knaus, R.M.

    1991-01-01

    The utilization of f-elements has a relatively minor status as a research tool in the biological sciences, especially ecology, because they play neither positive nor deleterious roles in plant and animal nutrition. Additionally, detection and quantification via instrumental neutron activation analysis (INAA) of environmental samples is not yet routine. At Louisiana State University, La, Sm, and Dy have been used successfully as activable stable tracers in a wide range of ecological studies including the quantification using Sm and Dy of short-term sedimentary and erosional processes in wetlands; and behavior studies using Sm on agricultural lands where radioisotopes are precluded; the sorption of Dy and La by roots of stream-side trees; and the quantification of exogenous Dy and Sm from animal decay products in streams. With advances in sample automation and standardization in INAA detection methods, the quantification of f-element tracers in complex biological matrices is within reach of ecological scientists

  5. Hypersensitive transition spectrum of f-element and coordination structure

    International Nuclear Information System (INIS)

    Cao Xuan; Song Chongli; Zhu Youngjun

    1992-10-01

    Some f-f transitions of Ln(An) metallic ions have particular super-sensitivity to the change of coordination environments. This is called super-sensitive transitions. Based on the irreducible tensor operator method, a computation model and corresponding computer program for calculating the hypersensitive transition spectrum of f-element were developed. By comparing the theoretical spectra of all possible coordination structures with experimental one, the possible coordination structures of complex can be determined. The coordination structures of Nd 3+ , Er 3 + hydrate and their extraction complex with H(DEHP) were successfully determined by this method, and the experimental spectra were also assigned

  6. f-Element Ion Chelation in Highly Basic Media

    International Nuclear Information System (INIS)

    Paine, R.T.

    2000-01-01

    A large body of data has been collected over the last fifty years on the chemical behavior of f-element ions. The ions undergo rapid hydrolysis reactions in neutral or basic aqueous solutions that produce poorly understood oxide-hydroxide species; therefore, most of the fundamental f-element solution chemistry has allowed synthetic and separations chemists to rationally design advanced organic chelating ligands useful for highly selective partitioning and separation of f-element ions from complex acidic solution matrices. These ligands and new examples under development allow for the safe use and treatment of solutions containing highly radioactive species. This DOE/EMSP project was undertaken to address the following fundamental objectives: (1) study the chemical speciation of Sr and lanthanide (Ln) ions in basic aqueous media containing classical counter anions found in waste matrices; (2) prepare pyridine N-oxide phosphonates and phosphonic acids that might act as selective chelators for Ln ions in model basic pH waste streams; (3) study the binding of the new chelators toward Ln ions and (4) examine the utility of the chelators as decontamination and dissolution agents under basic solution conditions. The project has been successful in attacking selected aspects of the very difficult problems associated with basic pH solution f-element waste chemistry. In particular, the project has (1) shed additional light on the initial stages of Ln ion sol-gel-precipitate formulation under basic solution conditions; (2) generated new families of pyridine phosphonic acid chelators; (3) characterized the function of the chelators and (4) examined their utility as oxide-hydroxide dissolution agents. These findings have contributed significantly to an improved understanding of the behavior of Ln ions in basic media containing anions found in typical waste sludges as well as to the development of sludge dissolution agents. The new chelating reagents are easily made and could be

  7. Separations chemistry for f elements: Recent developments and historical perspective

    International Nuclear Information System (INIS)

    Nash, K.L.; Choppin, G.R.

    1995-01-01

    With the end of the cold war, the principal mission in actinide separations has changed from production of plutonium to cleanup of the immense volume of moderately radioactive mixed wastes which resulted from fifty years of processing activities. In order to approach the cleanup task from a proper perspective, it is necessary to understand the nature of the problem and how the wastes were generated. In this report, the history of actinide separations, both the basic science and production aspects, is examined. Many of the separations techniques in use today were developed in the 40's and 50's for the identification and production of actinide elements. To respond to the modern world of actinide separations new techniques are being developed for separations ranging from analytical methods to detect ultra-trace concentrations (for bioassay and environmental monitoring) to large scale waste treatment procedures. Some of these new methods are ''improvements'' or adaptations of the historical techniques. Total actinide recovery, lanthanide/actinide separations, and selective partitioning of actinides from inert constituents are of primary concern. This report, offers a historical perspective, review the current status of f element separation processes, and suggest areas for continued research in both actinide separations and waste cleanup/environment remediation

  8. f-Element Ion Chelation in Highly Basic Media

    International Nuclear Information System (INIS)

    Paine, Robert T.

    1999-01-01

    High-level radioactive waste (HLW) generated in the DOE complex is stored in tanks at several sites, but predominantly it is found at the Hanford reservation. Much of the material has been exposed to high pHs, consequently the waste exists in a complex, poorly understood mixture of solids, gels and solutions. The final waste remediation plan may involve chemical separation of fractions and a suitable, well developed molecular chemistry basis for performing these separations is not available. Indeed, the fundamental chemical behavior of most radioactive nuclides in basic media is not known. The goal of this project is to undertake fundamental studies of the coordination chemistry of f-element species in basic aqueous solutions containing common waste treatment ions (e.g., NO3 -, CO3 2-, organic carboxylates, and EDTA), as well as new waste scrubbing chelators produced in this study. The experimental agenda includes: 1. Studies of the speciation of Sr and Ln ions in basic solutions wit h and without common counterions; 2. Preparations of new multifunctional ligands that may act as strong, ion-specific chelators for Sr and/or Ln ions in basic media; and 3. Studies of the coordination and dissolution behavior of oxide-hydroxide species, as well as in insoluble sols, gels, and precipitates in combination with new chelating ligands. It is anticipated that this coordination chemistry will facilitate the design of advanced separation schemes required for handling the complex waste matrices found at the Hanford HLW facility

  9. Retrotransposons Are the Major Contributors to the Expansion of the Drosophila ananassae Muller F Element.

    Science.gov (United States)

    Leung, Wilson; Shaffer, Christopher D; Chen, Elizabeth J; Quisenberry, Thomas J; Ko, Kevin; Braverman, John M; Giarla, Thomas C; Mortimer, Nathan T; Reed, Laura K; Smith, Sheryl T; Robic, Srebrenka; McCartha, Shannon R; Perry, Danielle R; Prescod, Lindsay M; Sheppard, Zenyth A; Saville, Ken J; McClish, Allison; Morlock, Emily A; Sochor, Victoria R; Stanton, Brittney; Veysey-White, Isaac C; Revie, Dennis; Jimenez, Luis A; Palomino, Jennifer J; Patao, Melissa D; Patao, Shane M; Himelblau, Edward T; Campbell, Jaclyn D; Hertz, Alexandra L; McEvilly, Maddison F; Wagner, Allison R; Youngblom, James; Bedi, Baljit; Bettincourt, Jeffery; Duso, Erin; Her, Maiye; Hilton, William; House, Samantha; Karimi, Masud; Kumimoto, Kevin; Lee, Rebekah; Lopez, Darryl; Odisho, George; Prasad, Ricky; Robbins, Holly Lyn; Sandhu, Tanveer; Selfridge, Tracy; Tsukashima, Kara; Yosif, Hani; Kokan, Nighat P; Britt, Latia; Zoellner, Alycia; Spana, Eric P; Chlebina, Ben T; Chong, Insun; Friedman, Harrison; Mammo, Danny A; Ng, Chun L; Nikam, Vinayak S; Schwartz, Nicholas U; Xu, Thomas Q; Burg, Martin G; Batten, Spencer M; Corbeill, Lindsay M; Enoch, Erica; Ensign, Jesse J; Franks, Mary E; Haiker, Breanna; Ingles, Judith A; Kirkland, Lyndsay D; Lorenz-Guertin, Joshua M; Matthews, Jordan; Mittig, Cody M; Monsma, Nicholaus; Olson, Katherine J; Perez-Aragon, Guillermo; Ramic, Alen; Ramirez, Jordan R; Scheiber, Christopher; Schneider, Patrick A; Schultz, Devon E; Simon, Matthew; Spencer, Eric; Wernette, Adam C; Wykle, Maxine E; Zavala-Arellano, Elizabeth; McDonald, Mitchell J; Ostby, Kristine; Wendland, Peter; DiAngelo, Justin R; Ceasrine, Alexis M; Cox, Amanda H; Docherty, James E B; Gingras, Robert M; Grieb, Stephanie M; Pavia, Michael J; Personius, Casey L; Polak, Grzegorz L; Beach, Dale L; Cerritos, Heaven L; Horansky, Edward A; Sharif, Karim A; Moran, Ryan; Parrish, Susan; Bickford, Kirsten; Bland, Jennifer; Broussard, Juliana; Campbell, Kerry; Deibel, Katelynn E; Forka, Richard; Lemke, Monika C; Nelson, Marlee B; O'Keeffe, Catherine; Ramey, S Mariel; Schmidt, Luke; Villegas, Paola; Jones, Christopher J; Christ, Stephanie L; Mamari, Sami; Rinaldi, Adam S; Stity, Ghazal; Hark, Amy T; Scheuerman, Mark; Silver Key, S Catherine; McRae, Briana D; Haberman, Adam S; Asinof, Sam; Carrington, Harriette; Drumm, Kelly; Embry, Terrance; McGuire, Richard; Miller-Foreman, Drew; Rosen, Stella; Safa, Nadia; Schultz, Darrin; Segal, Matt; Shevin, Yakov; Svoronos, Petros; Vuong, Tam; Skuse, Gary; Paetkau, Don W; Bridgman, Rachael K; Brown, Charlotte M; Carroll, Alicia R; Gifford, Francesca M; Gillespie, Julie Beth; Herman, Susan E; Holtcamp, Krystal L; Host, Misha A; Hussey, Gabrielle; Kramer, Danielle M; Lawrence, Joan Q; Martin, Madeline M; Niemiec, Ellen N; O'Reilly, Ashleigh P; Pahl, Olivia A; Quintana, Guadalupe; Rettie, Elizabeth A S; Richardson, Torie L; Rodriguez, Arianne E; Rodriguez, Mona O; Schiraldi, Laura; Smith, Joanna J; Sugrue, Kelsey F; Suriano, Lindsey J; Takach, Kaitlyn E; Vasquez, Arielle M; Velez, Ximena; Villafuerte, Elizabeth J; Vives, Laura T; Zellmer, Victoria R; Hauke, Jeanette; Hauser, Charles R; Barker, Karolyn; Cannon, Laurie; Parsamian, Perouza; Parsons, Samantha; Wichman, Zachariah; Bazinet, Christopher W; Johnson, Diana E; Bangura, Abubakarr; Black, Jordan A; Chevee, Victoria; Einsteen, Sarah A; Hilton, Sarah K; Kollmer, Max; Nadendla, Rahul; Stamm, Joyce; Fafara-Thompson, Antoinette E; Gygi, Amber M; Ogawa, Emmy E; Van Camp, Matt; Kocsisova, Zuzana; Leatherman, Judith L; Modahl, Cassie M; Rubin, Michael R; Apiz-Saab, Susana S; Arias-Mejias, Suzette M; Carrion-Ortiz, Carlos F; Claudio-Vazquez, Patricia N; Espada-Green, Debbie M; Feliciano-Camacho, Marium; Gonzalez-Bonilla, Karina M; Taboas-Arroyo, Mariela; Vargas-Franco, Dorianmarie; Montañez-Gonzalez, Raquel; Perez-Otero, Joseph; Rivera-Burgos, Myrielis; Rivera-Rosario, Francisco J; Eisler, Heather L; Alexander, Jackie; Begley, Samatha K; Gabbard, Deana; Allen, Robert J; Aung, Wint Yan; Barshop, William D; Boozalis, Amanda; Chu, Vanessa P; Davis, Jeremy S; Duggal, Ryan N; Franklin, Robert; Gavinski, Katherine; Gebreyesus, Heran; Gong, Henry Z; Greenstein, Rachel A; Guo, Averill D; Hanson, Casey; Homa, Kaitlin E; Hsu, Simon C; Huang, Yi; Huo, Lucy; Jacobs, Sarah; Jia, Sasha; Jung, Kyle L; Wai-Chee Kong, Sarah; Kroll, Matthew R; Lee, Brandon M; Lee, Paul F; Levine, Kevin M; Li, Amy S; Liu, Chengyu; Liu, Max Mian; Lousararian, Adam P; Lowery, Peter B; Mallya, Allyson P; Marcus, Joseph E; Ng, Patrick C; Nguyen, Hien P; Patel, Ruchik; Precht, Hashini; Rastogi, Suchita; Sarezky, Jonathan M; Schefkind, Adam; Schultz, Michael B; Shen, Delia; Skorupa, Tara; Spies, Nicholas C; Stancu, Gabriel; Vivian Tsang, Hiu Man; Turski, Alice L; Venkat, Rohit; Waldman, Leah E; Wang, Kaidi; Wang, Tracy; Wei, Jeffrey W; Wu, Dennis Y; Xiong, David D; Yu, Jack; Zhou, Karen; McNeil, Gerard P; Fernandez, Robert W; Menzies, Patrick Gomez; Gu, Tingting; Buhler, Jeremy; Mardis, Elaine R; Elgin, Sarah C R

    2017-08-07

    The discordance between genome size and the complexity of eukaryotes can partly be attributed to differences in repeat density. The Muller F element (∼5.2 Mb) is the smallest chromosome in Drosophila melanogaster , but it is substantially larger (>18.7 Mb) in D. ananassae To identify the major contributors to the expansion of the F element and to assess their impact, we improved the genome sequence and annotated the genes in a 1.4-Mb region of the D. ananassae F element, and a 1.7-Mb region from the D element for comparison. We find that transposons (particularly LTR and LINE retrotransposons) are major contributors to this expansion (78.6%), while Wolbachia sequences integrated into the D. ananassae genome are minor contributors (0.02%). Both D. melanogaster and D. ananassae F-element genes exhibit distinct characteristics compared to D-element genes ( e.g. , larger coding spans, larger introns, more coding exons, and lower codon bias), but these differences are exaggerated in D. ananassae Compared to D. melanogaster , the codon bias observed in D. ananassae F-element genes can primarily be attributed to mutational biases instead of selection. The 5' ends of F-element genes in both species are enriched in dimethylation of lysine 4 on histone 3 (H3K4me2), while the coding spans are enriched in H3K9me2. Despite differences in repeat density and gene characteristics, D. ananassae F-element genes show a similar range of expression levels compared to genes in euchromatic domains. This study improves our understanding of how transposons can affect genome size and how genes can function within highly repetitive domains. Copyright © 2017 Leung et al.

  10. Retrotransposons Are the Major Contributors to the Expansion of the Drosophila ananassae Muller F Element

    Directory of Open Access Journals (Sweden)

    Wilson Leung

    2017-08-01

    Full Text Available The discordance between genome size and the complexity of eukaryotes can partly be attributed to differences in repeat density. The Muller F element (∼5.2 Mb is the smallest chromosome in Drosophila melanogaster, but it is substantially larger (>18.7 Mb in D. ananassae. To identify the major contributors to the expansion of the F element and to assess their impact, we improved the genome sequence and annotated the genes in a 1.4-Mb region of the D. ananassae F element, and a 1.7-Mb region from the D element for comparison. We find that transposons (particularly LTR and LINE retrotransposons are major contributors to this expansion (78.6%, while Wolbachia sequences integrated into the D. ananassae genome are minor contributors (0.02%. Both D. melanogaster and D. ananassae F-element genes exhibit distinct characteristics compared to D-element genes (e.g., larger coding spans, larger introns, more coding exons, and lower codon bias, but these differences are exaggerated in D. ananassae. Compared to D. melanogaster, the codon bias observed in D. ananassae F-element genes can primarily be attributed to mutational biases instead of selection. The 5′ ends of F-element genes in both species are enriched in dimethylation of lysine 4 on histone 3 (H3K4me2, while the coding spans are enriched in H3K9me2. Despite differences in repeat density and gene characteristics, D. ananassae F-element genes show a similar range of expression levels compared to genes in euchromatic domains. This study improves our understanding of how transposons can affect genome size and how genes can function within highly repetitive domains.

  11. Retrotransposons Are the Major Contributors to the Expansion of the Drosophila ananassae Muller F Element

    Science.gov (United States)

    Shaffer, Christopher D.; Chen, Elizabeth J.; Quisenberry, Thomas J.; Ko, Kevin; Braverman, John M.; Giarla, Thomas C.; Mortimer, Nathan T.; Reed, Laura K.; Smith, Sheryl T.; Robic, Srebrenka; McCartha, Shannon R.; Perry, Danielle R.; Prescod, Lindsay M.; Sheppard, Zenyth A.; Saville, Ken J.; McClish, Allison; Morlock, Emily A.; Sochor, Victoria R.; Stanton, Brittney; Veysey-White, Isaac C.; Revie, Dennis; Jimenez, Luis A.; Palomino, Jennifer J.; Patao, Melissa D.; Patao, Shane M.; Himelblau, Edward T.; Campbell, Jaclyn D.; Hertz, Alexandra L.; McEvilly, Maddison F.; Wagner, Allison R.; Youngblom, James; Bedi, Baljit; Bettincourt, Jeffery; Duso, Erin; Her, Maiye; Hilton, William; House, Samantha; Karimi, Masud; Kumimoto, Kevin; Lee, Rebekah; Lopez, Darryl; Odisho, George; Prasad, Ricky; Robbins, Holly Lyn; Sandhu, Tanveer; Selfridge, Tracy; Tsukashima, Kara; Yosif, Hani; Kokan, Nighat P.; Britt, Latia; Zoellner, Alycia; Spana, Eric P.; Chlebina, Ben T.; Chong, Insun; Friedman, Harrison; Mammo, Danny A.; Ng, Chun L.; Nikam, Vinayak S.; Schwartz, Nicholas U.; Xu, Thomas Q.; Burg, Martin G.; Batten, Spencer M.; Corbeill, Lindsay M.; Enoch, Erica; Ensign, Jesse J.; Franks, Mary E.; Haiker, Breanna; Ingles, Judith A.; Kirkland, Lyndsay D.; Lorenz-Guertin, Joshua M.; Matthews, Jordan; Mittig, Cody M.; Monsma, Nicholaus; Olson, Katherine J.; Perez-Aragon, Guillermo; Ramic, Alen; Ramirez, Jordan R.; Scheiber, Christopher; Schneider, Patrick A.; Schultz, Devon E.; Simon, Matthew; Spencer, Eric; Wernette, Adam C.; Wykle, Maxine E.; Zavala-Arellano, Elizabeth; McDonald, Mitchell J.; Ostby, Kristine; Wendland, Peter; DiAngelo, Justin R.; Ceasrine, Alexis M.; Cox, Amanda H.; Docherty, James E.B.; Gingras, Robert M.; Grieb, Stephanie M.; Pavia, Michael J.; Personius, Casey L.; Polak, Grzegorz L.; Beach, Dale L.; Cerritos, Heaven L.; Horansky, Edward A.; Sharif, Karim A.; Moran, Ryan; Parrish, Susan; Bickford, Kirsten; Bland, Jennifer; Broussard, Juliana; Campbell, Kerry; Deibel, Katelynn E.; Forka, Richard; Lemke, Monika C.; Nelson, Marlee B.; O'Keeffe, Catherine; Ramey, S. Mariel; Schmidt, Luke; Villegas, Paola; Jones, Christopher J.; Christ, Stephanie L.; Mamari, Sami; Rinaldi, Adam S.; Stity, Ghazal; Hark, Amy T.; Scheuerman, Mark; Silver Key, S. Catherine; McRae, Briana D.; Haberman, Adam S.; Asinof, Sam; Carrington, Harriette; Drumm, Kelly; Embry, Terrance; McGuire, Richard; Miller-Foreman, Drew; Rosen, Stella; Safa, Nadia; Schultz, Darrin; Segal, Matt; Shevin, Yakov; Svoronos, Petros; Vuong, Tam; Skuse, Gary; Paetkau, Don W.; Bridgman, Rachael K.; Brown, Charlotte M.; Carroll, Alicia R.; Gifford, Francesca M.; Gillespie, Julie Beth; Herman, Susan E.; Holtcamp, Krystal L.; Host, Misha A.; Hussey, Gabrielle; Kramer, Danielle M.; Lawrence, Joan Q.; Martin, Madeline M.; Niemiec, Ellen N.; O'Reilly, Ashleigh P.; Pahl, Olivia A.; Quintana, Guadalupe; Rettie, Elizabeth A.S.; Richardson, Torie L.; Rodriguez, Arianne E.; Rodriguez, Mona O.; Schiraldi, Laura; Smith, Joanna J.; Sugrue, Kelsey F.; Suriano, Lindsey J.; Takach, Kaitlyn E.; Vasquez, Arielle M.; Velez, Ximena; Villafuerte, Elizabeth J.; Vives, Laura T.; Zellmer, Victoria R.; Hauke, Jeanette; Hauser, Charles R.; Barker, Karolyn; Cannon, Laurie; Parsamian, Perouza; Parsons, Samantha; Wichman, Zachariah; Bazinet, Christopher W.; Johnson, Diana E.; Bangura, Abubakarr; Black, Jordan A.; Chevee, Victoria; Einsteen, Sarah A.; Hilton, Sarah K.; Kollmer, Max; Nadendla, Rahul; Stamm, Joyce; Fafara-Thompson, Antoinette E.; Gygi, Amber M.; Ogawa, Emmy E.; Van Camp, Matt; Kocsisova, Zuzana; Leatherman, Judith L.; Modahl, Cassie M.; Rubin, Michael R.; Apiz-Saab, Susana S.; Arias-Mejias, Suzette M.; Carrion-Ortiz, Carlos F.; Claudio-Vazquez, Patricia N.; Espada-Green, Debbie M.; Feliciano-Camacho, Marium; Gonzalez-Bonilla, Karina M.; Taboas-Arroyo, Mariela; Vargas-Franco, Dorianmarie; Montañez-Gonzalez, Raquel; Perez-Otero, Joseph; Rivera-Burgos, Myrielis; Rivera-Rosario, Francisco J.; Eisler, Heather L.; Alexander, Jackie; Begley, Samatha K.; Gabbard, Deana; Allen, Robert J.; Aung, Wint Yan; Barshop, William D.; Boozalis, Amanda; Chu, Vanessa P.; Davis, Jeremy S.; Duggal, Ryan N.; Franklin, Robert; Gavinski, Katherine; Gebreyesus, Heran; Gong, Henry Z.; Greenstein, Rachel A.; Guo, Averill D.; Hanson, Casey; Homa, Kaitlin E.; Hsu, Simon C.; Huang, Yi; Huo, Lucy; Jacobs, Sarah; Jia, Sasha; Jung, Kyle L.; Wai-Chee Kong, Sarah; Kroll, Matthew R.; Lee, Brandon M.; Lee, Paul F.; Levine, Kevin M.; Li, Amy S.; Liu, Chengyu; Liu, Max Mian; Lousararian, Adam P.; Lowery, Peter B.; Mallya, Allyson P.; Marcus, Joseph E.; Ng, Patrick C.; Nguyen, Hien P.; Patel, Ruchik; Precht, Hashini; Rastogi, Suchita; Sarezky, Jonathan M.; Schefkind, Adam; Schultz, Michael B.; Shen, Delia; Skorupa, Tara; Spies, Nicholas C.; Stancu, Gabriel; Vivian Tsang, Hiu Man; Turski, Alice L.; Venkat, Rohit; Waldman, Leah E.; Wang, Kaidi; Wang, Tracy; Wei, Jeffrey W.; Wu, Dennis Y.; Xiong, David D.; Yu, Jack; Zhou, Karen; McNeil, Gerard P.; Fernandez, Robert W.; Menzies, Patrick Gomez; Gu, Tingting; Buhler, Jeremy; Mardis, Elaine R.; Elgin, Sarah C.R.

    2017-01-01

    The discordance between genome size and the complexity of eukaryotes can partly be attributed to differences in repeat density. The Muller F element (∼5.2 Mb) is the smallest chromosome in Drosophila melanogaster, but it is substantially larger (>18.7 Mb) in D. ananassae. To identify the major contributors to the expansion of the F element and to assess their impact, we improved the genome sequence and annotated the genes in a 1.4-Mb region of the D. ananassae F element, and a 1.7-Mb region from the D element for comparison. We find that transposons (particularly LTR and LINE retrotransposons) are major contributors to this expansion (78.6%), while Wolbachia sequences integrated into the D. ananassae genome are minor contributors (0.02%). Both D. melanogaster and D. ananassae F-element genes exhibit distinct characteristics compared to D-element genes (e.g., larger coding spans, larger introns, more coding exons, and lower codon bias), but these differences are exaggerated in D. ananassae. Compared to D. melanogaster, the codon bias observed in D. ananassae F-element genes can primarily be attributed to mutational biases instead of selection. The 5′ ends of F-element genes in both species are enriched in dimethylation of lysine 4 on histone 3 (H3K4me2), while the coding spans are enriched in H3K9me2. Despite differences in repeat density and gene characteristics, D. ananassae F-element genes show a similar range of expression levels compared to genes in euchromatic domains. This study improves our understanding of how transposons can affect genome size and how genes can function within highly repetitive domains. PMID:28667019

  12. Cytogenetic mapping of the Muller F element genes in Drosophila willistoni group.

    Science.gov (United States)

    Pita, Sebastián; Panzera, Yanina; Lúcia da Silva Valente, Vera; de Melo, Zilpa das Graças Silva; Garcia, Carolina; Garcia, Ana Cristina Lauer; Montes, Martín Alejandro; Rohde, Claudia

    2014-10-01

    Comparative genomics in Drosophila began in 1940, when Muller stated that the ancestral haploid karyotype of this genus is constituted by five acrocentric chromosomes and one dot chromosome, named A to F elements. In some species of the willistoni group such as Drosophila willistoni and D. insularis, the F element, instead of a dot chromosome, has been incorporated into the E element, forming chromosome III (E + F fusion). The aim of this study was to investigate the scope of the E + F fusion in the willistoni group, evaluating six other species. Fluorescent in situ hybridization was used to locate two genes of the F element previously studied-cubitus interruptus (ci) and eyeless (ey)-in species of the willistoni and bocainensis subgroups. Moreover, polytene chromosome photomaps corresponding to the F element (basal portion of chromosome III) were constructed for each species studied. In D. willistoni, D. paulistorum and D. equinoxialis, the ci gene was located in subSectction 78B and the ey gene in 78C. In D. tropicalis, ci was located in subSection 76B and ey in 76C. In species of the bocainensis subgroup, ci and ey were localized, respectively, at subsections 76B and 76C in D. nebulosa and D. capricorni, and 76A and 76C in D. fumipennis. Despite the differences in the subsection numbers, all species showed the same position for ci and ey. The results confirm the synteny of E + F fusion in willistoni and bocainensis subgroups, and allow estimating the occurrence of this event at 15 Mya, at least.

  13. Drosophila Muller F Elements Maintain a Distinct Set of Genomic Properties Over 40 Million Years of Evolution

    Science.gov (United States)

    Leung, Wilson; Shaffer, Christopher D.; Reed, Laura K.; Smith, Sheryl T.; Barshop, William; Dirkes, William; Dothager, Matthew; Lee, Paul; Wong, Jeannette; Xiong, David; Yuan, Han; Bedard, James E. J.; Machone, Joshua F.; Patterson, Seantay D.; Price, Amber L.; Turner, Bryce A.; Robic, Srebrenka; Luippold, Erin K.; McCartha, Shannon R.; Walji, Tezin A.; Walker, Chelsea A.; Saville, Kenneth; Abrams, Marita K.; Armstrong, Andrew R.; Armstrong, William; Bailey, Robert J.; Barberi, Chelsea R.; Beck, Lauren R.; Blaker, Amanda L.; Blunden, Christopher E.; Brand, Jordan P.; Brock, Ethan J.; Brooks, Dana W.; Brown, Marie; Butzler, Sarah C.; Clark, Eric M.; Clark, Nicole B.; Collins, Ashley A.; Cotteleer, Rebecca J.; Cullimore, Peterson R.; Dawson, Seth G.; Docking, Carter T.; Dorsett, Sasha L.; Dougherty, Grace A.; Downey, Kaitlyn A.; Drake, Andrew P.; Earl, Erica K.; Floyd, Trevor G.; Forsyth, Joshua D.; Foust, Jonathan D.; Franchi, Spencer L.; Geary, James F.; Hanson, Cynthia K.; Harding, Taylor S.; Harris, Cameron B.; Heckman, Jonathan M.; Holderness, Heather L.; Howey, Nicole A.; Jacobs, Dontae A.; Jewell, Elizabeth S.; Kaisler, Maria; Karaska, Elizabeth A.; Kehoe, James L.; Koaches, Hannah C.; Koehler, Jessica; Koenig, Dana; Kujawski, Alexander J.; Kus, Jordan E.; Lammers, Jennifer A.; Leads, Rachel R.; Leatherman, Emily C.; Lippert, Rachel N.; Messenger, Gregory S.; Morrow, Adam T.; Newcomb, Victoria; Plasman, Haley J.; Potocny, Stephanie J.; Powers, Michelle K.; Reem, Rachel M.; Rennhack, Jonathan P.; Reynolds, Katherine R.; Reynolds, Lyndsey A.; Rhee, Dong K.; Rivard, Allyson B.; Ronk, Adam J.; Rooney, Meghan B.; Rubin, Lainey S.; Salbert, Luke R.; Saluja, Rasleen K.; Schauder, Taylor; Schneiter, Allison R.; Schulz, Robert W.; Smith, Karl E.; Spencer, Sarah; Swanson, Bryant R.; Tache, Melissa A.; Tewilliager, Ashley A.; Tilot, Amanda K.; VanEck, Eve; Villerot, Matthew M.; Vylonis, Megan B.; Watson, David T.; Wurzler, Juliana A.; Wysocki, Lauren M.; Yalamanchili, Monica; Zaborowicz, Matthew A.; Emerson, Julia A.; Ortiz, Carlos; Deuschle, Frederic J.; DiLorenzo, Lauren A.; Goeller, Katie L.; Macchi, Christopher R.; Muller, Sarah E.; Pasierb, Brittany D.; Sable, Joseph E.; Tucci, Jessica M.; Tynon, Marykathryn; Dunbar, David A.; Beken, Levent H.; Conturso, Alaina C.; Danner, Benjamin L.; DeMichele, Gabriella A.; Gonzales, Justin A.; Hammond, Maureen S.; Kelley, Colleen V.; Kelly, Elisabeth A.; Kulich, Danielle; Mageeney, Catherine M.; McCabe, Nikie L.; Newman, Alyssa M.; Spaeder, Lindsay A.; Tumminello, Richard A.; Revie, Dennis; Benson, Jonathon M.; Cristostomo, Michael C.; DaSilva, Paolo A.; Harker, Katherine S.; Jarrell, Jenifer N.; Jimenez, Luis A.; Katz, Brandon M.; Kennedy, William R.; Kolibas, Kimberly S.; LeBlanc, Mark T.; Nguyen, Trung T.; Nicolas, Daniel S.; Patao, Melissa D.; Patao, Shane M.; Rupley, Bryan J.; Sessions, Bridget J.; Weaver, Jennifer A.; Goodman, Anya L.; Alvendia, Erica L.; Baldassari, Shana M.; Brown, Ashley S.; Chase, Ian O.; Chen, Maida; Chiang, Scott; Cromwell, Avery B.; Custer, Ashley F.; DiTommaso, Tia M.; El-Adaimi, Jad; Goscinski, Nora C.; Grove, Ryan A.; Gutierrez, Nestor; Harnoto, Raechel S.; Hedeen, Heather; Hong, Emily L.; Hopkins, Barbara L.; Huerta, Vilma F.; Khoshabian, Colin; LaForge, Kristin M.; Lee, Cassidy T.; Lewis, Benjamin M.; Lydon, Anniken M.; Maniaci, Brian J.; Mitchell, Ryan D.; Morlock, Elaine V.; Morris, William M.; Naik, Priyanka; Olson, Nicole C.; Osterloh, Jeannette M.; Perez, Marcos A.; Presley, Jonathan D.; Randazzo, Matt J.; Regan, Melanie K.; Rossi, Franca G.; Smith, Melanie A.; Soliterman, Eugenia A.; Sparks, Ciani J.; Tran, Danny L.; Wan, Tiffany; Welker, Anne A.; Wong, Jeremy N.; Sreenivasan, Aparna; Youngblom, Jim; Adams, Andrew; Alldredge, Justin; Bryant, Ashley; Carranza, David; Cifelli, Alyssa; Coulson, Kevin; Debow, Calise; Delacruz, Noelle; Emerson, Charlene; Farrar, Cassandra; Foret, Don; Garibay, Edgar; Gooch, John; Heslop, Michelle; Kaur, Sukhjit; Khan, Ambreen; Kim, Van; Lamb, Travis; Lindbeck, Peter; Lucas, Gabi; Macias, Elizabeth; Martiniuc, Daniela; Mayorga, Lissett; Medina, Joseph; Membreno, Nelson; Messiah, Shady; Neufeld, Lacey; Nguyen, San Francisco; Nichols, Zachary; Odisho, George; Peterson, Daymon; Rodela, Laura; Rodriguez, Priscilla; Rodriguez, Vanessa; Ruiz, Jorge; Sherrill, Will; Silva, Valeria; Sparks, Jeri; Statton, Geeta; Townsend, Ashley; Valdez, Isabel; Waters, Mary; Westphal, Kyle; Winkler, Stacey; Zumkehr, Joannee; DeJong, Randall J.; Hoogewerf, Arlene J.; Ackerman, Cheri M.; Armistead, Isaac O.; Baatenburg, Lara; Borr, Matthew J.; Brouwer, Lindsay K.; Burkhart, Brandon J.; Bushhouse, Kelsey T.; Cesko, Lejla; Choi, Tiffany Y. Y.; Cohen, Heather; Damsteegt, Amanda M.; Darusz, Jess M.; Dauphin, Cory M.; Davis, Yelena P.; Diekema, Emily J.; Drewry, Melissa; Eisen, Michelle E. M.; Faber, Hayley M.; Faber, Katherine J.; Feenstra, Elizabeth; Felzer-Kim, Isabella T.; Hammond, Brandy L.; Hendriksma, Jesse; Herrold, Milton R.; Hilbrands, Julia A.; Howell, Emily J.; Jelgerhuis, Sarah A.; Jelsema, Timothy R.; Johnson, Benjamin K.; Jones, Kelly K.; Kim, Anna; Kooienga, Ross D.; Menyes, Erika E.; Nollet, Eric A.; Plescher, Brittany E.; Rios, Lindsay; Rose, Jenny L.; Schepers, Allison J.; Scott, Geoff; Smith, Joshua R.; Sterling, Allison M.; Tenney, Jenna C.; Uitvlugt, Chris; VanDyken, Rachel E.; VanderVennen, Marielle; Vue, Samantha; Kokan, Nighat P.; Agbley, Kwabea; Boham, Sampson K.; Broomfield, Daniel; Chapman, Kayla; Dobbe, Ali; Dobbe, Ian; Harrington, William; Ibrahem, Marwan; Kennedy, Andre; Koplinsky, Chad A.; Kubricky, Cassandra; Ladzekpo, Danielle; Pattison, Claire; Ramirez, Roman E.; Wande, Lucia; Woehlke, Sarah; Wawersik, Matthew; Kiernan, Elizabeth; Thompson, Jeffrey S.; Banker, Roxanne; Bartling, Justina R.; Bhatiya, Chinmoy I.; Boudoures, Anna L.; Christiansen, Lena; Fosselman, Daniel S.; French, Kristin M.; Gill, Ishwar S.; Havill, Jessen T.; Johnson, Jaelyn L.; Keny, Lauren J.; Kerber, John M.; Klett, Bethany M.; Kufel, Christina N.; May, Francis J.; Mecoli, Jonathan P.; Merry, Callie R.; Meyer, Lauren R.; Miller, Emily G.; Mullen, Gregory J.; Palozola, Katherine C.; Pfeil, Jacob J.; Thomas, Jessica G.; Verbofsky, Evan M.; Spana, Eric P.; Agarwalla, Anant; Chapman, Julia; Chlebina, Ben; Chong, Insun; Falk, I.N.; Fitzgibbons, John D.; Friedman, Harrison; Ighile, Osagie; Kim, Andrew J.; Knouse, Kristin A.; Kung, Faith; Mammo, Danny; Ng, Chun Leung; Nikam, Vinayak S.; Norton, Diana; Pham, Philip; Polk, Jessica W.; Prasad, Shreya; Rankin, Helen; Ratliff, Camille D.; Scala, Victoria; Schwartz, Nicholas U.; Shuen, Jessica A.; Xu, Amy; Xu, Thomas Q.; Zhang, Yi; Rosenwald, Anne G.; Burg, Martin G.; Adams, Stephanie J.; Baker, Morgan; Botsford, Bobbi; Brinkley, Briana; Brown, Carter; Emiah, Shadie; Enoch, Erica; Gier, Chad; Greenwell, Alyson; Hoogenboom, Lindsay; Matthews, Jordan E.; McDonald, Mitchell; Mercer, Amanda; Monsma, Nicholaus; Ostby, Kristine; Ramic, Alen; Shallman, Devon; Simon, Matthew; Spencer, Eric; Tomkins, Trisha; Wendland, Pete; Wylie, Anna; Wolyniak, Michael J.; Robertson, Gregory M.; Smith, Samuel I.; DiAngelo, Justin R.; Sassu, Eric D.; Bhalla, Satish C.; Sharif, Karim A.; Choeying, Tenzin; Macias, Jason S.; Sanusi, Fareed; Torchon, Karvyn; Bednarski, April E.; Alvarez, Consuelo J.; Davis, Kristen C.; Dunham, Carrie A.; Grantham, Alaina J.; Hare, Amber N.; Schottler, Jennifer; Scott, Zackary W.; Kuleck, Gary A.; Yu, Nicole S.; Kaehler, Marian M.; Jipp, Jacob; Overvoorde, Paul J.; Shoop, Elizabeth; Cyrankowski, Olivia; Hoover, Betsy; Kusner, Matt; Lin, Devry; Martinov, Tijana; Misch, Jonathan; Salzman, Garrett; Schiedermayer, Holly; Snavely, Michael; Zarrasola, Stephanie; Parrish, Susan; Baker, Atlee; Beckett, Alissa; Belella, Carissa; Bryant, Julie; Conrad, Turner; Fearnow, Adam; Gomez, Carolina; Herbstsomer, Robert A.; Hirsch, Sarah; Johnson, Christen; Jones, Melissa; Kabaso, Rita; Lemmon, Eric; Vieira, Carolina Marques dos Santos; McFarland, Darryl; McLaughlin, Christopher; Morgan, Abbie; Musokotwane, Sepo; Neutzling, William; Nietmann, Jana; Paluskievicz, Christina; Penn, Jessica; Peoples, Emily; Pozmanter, Caitlin; Reed, Emily; Rigby, Nichole; Schmidt, Lasse; Shelton, Micah; Shuford, Rebecca; Tirasawasdichai, Tiara; Undem, Blair; Urick, Damian; Vondy, Kayla; Yarrington, Bryan; Eckdahl, Todd T.; Poet, Jeffrey L.; Allen, Alica B.; Anderson, John E.; Barnett, Jason M.; Baumgardner, Jordan S.; Brown, Adam D.; Carney, Jordan E.; Chavez, Ramiro A.; Christgen, Shelbi L.; Christie, Jordan S.; Clary, Andrea N.; Conn, Michel A.; Cooper, Kristen M.; Crowley, Matt J.; Crowley, Samuel T.; Doty, Jennifer S.; Dow, Brian A.; Edwards, Curtis R.; Elder, Darcie D.; Fanning, John P.; Janssen, Bridget M.; Lambright, Anthony K.; Lane, Curtiss E.; Limle, Austin B.; Mazur, Tammy; McCracken, Marly R.; McDonough, Alexa M.; Melton, Amy D.; Minnick, Phillip J.; Musick, Adam E.; Newhart, William H.; Noynaert, Joseph W.; Ogden, Bradley J.; Sandusky, Michael W.; Schmuecker, Samantha M.; Shipman, Anna L.; Smith, Anna L.; Thomsen, Kristen M.; Unzicker, Matthew R.; Vernon, William B.; Winn, Wesley W.; Woyski, Dustin S.; Zhu, Xiao; Du, Chunguang; Ament, Caitlin; Aso, Soham; Bisogno, Laura Simone; Caronna, Jason; Fefelova, Nadezhda; Lopez, Lenin; Malkowitz, Lorraine; Marra, Jonathan; Menillo, Daniella; Obiorah, Ifeanyi; Onsarigo, Eric Nyabeta; Primus, Shekerah; Soos, Mahdi; Tare, Archana; Zidan, Ameer; Jones, Christopher J.; Aronhalt, Todd; Bellush, James M.; Burke, Christa; DeFazio, Steve; Does, Benjamin R.; Johnson, Todd D.; Keysock, Nicholas; Knudsen, Nelson H.; Messler, James; Myirski, Kevin; Rekai, Jade Lea; Rempe, Ryan Michael; Salgado, Michael S.; Stagaard, Erica; Starcher, Justin R.; Waggoner, Andrew W.; Yemelyanova, Anastasia K.; Hark, Amy T.; Bertolet, Anne; Kuschner, Cyrus E.; Parry, Kesley; Quach, Michael; Shantzer, Lindsey; Shaw, Mary E.; Smith, Mary A.; Glenn, Omolara; Mason, Portia; Williams, Charlotte; Key, S. Catherine Silver; Henry, Tyneshia C. P.; Johnson, Ashlee G.; White, Jackie X.; Haberman, Adam; Asinof, Sam; Drumm, Kelly; Freeburg, Trip; Safa, Nadia; Schultz, Darrin; Shevin, Yakov; Svoronos, Petros; Vuong, Tam; Wellinghoff, Jules; Hoopes, Laura L. M.; Chau, Kim M.; Ward, Alyssa; Regisford, E. Gloria C.; Augustine, LaJerald; Davis-Reyes, Brionna; Echendu, Vivienne; Hales, Jasmine; Ibarra, Sharon; Johnson, Lauriaun; Ovu, Steven; Braverman, John M.; Bahr, Thomas J.; Caesar, Nicole M.; Campana, Christopher; Cassidy, Daniel W.; Cognetti, Peter A.; English, Johnathan D.; Fadus, Matthew C.; Fick, Cameron N.; Freda, Philip J.; Hennessy, Bryan M.; Hockenberger, Kelsey; Jones, Jennifer K.; King, Jessica E.; Knob, Christopher R.; Kraftmann, Karen J.; Li, Linghui; Lupey, Lena N.; Minniti, Carl J.; Minton, Thomas F.; Moran, Joseph V.; Mudumbi, Krishna; Nordman, Elizabeth C.; Puetz, William J.; Robinson, Lauren M.; Rose, Thomas J.; Sweeney, Edward P.; Timko, Ashley S.; Paetkau, Don W.; Eisler, Heather L.; Aldrup, Megan E.; Bodenberg, Jessica M.; Cole, Mara G.; Deranek, Kelly M.; DeShetler, Megan; Dowd, Rose M.; Eckardt, Alexandra K.; Ehret, Sharon C.; Fese, Jessica; Garrett, Amanda D.; Kammrath, Anna; Kappes, Michelle L.; Light, Morgan R.; Meier, Anne C.; O’Rouke, Allison; Perella, Mallory; Ramsey, Kimberley; Ramthun, Jennifer R.; Reilly, Mary T.; Robinett, Deirdre; Rossi, Nadine L.; Schueler, Mary Grace; Shoemaker, Emma; Starkey, Kristin M.; Vetor, Ashley; Vrable, Abby; Chandrasekaran, Vidya; Beck, Christopher; Hatfield, Kristen R.; Herrick, Douglas A.; Khoury, Christopher B.; Lea, Charlotte; Louie, Christopher A.; Lowell, Shannon M.; Reynolds, Thomas J.; Schibler, Jeanine; Scoma, Alexandra H.; Smith-Gee, Maxwell T.; Tuberty, Sarah; Smith, Christopher D.; Lopilato, Jane E.; Hauke, Jeanette; Roecklein-Canfield, Jennifer A.; Corrielus, Maureen; Gilman, Hannah; Intriago, Stephanie; Maffa, Amanda; Rauf, Sabya A.; Thistle, Katrina; Trieu, Melissa; Winters, Jenifer; Yang, Bib; Hauser, Charles R.; Abusheikh, Tariq; Ashrawi, Yara; Benitez, Pedro; Boudreaux, Lauren R.; Bourland, Megan; Chavez, Miranda; Cruz, Samantha; Elliott, GiNell; Farek, Jesse R.; Flohr, Sarah; Flores, Amanda H.; Friedrichs, Chelsey; Fusco, Zach; Goodwin, Zane; Helmreich, Eric; Kiley, John; Knepper, John Mark; Langner, Christine; Martinez, Megan; Mendoza, Carlos; Naik, Monal; Ochoa, Andrea; Ragland, Nicolas; Raimey, England; Rathore, Sunil; Reza, Evangelina; Sadovsky, Griffin; Seydoux, Marie-Isabelle B.; Smith, Jonathan E.; Unruh, Anna K.; Velasquez, Vicente; Wolski, Matthew W.; Gosser, Yuying; Govind, Shubha; Clarke-Medley, Nicole; Guadron, Leslie; Lau, Dawn; Lu, Alvin; Mazzeo, Cheryl; Meghdari, Mariam; Ng, Simon; Pamnani, Brad; Plante, Olivia; Shum, Yuki Kwan Wa; Song, Roy; Johnson, Diana E.; Abdelnabi, Mai; Archambault, Alexi; Chamma, Norma; Gaur, Shailly; Hammett, Deborah; Kandahari, Adrese; Khayrullina, Guzal; Kumar, Sonali; Lawrence, Samantha; Madden, Nigel; Mandelbaum, Max; Milnthorp, Heather; Mohini, Shiv; Patel, Roshni; Peacock, Sarah J.; Perling, Emily; Quintana, Amber; Rahimi, Michael; Ramirez, Kristen; Singhal, Rishi; Weeks, Corinne; Wong, Tiffany; Gillis, Aubree T.; Moore, Zachary D.; Savell, Christopher D.; Watson, Reece; Mel, Stephanie F.; Anilkumar, Arjun A.; Bilinski, Paul; Castillo, Rostislav; Closser, Michael; Cruz, Nathalia M.; Dai, Tiffany; Garbagnati, Giancarlo F.; Horton, Lanor S.; Kim, Dongyeon; Lau, Joyce H.; Liu, James Z.; Mach, Sandy D.; Phan, Thu A.; Ren, Yi; Stapleton, Kenneth E.; Strelitz, Jean M.; Sunjed, Ray; Stamm, Joyce; Anderson, Morgan C.; Bonifield, Bethany Grace; Coomes, Daniel; Dillman, Adam; Durchholz, Elaine J.; Fafara-Thompson, Antoinette E.; Gross, Meleah J.; Gygi, Amber M.; Jackson, Lesley E.; Johnson, Amy; Kocsisova, Zuzana; Manghelli, Joshua L.; McNeil, Kylie; Murillo, Michael; Naylor, Kierstin L.; Neely, Jessica; Ogawa, Emmy E.; Rich, Ashley; Rogers, Anna; Spencer, J. Devin; Stemler, Kristina M.; Throm, Allison A.; Van Camp, Matt; Weihbrecht, Katie; Wiles, T. Aaron; Williams, Mallory A.; Williams, Matthew; Zoll, Kyle; Bailey, Cheryl; Zhou, Leming; Balthaser, Darla M.; Bashiri, Azita; Bower, Mindy E.; Florian, Kayla A.; Ghavam, Nazanin; Greiner-Sosanko, Elizabeth S.; Karim, Helmet; Mullen, Victor W.; Pelchen, Carly E.; Yenerall, Paul M.; Zhang, Jiayu; Rubin, Michael R.; Arias-Mejias, Suzette M.; Bermudez-Capo, Armando G.; Bernal-Vega, Gabriela V.; Colon-Vazquez, Mariela; Flores-Vazquez, Arelys; Gines-Rosario, Mariela; Llavona-Cartagena, Ivan G.; Martinez-Rodriguez, Javier O.; Ortiz-Fuentes, Lionel; Perez-Colomba, Eliezer O.; Perez-Otero, Joseph; Rivera, Elisandra; Rodriguez-Giron, Luke J.; Santiago-Sanabria, Arnaldo J.; Senquiz-Gonzalez, Andrea M.; delValle, Frank R. Soto; Vargas-Franco, Dorianmarie; Velázquez-Soto, Karla I.; Zambrana-Burgos, Joan D.; Martinez-Cruzado, Juan Carlos; Asencio-Zayas, Lillyann; Babilonia-Figueroa, Kevin; Beauchamp-Pérez, Francis D.; Belén-Rodríguez, Juliana; Bracero-Quiñones, Luciann; Burgos-Bula, Andrea P.; Collado-Méndez, Xavier A.; Colón-Cruz, Luis R.; Correa-Muller, Ana I.; Crooke-Rosado, Jonathan L.; Cruz-García, José M.; Defendini-Ávila, Marianna; Delgado-Peraza, Francheska M.; Feliciano-Cancela, Alex J.; Gónzalez-Pérez, Valerie M.; Guiblet, Wilfried; Heredia-Negrón, Aldo; Hernández-Muñiz, Jennifer; Irizarry-González, Lourdes N.; Laboy-Corales, Ángel L.; Llaurador-Caraballo, Gabriela A.; Marín-Maldonado, Frances; Marrero-Llerena, Ulises; Martell-Martínez, Héctor A.; Martínez-Traverso, Idaliz M.; Medina-Ortega, Kiara N.; Méndez-Castellanos, Sonya G.; Menéndez-Serrano, Krizia C.; Morales-Caraballo, Carol I.; Ortiz-DeChoudens, Saryleine; Ortiz-Ortiz, Patricia; Pagán-Torres, Hendrick; Pérez-Afanador, Diana; Quintana-Torres, Enid M.; Ramírez-Aponte, Edwin G.; Riascos-Cuero, Carolina; Rivera-Llovet, Michelle S.; Rivera-Pagán, Ingrid T.; Rivera-Vicéns, Ramón E.; Robles-Juarbe, Fabiola; Rodríguez-Bonilla, Lorraine; Rodríguez-Echevarría, Brian O.; Rodríguez-García, Priscila M.; Rodríguez-Laboy, Abneris E.; Rodríguez-Santiago, Susana; Rojas-Vargas, Michael L.; Rubio-Marrero, Eva N.; Santiago-Colón, Albeliz; Santiago-Ortiz, Jorge L.; Santos-Ramos, Carlos E.; Serrano-González, Joseline; Tamayo-Figueroa, Alina M.; Tascón-Peñaranda, Edna P.; Torres-Castillo, José L.; Valentín-Feliciano, Nelson A.; Valentín-Feliciano, Yashira M.; Vargas-Barreto, Nadyan M.; Vélez-Vázquez, Miguel; Vilanova-Vélez, Luis R.; Zambrana-Echevarría, Cristina; MacKinnon, Christy; Chung, Hui-Min; Kay, Chris; Pinto, Anthony; Kopp, Olga R.; Burkhardt, Joshua; Harward, Chris; Allen, Robert; Bhat, Pavan; Chang, Jimmy Hsiang-Chun; Chen, York; Chesley, Christopher; Cohn, Dara; DuPuis, David; Fasano, Michael; Fazzio, Nicholas; Gavinski, Katherine; Gebreyesus, Heran; Giarla, Thomas; Gostelow, Marcus; Greenstein, Rachel; Gunasinghe, Hashini; Hanson, Casey; Hay, Amanda; He, Tao Jian; Homa, Katie; Howe, Ruth; Howenstein, Jeff; Huang, Henry; Khatri, Aaditya; Kim, Young Lu; Knowles, Olivia; Kong, Sarah; Krock, Rebecca; Kroll, Matt; Kuhn, Julia; Kwong, Matthew; Lee, Brandon; Lee, Ryan; Levine, Kevin; Li, Yedda; Liu, Bo; Liu, Lucy; Liu, Max; Lousararian, Adam; Ma, Jimmy; Mallya, Allyson; Manchee, Charlie; Marcus, Joseph; McDaniel, Stephen; Miller, Michelle L.; Molleston, Jerome M.; Diez, Cristina Montero; Ng, Patrick; Ngai, Natalie; Nguyen, Hien; Nylander, Andrew; Pollack, Jason; Rastogi, Suchita; Reddy, Himabindu; Regenold, Nathaniel; Sarezky, Jon; Schultz, Michael; Shim, Jien; Skorupa, Tara; Smith, Kenneth; Spencer, Sarah J.; Srikanth, Priya; Stancu, Gabriel; Stein, Andrew P.; Strother, Marshall; Sudmeier, Lisa; Sun, Mengyang; Sundaram, Varun; Tazudeen, Noor; Tseng, Alan; Tzeng, Albert; Venkat, Rohit; Venkataram, Sandeep; Waldman, Leah; Wang, Tracy; Yang, Hao; Yu, Jack Y.; Zheng, Yin; Preuss, Mary L.; Garcia, Angelica; Juergens, Matt; Morris, Robert W.; Nagengast, Alexis A.; Azarewicz, Julie; Carr, Thomas J.; Chichearo, Nicole; Colgan, Mike; Donegan, Megan; Gardner, Bob; Kolba, Nik; Krumm, Janice L.; Lytle, Stacey; MacMillian, Laurell; Miller, Mary; Montgomery, Andrew; Moretti, Alysha; Offenbacker, Brittney; Polen, Mike; Toth, John; Woytanowski, John; Kadlec, Lisa; Crawford, Justin; Spratt, Mary L.; Adams, Ashley L.; Barnard, Brianna K.; Cheramie, Martin N.; Eime, Anne M.; Golden, Kathryn L.; Hawkins, Allyson P.; Hill, Jessica E.; Kampmeier, Jessica A.; Kern, Cody D.; Magnuson, Emily E.; Miller, Ashley R.; Morrow, Cody M.; Peairs, Julia C.; Pickett, Gentry L.; Popelka, Sarah A.; Scott, Alexis J.; Teepe, Emily J.; TerMeer, Katie A.; Watchinski, Carmen A.; Watson, Lucas A.; Weber, Rachel E.; Woodard, Kate A.; Barnard, Daron C.; Appiah, Isaac; Giddens, Michelle M.; McNeil, Gerard P.; Adebayo, Adeola; Bagaeva, Kate; Chinwong, Justina; Dol, Chrystel; George, Eunice; Haltaufderhyde, Kirk; Haye, Joanna; Kaur, Manpreet; Semon, Max; Serjanov, Dmitri; Toorie, Anika; Wilson, Christopher; Riddle, Nicole C.; Buhler, Jeremy; Mardis, Elaine R.

    2015-01-01

    The Muller F element (4.2 Mb, ~80 protein-coding genes) is an unusual autosome of Drosophila melanogaster; it is mostly heterochromatic with a low recombination rate. To investigate how these properties impact the evolution of repeats and genes, we manually improved the sequence and annotated the genes on the D. erecta, D. mojavensis, and D. grimshawi F elements and euchromatic domains from the Muller D element. We find that F elements have greater transposon density (25–50%) than euchromatic reference regions (3–11%). Among the F elements, D. grimshawi has the lowest transposon density (particularly DINE-1: 2% vs. 11–27%). F element genes have larger coding spans, more coding exons, larger introns, and lower codon bias. Comparison of the Effective Number of Codons with the Codon Adaptation Index shows that, in contrast to the other species, codon bias in D. grimshawi F element genes can be attributed primarily to selection instead of mutational biases, suggesting that density and types of transposons affect the degree of local heterochromatin formation. F element genes have lower estimated DNA melting temperatures than D element genes, potentially facilitating transcription through heterochromatin. Most F element genes (~90%) have remained on that element, but the F element has smaller syntenic blocks than genome averages (3.4–3.6 vs. 8.4–8.8 genes per block), indicating greater rates of inversion despite lower rates of recombination. Overall, the F element has maintained characteristics that are distinct from other autosomes in the Drosophila lineage, illuminating the constraints imposed by a heterochromatic milieu. PMID:25740935

  14. Drosophila muller f elements maintain a distinct set of genomic properties over 40 million years of evolution.

    Science.gov (United States)

    Leung, Wilson; Shaffer, Christopher D; Reed, Laura K; Smith, Sheryl T; Barshop, William; Dirkes, William; Dothager, Matthew; Lee, Paul; Wong, Jeannette; Xiong, David; Yuan, Han; Bedard, James E J; Machone, Joshua F; Patterson, Seantay D; Price, Amber L; Turner, Bryce A; Robic, Srebrenka; Luippold, Erin K; McCartha, Shannon R; Walji, Tezin A; Walker, Chelsea A; Saville, Kenneth; Abrams, Marita K; Armstrong, Andrew R; Armstrong, William; Bailey, Robert J; Barberi, Chelsea R; Beck, Lauren R; Blaker, Amanda L; Blunden, Christopher E; Brand, Jordan P; Brock, Ethan J; Brooks, Dana W; Brown, Marie; Butzler, Sarah C; Clark, Eric M; Clark, Nicole B; Collins, Ashley A; Cotteleer, Rebecca J; Cullimore, Peterson R; Dawson, Seth G; Docking, Carter T; Dorsett, Sasha L; Dougherty, Grace A; Downey, Kaitlyn A; Drake, Andrew P; Earl, Erica K; Floyd, Trevor G; Forsyth, Joshua D; Foust, Jonathan D; Franchi, Spencer L; Geary, James F; Hanson, Cynthia K; Harding, Taylor S; Harris, Cameron B; Heckman, Jonathan M; Holderness, Heather L; Howey, Nicole A; Jacobs, Dontae A; Jewell, Elizabeth S; Kaisler, Maria; Karaska, Elizabeth A; Kehoe, James L; Koaches, Hannah C; Koehler, Jessica; Koenig, Dana; Kujawski, Alexander J; Kus, Jordan E; Lammers, Jennifer A; Leads, Rachel R; Leatherman, Emily C; Lippert, Rachel N; Messenger, Gregory S; Morrow, Adam T; Newcomb, Victoria; Plasman, Haley J; Potocny, Stephanie J; Powers, Michelle K; Reem, Rachel M; Rennhack, Jonathan P; Reynolds, Katherine R; Reynolds, Lyndsey A; Rhee, Dong K; Rivard, Allyson B; Ronk, Adam J; Rooney, Meghan B; Rubin, Lainey S; Salbert, Luke R; Saluja, Rasleen K; Schauder, Taylor; Schneiter, Allison R; Schulz, Robert W; Smith, Karl E; Spencer, Sarah; Swanson, Bryant R; Tache, Melissa A; Tewilliager, Ashley A; Tilot, Amanda K; VanEck, Eve; Villerot, Matthew M; Vylonis, Megan B; Watson, David T; Wurzler, Juliana A; Wysocki, Lauren M; Yalamanchili, Monica; Zaborowicz, Matthew A; Emerson, Julia A; Ortiz, Carlos; Deuschle, Frederic J; DiLorenzo, Lauren A; Goeller, Katie L; Macchi, Christopher R; Muller, Sarah E; Pasierb, Brittany D; Sable, Joseph E; Tucci, Jessica M; Tynon, Marykathryn; Dunbar, David A; Beken, Levent H; Conturso, Alaina C; Danner, Benjamin L; DeMichele, Gabriella A; Gonzales, Justin A; Hammond, Maureen S; Kelley, Colleen V; Kelly, Elisabeth A; Kulich, Danielle; Mageeney, Catherine M; McCabe, Nikie L; Newman, Alyssa M; Spaeder, Lindsay A; Tumminello, Richard A; Revie, Dennis; Benson, Jonathon M; Cristostomo, Michael C; DaSilva, Paolo A; Harker, Katherine S; Jarrell, Jenifer N; Jimenez, Luis A; Katz, Brandon M; Kennedy, William R; Kolibas, Kimberly S; LeBlanc, Mark T; Nguyen, Trung T; Nicolas, Daniel S; Patao, Melissa D; Patao, Shane M; Rupley, Bryan J; Sessions, Bridget J; Weaver, Jennifer A; Goodman, Anya L; Alvendia, Erica L; Baldassari, Shana M; Brown, Ashley S; Chase, Ian O; Chen, Maida; Chiang, Scott; Cromwell, Avery B; Custer, Ashley F; DiTommaso, Tia M; El-Adaimi, Jad; Goscinski, Nora C; Grove, Ryan A; Gutierrez, Nestor; Harnoto, Raechel S; Hedeen, Heather; Hong, Emily L; Hopkins, Barbara L; Huerta, Vilma F; Khoshabian, Colin; LaForge, Kristin M; Lee, Cassidy T; Lewis, Benjamin M; Lydon, Anniken M; Maniaci, Brian J; Mitchell, Ryan D; Morlock, Elaine V; Morris, William M; Naik, Priyanka; Olson, Nicole C; Osterloh, Jeannette M; Perez, Marcos A; Presley, Jonathan D; Randazzo, Matt J; Regan, Melanie K; Rossi, Franca G; Smith, Melanie A; Soliterman, Eugenia A; Sparks, Ciani J; Tran, Danny L; Wan, Tiffany; Welker, Anne A; Wong, Jeremy N; Sreenivasan, Aparna; Youngblom, Jim; Adams, Andrew; Alldredge, Justin; Bryant, Ashley; Carranza, David; Cifelli, Alyssa; Coulson, Kevin; Debow, Calise; Delacruz, Noelle; Emerson, Charlene; Farrar, Cassandra; Foret, Don; Garibay, Edgar; Gooch, John; Heslop, Michelle; Kaur, Sukhjit; Khan, Ambreen; Kim, Van; Lamb, Travis; Lindbeck, Peter; Lucas, Gabi; Macias, Elizabeth; Martiniuc, Daniela; Mayorga, Lissett; Medina, Joseph; Membreno, Nelson; Messiah, Shady; Neufeld, Lacey; Nguyen, San Francisco; 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Schepers, Allison J; Scott, Geoff; Smith, Joshua R; Sterling, Allison M; Tenney, Jenna C; Uitvlugt, Chris; VanDyken, Rachel E; VanderVennen, Marielle; Vue, Samantha; Kokan, Nighat P; Agbley, Kwabea; Boham, Sampson K; Broomfield, Daniel; Chapman, Kayla; Dobbe, Ali; Dobbe, Ian; Harrington, William; Ibrahem, Marwan; Kennedy, Andre; Koplinsky, Chad A; Kubricky, Cassandra; Ladzekpo, Danielle; Pattison, Claire; Ramirez, Roman E; Wande, Lucia; Woehlke, Sarah; Wawersik, Matthew; Kiernan, Elizabeth; Thompson, Jeffrey S; Banker, Roxanne; Bartling, Justina R; Bhatiya, Chinmoy I; Boudoures, Anna L; Christiansen, Lena; Fosselman, Daniel S; French, Kristin M; Gill, Ishwar S; Havill, Jessen T; Johnson, Jaelyn L; Keny, Lauren J; Kerber, John M; Klett, Bethany M; Kufel, Christina N; May, Francis J; Mecoli, Jonathan P; Merry, Callie R; Meyer, Lauren R; Miller, Emily G; Mullen, Gregory J; Palozola, Katherine C; Pfeil, Jacob J; Thomas, Jessica G; Verbofsky, Evan M; Spana, Eric P; Agarwalla, Anant; Chapman, Julia; Chlebina, Ben; Chong, Insun; Falk, I N; Fitzgibbons, John D; Friedman, Harrison; Ighile, Osagie; Kim, Andrew J; Knouse, Kristin A; Kung, Faith; Mammo, Danny; Ng, Chun Leung; Nikam, Vinayak S; Norton, Diana; Pham, Philip; Polk, Jessica W; Prasad, Shreya; Rankin, Helen; Ratliff, Camille D; Scala, Victoria; Schwartz, Nicholas U; Shuen, Jessica A; Xu, Amy; Xu, Thomas Q; Zhang, Yi; Rosenwald, Anne G; Burg, Martin G; Adams, Stephanie J; Baker, Morgan; Botsford, Bobbi; Brinkley, Briana; Brown, Carter; Emiah, Shadie; Enoch, Erica; Gier, Chad; Greenwell, Alyson; Hoogenboom, Lindsay; Matthews, Jordan E; McDonald, Mitchell; Mercer, Amanda; Monsma, Nicholaus; Ostby, Kristine; Ramic, Alen; Shallman, Devon; Simon, Matthew; Spencer, Eric; Tomkins, Trisha; Wendland, Pete; Wylie, Anna; Wolyniak, Michael J; Robertson, Gregory M; Smith, Samuel I; DiAngelo, Justin R; Sassu, Eric D; Bhalla, Satish C; Sharif, Karim A; Choeying, Tenzin; Macias, Jason S; Sanusi, Fareed; Torchon, Karvyn; Bednarski, April E; Alvarez, Consuelo J; Davis, Kristen C; Dunham, Carrie A; Grantham, Alaina J; Hare, Amber N; Schottler, Jennifer; Scott, Zackary W; Kuleck, Gary A; Yu, Nicole S; Kaehler, Marian M; Jipp, Jacob; Overvoorde, Paul J; Shoop, Elizabeth; Cyrankowski, Olivia; Hoover, Betsy; Kusner, Matt; Lin, Devry; Martinov, Tijana; Misch, Jonathan; Salzman, Garrett; Schiedermayer, Holly; Snavely, Michael; Zarrasola, Stephanie; Parrish, Susan; Baker, Atlee; Beckett, Alissa; Belella, Carissa; Bryant, Julie; Conrad, Turner; Fearnow, Adam; Gomez, Carolina; Herbstsomer, Robert A; Hirsch, Sarah; Johnson, Christen; Jones, Melissa; Kabaso, Rita; Lemmon, Eric; Vieira, Carolina Marques Dos Santos; McFarland, Darryl; McLaughlin, Christopher; Morgan, Abbie; Musokotwane, Sepo; Neutzling, William; Nietmann, Jana; Paluskievicz, Christina; Penn, Jessica; Peoples, Emily; Pozmanter, Caitlin; Reed, Emily; Rigby, Nichole; Schmidt, Lasse; Shelton, Micah; Shuford, Rebecca; Tirasawasdichai, Tiara; Undem, Blair; Urick, Damian; Vondy, Kayla; Yarrington, Bryan; Eckdahl, Todd T; Poet, Jeffrey L; Allen, Alica B; Anderson, John E; Barnett, Jason M; Baumgardner, Jordan S; Brown, Adam D; Carney, Jordan E; Chavez, Ramiro A; Christgen, Shelbi L; Christie, Jordan S; Clary, Andrea N; Conn, Michel A; Cooper, Kristen M; Crowley, Matt J; Crowley, Samuel T; Doty, Jennifer S; Dow, Brian A; Edwards, Curtis R; Elder, Darcie D; Fanning, John P; Janssen, Bridget M; Lambright, Anthony K; Lane, Curtiss E; Limle, Austin B; Mazur, Tammy; McCracken, Marly R; McDonough, Alexa M; Melton, Amy D; Minnick, Phillip J; Musick, Adam E; Newhart, William H; Noynaert, Joseph W; Ogden, Bradley J; Sandusky, Michael W; Schmuecker, Samantha M; Shipman, Anna L; Smith, Anna L; Thomsen, Kristen M; Unzicker, Matthew R; Vernon, William B; Winn, Wesley W; Woyski, Dustin S; Zhu, Xiao; Du, Chunguang; Ament, Caitlin; Aso, Soham; Bisogno, Laura Simone; Caronna, Jason; Fefelova, Nadezhda; Lopez, Lenin; Malkowitz, Lorraine; Marra, Jonathan; Menillo, Daniella; Obiorah, Ifeanyi; Onsarigo, Eric Nyabeta; 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Chandrasekaran, Vidya; Beck, Christopher; Hatfield, Kristen R; Herrick, Douglas A; Khoury, Christopher B; Lea, Charlotte; Louie, Christopher A; Lowell, Shannon M; Reynolds, Thomas J; Schibler, Jeanine; Scoma, Alexandra H; Smith-Gee, Maxwell T; Tuberty, Sarah; Smith, Christopher D; Lopilato, Jane E; Hauke, Jeanette; Roecklein-Canfield, Jennifer A; Corrielus, Maureen; Gilman, Hannah; Intriago, Stephanie; Maffa, Amanda; Rauf, Sabya A; Thistle, Katrina; Trieu, Melissa; Winters, Jenifer; Yang, Bib; Hauser, Charles R; Abusheikh, Tariq; Ashrawi, Yara; Benitez, Pedro; Boudreaux, Lauren R; Bourland, Megan; Chavez, Miranda; Cruz, Samantha; Elliott, GiNell; Farek, Jesse R; Flohr, Sarah; Flores, Amanda H; Friedrichs, Chelsey; Fusco, Zach; Goodwin, Zane; Helmreich, Eric; Kiley, John; Knepper, John Mark; Langner, Christine; Martinez, Megan; Mendoza, Carlos; Naik, Monal; Ochoa, Andrea; Ragland, Nicolas; Raimey, England; Rathore, Sunil; Reza, Evangelina; Sadovsky, Griffin; Seydoux, Marie-Isabelle B; Smith, Jonathan E; 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Chen, York; Chesley, Christopher; Cohn, Dara; DuPuis, David; Fasano, Michael; Fazzio, Nicholas; Gavinski, Katherine; Gebreyesus, Heran; Giarla, Thomas; Gostelow, Marcus; Greenstein, Rachel; Gunasinghe, Hashini; Hanson, Casey; Hay, Amanda; He, Tao Jian; Homa, Katie; Howe, Ruth; Howenstein, Jeff; Huang, Henry; Khatri, Aaditya; Kim, Young Lu; Knowles, Olivia; Kong, Sarah; Krock, Rebecca; Kroll, Matt; Kuhn, Julia; Kwong, Matthew; Lee, Brandon; Lee, Ryan; Levine, Kevin; Li, Yedda; Liu, Bo; Liu, Lucy; Liu, Max; Lousararian, Adam; Ma, Jimmy; Mallya, Allyson; Manchee, Charlie; Marcus, Joseph; McDaniel, Stephen; Miller, Michelle L; Molleston, Jerome M; Diez, Cristina Montero; Ng, Patrick; Ngai, Natalie; Nguyen, Hien; Nylander, Andrew; Pollack, Jason; Rastogi, Suchita; Reddy, Himabindu; Regenold, Nathaniel; Sarezky, Jon; Schultz, Michael; Shim, Jien; Skorupa, Tara; Smith, Kenneth; Spencer, Sarah J; Srikanth, Priya; Stancu, Gabriel; Stein, Andrew P; Strother, Marshall; Sudmeier, Lisa; Sun, Mengyang; 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Giddens, Michelle M; McNeil, Gerard P; Adebayo, Adeola; Bagaeva, Kate; Chinwong, Justina; Dol, Chrystel; George, Eunice; Haltaufderhyde, Kirk; Haye, Joanna; Kaur, Manpreet; Semon, Max; Serjanov, Dmitri; Toorie, Anika; Wilson, Christopher; Riddle, Nicole C; Buhler, Jeremy; Mardis, Elaine R; Elgin, Sarah C R

    2015-03-04

    The Muller F element (4.2 Mb, ~80 protein-coding genes) is an unusual autosome of Drosophila melanogaster; it is mostly heterochromatic with a low recombination rate. To investigate how these properties impact the evolution of repeats and genes, we manually improved the sequence and annotated the genes on the D. erecta, D. mojavensis, and D. grimshawi F elements and euchromatic domains from the Muller D element. We find that F elements have greater transposon density (25-50%) than euchromatic reference regions (3-11%). Among the F elements, D. grimshawi has the lowest transposon density (particularly DINE-1: 2% vs. 11-27%). F element genes have larger coding spans, more coding exons, larger introns, and lower codon bias. Comparison of the Effective Number of Codons with the Codon Adaptation Index shows that, in contrast to the other species, codon bias in D. grimshawi F element genes can be attributed primarily to selection instead of mutational biases, suggesting that density and types of transposons affect the degree of local heterochromatin formation. F element genes have lower estimated DNA melting temperatures than D element genes, potentially facilitating transcription through heterochromatin. Most F element genes (~90%) have remained on that element, but the F element has smaller syntenic blocks than genome averages (3.4-3.6 vs. 8.4-8.8 genes per block), indicating greater rates of inversion despite lower rates of recombination. Overall, the F element has maintained characteristics that are distinct from other autosomes in the Drosophila lineage, illuminating the constraints imposed by a heterochromatic milieu. Copyright © 2015 Leung et al.

  15. f-Element Ion Chelation in Highly Basic Media - Final Report

    International Nuclear Information System (INIS)

    Paine, R.T.

    2000-01-01

    A large body of data has been collected over the last fifty years on the chemical behavior of f-element ions. The ions undergo rapid hydrolysis reactions in neutral or basic aqueous solutions that produce poorly understood oxide-hydroxide species; therefore, most of the fundamental f-element solution chemistry has allowed synthetic and separations chemists to rationally design advanced organic chelating ligands useful for highly selective partitioning and separation of f-element ions from complex acidic solution matrices. These ligands and new examples under development allow for the safe use and treatment of solutions containing highly radioactive species. This DOE/EMSP project was undertaken to address the following fundamental objectives: (1) study the chemical speciation of Sr and lanthanide (Ln) ions in basic aqueous media containing classical counter anions found in waste matrices; (2) prepare pyridine N-oxide phosphonates and phosphonic acids that might act as selective chelator s for Ln ions in model basic pH waste streams; (3) study the binding of the new chelators toward Ln ions and (4) examine the utility of the chelators as decontamination and dissolution agents under basic solution conditions. The project has been successful in attacking selected aspects of the very difficult problems associated with basic pH solution f-element waste chemistry. In particular, the project has (1) shed additional light on the initial stages of Ln ion sol-gel-precipitate formulation under basic solution conditions; (2) generated new families of pyridine phosphonic acid chelators; (3) characterized the function of the chelators and (4) examined their utility as oxide-hydroxide dissolution agents. These findings have contributed significantly to an improved understanding of the behavior of Ln ions in basic media containing anions found in typical waste sludges as well as to the development of sludge dissolution agents. The new chelating reagents are easily made and could be

  16. Some experiences with absorption, phonon Raman, and luminescence spectroscopic probes of crystal structure of f-element compounds

    International Nuclear Information System (INIS)

    Peterson, J.R.

    1992-01-01

    Structural information is crucial to the study and understanding of the basic chemical properties of the f elements. X-ray diffraction (XRD) techniques are usually used to obtain crystal structure information. However, the transuranium (5f) elements, because of their radioactivity and limited availability, present problems for standard XRD analysis. For some time now we have been developing and using various spectroscopic probes of crystal structure; an overview of our research in this area is presented here

  17. Bond lengths and bond strengths in compounds of the 5f elements

    International Nuclear Information System (INIS)

    Zachariasen, W.H.

    1975-01-01

    The variation of bond length (D) with bond strength (S) in normal valence compounds of 3d, 4d, 5d-4f, and 6d-5f elements can be represented approximately as D(S)=D(0.5) F(S), where D(0.5) is a characteristic constant for a given bond and F(S) an empirical function which is the same for all bonds. A bond strength Ssub(ij)=ssub(ji) is assigned to the bond between atoms i and j such that Σsub(j) Ssub(ij)=vsub(i) and Σsub(i) Ssub(ij)=vsub(j), where vsub(i) and vsub(j) are the normal valences of the two atoms. The function F(S) decreases monotonically with increasing S, and is normalized to unity at S=0.5, so that the constant D(0.5) has the physical meaning of being the bond length adjusted to S=0.5. The method described above was used to interpret and systematize the experimental results on bond lengths in oxides, halides, and oxyhalides of the 5f elements. (U.S.)

  18. NATO Advanced Study Institute on Fundamental and Technological Aspects of Organo-f-Element Chemistry

    CERN Document Server

    Fragalà, Ignazio

    1985-01-01

    The past decade has seen a dramatic acceleration of activity and interest in phenomena surrounding lanthanide and actinide organo­ metallic compounds. Around the world, active research in organo-f­ element synthesis, chemistry, catalysis, crystallography, and quantum chemistry is in progress. This activity has spanned a remarkably wide range of disciplines, from synthetic/mechanistic inorganic and organic chemistry to radiochemistry, catalytic chemistry, spectroscopy (vibra­ tional, optical, magnetic resonance, photoelectron, Mossbauer), X-ray and neutron diffraction structural analysis, as well as to crystal field and molecular orbital theoretical studies at the interface of chemistry and physics. These investigations have been motivated both by fundamental and applied goals. The evidence that f-element organo­ metallic compounds have unique chemical and physical properties which cannot be duplicated by organometallic compounds of d-block elements has suggested many new areas of endeavor and application....

  19. F-Element ion chelation in highly basic media. 1998 annual progress report

    International Nuclear Information System (INIS)

    Paine, R.T.

    1998-01-01

    'A large percentage of high-level radioactive waste (HLW) produced in the DOE complex over the last thirty years temporarily resides in storage tanks maintained at highly basic pH. The final permanent waste remediation plan will probably require that liquid and solid fractions be chemically treated in order to partition and concentrate the dominate hazardous emitters from the bulk of the waste. This is no small task. Indeed, there does not exist a well developed molecular chemistry knowledge base to guide the development of suitable separations for actinide and fission products present in the strongly basic media. The goal of this project is to undertake fundamental studies of the coordination chemistry of f-element ions and their species formed in basic aqueous solutions containing common waste treatment ions (e.g., NO 3 - , CO 3 2- , organic carboxylates, and EDTA), as well as new waste scrubbing chelators produced in this study.'

  20. Contribution to the coordination chemistry of penta, hexa and heptavalent ions of 5f elements

    International Nuclear Information System (INIS)

    Musikas, Claude.

    1978-01-01

    This report has two main parts in which are discussed results dealing with: - aquo and hydroxo complexes of penta, hexa and heptavalent ions of 5f elements - pseuso halides complexes of these ions (SCN - , N 3 - , CN - ). It has been shown, by spectrophotometric and electrochemical measurements that U (V) possesses an aquo ion more acid than the known UO 2 + ion. This form is observed as insoluble hydroxid near pH 3.0 or as soluble polynuclear hydroxo complexes at lower pH. Hydroxo anionic complexes of U (VI) have been observed and one can precise the mecanism of hydrolysis of UO 2 ++ ions beyond he hydroxid UO 2 (OH) 2 . At pH 9 to 12, polynuclear species with low negative charge have been observed. At pH 13, others OH - ions enter in the coordination sphere of UO 2 ++ and mononuclear species are obtained. Reduction of polynuclear species leads to mixed hydroxo complexes of 'blue type'. Studies of hydrolysis of NpO 2 + allow to propose an hydrolysis mechanism similar to UO 2 ++ one. With electrochemical methods that in acidic media Np (VII) is present as NpO 3 + ions. Solubility product of NpO 3 OH has been measured. The second part is devoted to pseudohalides complexes of UO 2 ++ , UO 2 + and NpO 2 + ions [fr

  1. Solid-state quantum chemistry and materials science: Solid compounds of the d and f elements

    International Nuclear Information System (INIS)

    Gubanov, V.A.

    1989-01-01

    Methods have been developed for calculating electron structures for solid compounds of d and f elements and for simulating physicochemical properties of materials based on them. Cluster and band calculations are considered for refractory compounds of d metals formed with light elements. There are bond and property regularities in doping by meals and metalloids, and defects and impurities have certain effects, where studies have been made on the electron structures for disordered phases and solid solutions in relation to sublattice compositions. Quantum-chemical simulation methods have been developed for optically active and fluorescent materials based on d and f metal oxides, fluorides, and chalcogenides, and compositions have been proposed for new optically active composites and protective coatings. New approaches have been defined to the magnetic parameters of metals, alloys, and compounds; these can be applied in simulating new magnetic materials. Calculations are given on energy spectra for high-temperature oxide superconductors. There is interesting scope for quantum-chemical methods in application to many topics in materials science

  2. On the nature of the outer-sphere coordination of bivalent f-elements with tetraphenylborate ion

    International Nuclear Information System (INIS)

    Mikheev, N.B.; Kulyukhin, S.A.

    1993-01-01

    On the basis of the data on complex formation of Eu 2+ , Yb 2+ and Es 2+ with tetraphenylborate ion (BPh 4 - ) in different media a conclusion is made that formation of outerspheric complexes between bivalent f-elements and BPh 4 :-ions occurs due to electron channeling from cation in unsaturated π-bonds of BPh 4 - ion with formation of exchangeable single-electron chemical bond. 9 refs.,1 tab

  3. Quantum chemistry of solids and materials technology: solid-phase compounds of d- and f-elements

    International Nuclear Information System (INIS)

    Gubanov, V.A.

    1988-01-01

    The results of studies aimed at the development of methods of theoretical calculations of the electronic structure of solid phase compounds of α- and f-elements and the modelling of physicochemical properties of materials developed on their basis, are presented. The possibilities of cluster and zone calculations of the electronic structure of refractory compounds of d-metals with light elements are considered. The regularities of changes in the chemical bond and properties during crystal lattice alloying with metals, metalloids are found. The methods of quantum chemical modeling of optically active and luminescent materials on the base of oxides, fluorides, chalcogenides of d- and f-metals are developed. The compositions of new optically active compositions and protective coatings are suggested. New approaches to the study of magnetic properties of metals, alloys and compounds are developed. The results of calculations of the energy spectra of high-temperature oxide superconductors are given

  4. On the use of spectroscopic techniques to determine the crystal structure of compounds of the artificial f elements

    International Nuclear Information System (INIS)

    Peterson, J.R.

    1989-01-01

    For some time the author has been using solid state absorption spectrophotometry to identify the crystal structure of selected transuranium (5f) and promethium (4f) compounds, based on spectral-structural correlations in his data base. More recently he has shown that Raman phonon spectroscopy is also very useful in this regard. These spectral probes of structure have their specific advantages and disadvantages; however, both are applicable to the structural characterization of radioactive compounds and can provide data for interpretation faster and more reliably than the commonly used X-ray powder diffraction method. The experimental methods, examples from the growing data bases, successes and limitations of these spectral probes of crystal structure, and some useful applications to the study of f-element compounds under varying conditions of temperature and pressure are presented

  5. Evolutionary Significance of Wolbachia-to-Animal Horizontal Gene Transfer: Female Sex Determination and the f Element in the Isopod Armadillidium vulgare.

    Science.gov (United States)

    Cordaux, Richard; Gilbert, Clément

    2017-07-21

    An increasing number of horizontal gene transfer (HGT) events from bacteria to animals have been reported in the past years, many of which involve Wolbachia bacterial endosymbionts and their invertebrate hosts. Most transferred Wolbachia genes are neutrally-evolving fossils embedded in host genomes. A remarkable case of Wolbachia HGT for which a clear evolutionary significance has been demonstrated is the " f element", a nuclear Wolbachia insert involved in female sex determination in the terrestrial isopod Armadillidium vulgare . The f element represents an instance of bacteria-to-animal HGT that has occurred so recently that it was possible to infer the donor (feminizing Wolbachia closely related to the w VulC Wolbachia strain of A. vulgare ) and the mechanism of integration (a nearly complete genome inserted by micro-homology-mediated recombination). In this review, we summarize our current knowledge of the f element and discuss arising perspectives regarding female sex determination, unstable inheritance, population dynamics and the molecular evolution of the f element. Overall, the f element unifies three major areas in evolutionary biology: symbiosis, HGT and sex determination. Its characterization highlights the tremendous impact sex ratio distorters can have on the evolution of sex determination mechanisms and sex chromosomes in animals and plants.

  6. Evolutionary Significance of Wolbachia-to-Animal Horizontal Gene Transfer: Female Sex Determination and the f Element in the Isopod Armadillidium vulgare

    Directory of Open Access Journals (Sweden)

    Richard Cordaux

    2017-07-01

    Full Text Available An increasing number of horizontal gene transfer (HGT events from bacteria to animals have been reported in the past years, many of which involve Wolbachia bacterial endosymbionts and their invertebrate hosts. Most transferred Wolbachia genes are neutrally-evolving fossils embedded in host genomes. A remarkable case of Wolbachia HGT for which a clear evolutionary significance has been demonstrated is the “f element”, a nuclear Wolbachia insert involved in female sex determination in the terrestrial isopod Armadillidium vulgare. The f element represents an instance of bacteria-to-animal HGT that has occurred so recently that it was possible to infer the donor (feminizing Wolbachia closely related to the wVulC Wolbachia strain of A. vulgare and the mechanism of integration (a nearly complete genome inserted by micro-homology-mediated recombination. In this review, we summarize our current knowledge of the f element and discuss arising perspectives regarding female sex determination, unstable inheritance, population dynamics and the molecular evolution of the f element. Overall, the f element unifies three major areas in evolutionary biology: symbiosis, HGT and sex determination. Its characterization highlights the tremendous impact sex ratio distorters can have on the evolution of sex determination mechanisms and sex chromosomes in animals and plants.

  7. Solubility and transport measurements as tools for the speciation of f-elements at tracer-scale amounts; application to Eu and Th in phosphate media

    International Nuclear Information System (INIS)

    Fourest, B.; David, F.; Lagarde, G.; Lindecker, C.; Du, J.F. Le; Tarapcik, P.; Trskova, R.

    1998-01-01

    The speciation of f-elements can be examined by methods which are based either on the distribution of the radionuclide of interest between two phases (solubility measurements) or on its moving in solution (capillary diffusion and migration). Predictive curves giving the variation of the mobility and the concentration of Europium as a function of pH and/or phosphate concentration can be proposed from selected literature data. Capillary electrophoresis experiments show that the mobility decrease due to hydrolysis occurs at a pH value lower than expected. The peak intensity is correspondingly smaller, but this observation cannot be simply related to a change in the charge of the migrating species because of sorption and precipitation phenomena on the capillary walls. Diffusion coefficient measurements by the 'open end capillary' method confirm the formation of larger and/or less charged species starting at a similar pH value. In the presence of phosphate anions, both transport methods should indicate the presence in solution of species having a larger size than expected, which could be polynuclear. Solubility measurements give more information but require the synthesis of a well-defined labelled phosphate compound. The total concentration of f-elements detected in the solutions equilibrated with such compounds allow to deduce, by varying only one parameter in the solution (pH or phosphate concentration), the form and the charge of the different species prevailing in the solution. The solubility method appears particularly interesting in the case of concentrated phosphate media

  8. Stereoselective and stereospecific effects in the formation of heteronuclear tartrate complexes of 3d- and 4f-elements from proton magnetic relaxation data

    International Nuclear Information System (INIS)

    Sal'nikov, Yu.I.; Chevela, V.V.

    1987-01-01

    A new approach to identification of stereoselective and stereospecific effects in the formation of heteronuclear tartrate complexes of 3d- and 4f-elements according to proton magnetic relaxation data is developed. At the first stage comparison of experimental dependences of the property measured (relaxation efficiency coefficient, Bjerrum function etc.) on the consentrational parameters is conducted. Their different course in systems with dH 4 L (d-tartaric acid) and dlH 4 L (dl-tartaric acid) points out to the presence of stereoeffects. Then, using mathematical simulation the most true stoichiometry of complex particles is determined as well as optimized values of their stability constants and intensity factors. The method is used when investigating the following systems: Fe 3+ -dH 4 L(dlH 4 L), Ln 3+ -dH 4 L(dlH 4 L), Fe 3+ -Ln 3+ -dH 4 L(dlH 4 L)(Ln 3+ -Gd 3+ , Ho 3+ , Er 3+ , Tm 3+ )

  9. Synthesis and characterization of f-element iodate architectures with variable dimensionality, alpha- and beta-Am(IO3)3.

    Science.gov (United States)

    Runde, Wolfgang; Bean, Amanda C; Brodnax, Lia F; Scott, Brian L

    2006-03-20

    Two americium(III) iodates, beta-Am(IO3)3 (I) and alpha-Am(IO3)3 (II), have been prepared from the aqueous reactions of Am(III) with KIO(4) at 180 degrees C and have been characterized by single-crystal X-ray diffraction, diffuse reflectance, and Raman spectroscopy. The alpha-form is consistent with the known structure type I of anhydrous lanthanide iodates. It consists of a three-dimensional network of pyramidal iodate groups bridging [AmO8] polyhedra where each of the americium ions are coordinated to eight iodate ligands. The beta-form reveals a novel architecture that is unknown within the f-element iodate series. beta-Am(IO3)3 exhibits a two-dimensional layered structure with nine-coordinate Am(III) atoms. Three crystallographically unique pyramidal iodate anions link the Am atoms into corrugated sheets that interact with one another through intermolecular IO3-...IO3- interactions forming dimeric I2O10 units. One of these anions utilizes all three O atoms to simultaneously bridge three Am atoms. The other two iodate ligands bridge only two Am atoms and have one terminal O atom. In contrast to alpha-Am(IO3)3, where the [IO3] ligands are solely corner-sharing with [AmO8] polyhedra, a complex arrangement of corner- and edge-sharing mu2- and mu3-[IO3] pyramids can be found in beta-Am(IO3)3. Crystallographic data: I, monoclinic, space group P2(1)/n, a = 8.871(3) A, b = 5.933(2) A, c = 15.315(4) A, beta = 96.948(4) degrees , V = 800.1(4) A(3), Z = 4; II, monoclinic, space group P2(1)/c, a = 7.243(2) A, b = 8.538(3) A, c = 13.513(5) A, beta = 100.123(6) degrees , V = 822.7(5) A(3), Z = 4.

  10. Comparative Study of f-Element Electronic Structure across a Series of Multimetallic Actinide, Lanthanide-Actinide and Lanthanum-Actinide Complexes Possessing Redox-Active Bridging Ligands

    Energy Technology Data Exchange (ETDEWEB)

    Schelter, Eric J.; Wu, Ruilian; Veauthier, Jacqueline M.; Bauer, Eric D.; Booth, Corwin H.; Thomson, Robert K.; Graves, Christopher R.; John, Kevin D.; Scott, Brian L.; Thompson, Joe D.; Morris, David E.; Kiplinger, Jaqueline L.

    2010-02-24

    A comparative examination of the electronic interactions across a series of trimetallic actinide and mixed lanthanide-actinide and lanthanum-actinide complexes is presented. Using reduced, radical terpyridyl ligands as conduits in a bridging framework to promote intramolecular metal-metal communication, studies containing structural, electrochemical, and X-ray absorption spectroscopy are presented for (C{sub 5}Me{sub 5}){sub 2}An[-N=C(Bn)(tpy-M{l_brace}C{sub 5}Me4R{r_brace}{sub 2})]{sub 2} (where An = Th{sup IV}, U{sup IV}; Bn = CH{sub 2}C{sub 6}H{sub 5}; M = La{sup III}, Sm{sup III}, Yb{sup III}, U{sup III}; R = H, Me, Et) to reveal effects dependent on the identities of the metal ions and R-groups. The electrochemical results show differences in redox energetics at the peripheral 'M' site between complexes and significant wave splitting of the metal- and ligand-based processes indicating substantial electronic interactions between multiple redox sites across the actinide-containing bridge. Most striking is the appearance of strong electronic coupling for the trimetallic Yb{sup III}-U{sup IV}-Yb{sup III}, Sm{sup III}-U{sup IV}-Sm{sup III}, and La{sup III}-U{sup IV}-La{sup III} complexes, [8]{sup -}, [9b]{sup -} and [10b]{sup -}, respectively, whose calculated comproportionation constant K{sub c} is slightly larger than that reported for the benchmark Creutz-Taube ion. X-ray absorption studies for monometallic metallocene complexes of U{sup III}, U{sup IV}, and U{sup V} reveal small but detectable energy differences in the 'white-line' feature of the uranium L{sub III}-edges consistent with these variations in nominal oxidation state. The sum of this data provides evidence of 5f/6d-orbital participation in bonding and electronic delocalization in these multimetallic f-element complexes. An improved, high-yielding synthesis of 4{prime}-cyano-2,2{prime}:6{prime},2{double_prime}-terpyridine is also reported.

  11. Osobennosti khirurgicheskogo lecheniya katarakty u bol'nykh sakharnym diabetom

    Directory of Open Access Journals (Sweden)

    Dmitriy Valentinovich Lipatov

    2008-09-01

    Full Text Available Цель. Разработка тактики ведения пациентов с СД в до-, интра- и послео- перационном периоде при хирургии катаракты. Материалы и методы. Были проанализированы истории болезни 57 пациентов (63 глаза с СД, прооперированных по поводу катаракты. Всем пациентам была выполнена факоэмульсификация катаракты (ФЭК. За 30 минут до операции выполнялась премедикация реланиумом 0,1?0,15 мг/кг в/м. Для обезболивания проводились ретробульбарная анестезия и анестезиологическое пособие посредством атараксии и атаралгезии: дормикум 0,04?0,06 мг/кг в сочетании с ненаркотическими анальгетиками. В план подготовки к оперативному вмешательству был включен перечень обязательных обследований: оценка остроты зрения (визометрия, измерение внутриглазного давления (ВГД, определение периферических полей зрения (периметрия, ультразвуковое исследование орбит, биомикроскопия, офтальмоскопия, офтальмохромоскопия. Результаты. Для анализа полученных данных пациенты были разделены на две группы. Первую группу составили 12 пациентов с компенсированным СД (27%, из них 6 находились на терапии инсулином. Во второй группе были больные с субкомпенсированным СД ? 45 больных (73%, из них 10 до операции получали инсулин. В первой группе только у двух больных в послеоперационном периоде отмечалась резкая гипергликемия (до 20 ммоль/л, что потребовало присоединения препаратов инсулина для коррекции гликемии. Во второй группе у 5 пациентов повышение уровня глюкозы в крови потребовало назначения препаратов инсулина. У 50% пациентов острота зрения оперированного глаза повысилась в среднем на 4?5 строчек. Выводы. Пациентам с СД не противопоказана хирургия катаракты с имплантацией ИОЛ при правильном до-, интра- и послеоперационном ведении этих больных. Пациенты с СД должны быть прооперированы только при удовлетворительных показателях углеводного обмена (HbA1C ? менее 7,5%, гликемия натощак ? менее 7,5 ммоль/л, после приема пищи ? менее 9 ммоль/л. Пациентам с диабетической нефропатией в послеопера- ционном периоде показана профилактическая антибактериаль- ная терапия в половинной дозировке.

  12. Optical spectroscopy of f-element compounds

    International Nuclear Information System (INIS)

    Carnall, W.T.

    1978-01-01

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

  13. Synthesis and characterization of a novel aminopolycarboxylate complexant for efficient trivalent f-element differentiation: N-butyl-2-acetamide-diethylenetriamine-N,N',N",N"-tetraacetic acid

    Energy Technology Data Exchange (ETDEWEB)

    Heathman, Colt R. [Idaho National Lab. (INL), Idaho Falls, ID (United States). Aqueous Separations and Radiochemistry Dept.; Grimes, Travis S. [Idaho National Lab. (INL), Idaho Falls, ID (United States). Aqueous Separations and Radiochemistry Dept.; Jansone-Popova, Santa [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Ivanov, Alexander S. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Bryantsev, Vyacheslav S. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Zalupski, Peter R. [Idaho National Lab. (INL), Idaho Falls, ID (United States). Aqueous Separations and Radiochemistry Dept.

    2017-12-14

    The novel metal ion complexant N-butyl-2-acetamide-diethylenetriamine-N,N',N",N"-tetraacetic acid (DTTA-BuA) uses an amide functionalization to increase the total ligand acidity and attain efficient 4f/5f differentiation in low pH conditions. The amide, when located on the diethylenetriamine platform containing four acetate pendant arms maintains the octadentate coordination sphere for all investigated trivalent f-elements. This compact coordination environment inhibits the protonation of LnL- complexes, as indicated by lower K111 constants relative to the corresponding protonation site of the free ligand. For actinide ions, the enhanced stability of AnL- lowers the K111 for americium and curium beyond the aptitude of potentiometric detection. Density functional theory computations indicate the difference in the back-donation ability of Am3+ and Eu3+ f-orbitals is mainly responsible for stronger proton affinity of EuL- compared to AmL-. The measured stability constants for the formation of AmL- and CmL- complexes are consistently higher, relative to ML- complexes with lanthanides of similar charge density. When compared with the conventional aminopolycarboxylate diethylenetriamine pentaacetic acid (DTPA), the modified DTTA-BuA complexant features higher ligand acidity and the important An3+/Ln3+ differentiation when deployed on a liquid–liquid distribution platform.

  14. New functionalized β-diketiminate ligands and f elements

    International Nuclear Information System (INIS)

    Dulong, Florian

    2013-01-01

    β-diketiminate ligands have received increased interest in coordination chemistry, especially for homogeneous catalysis. Their successful applications arise from an easy and fine tuning of the ligand electronic and geometric properties. However, these modifications are limited to the introduction of neutral donors (ethers or amines), on the nitrogen substituents of the β-diketiminate skeleton. The main focus of this research project is to overcome this limitation by synthesizing new β-diketiminate ligands functionalized by one or two anionic aryl-oxide groups, and to study their coordination chemistry with lanthanide and actinide ions. Access to these species relies on a fine understanding of the mechanism underlying their formation, and the sensitivity of the β-di-iminium skeleton towards nucleophiles (phenols) has been identified as the limiting side reaction in the synthetic route. Addition of reactants in well defined order allowed the formation of two new N-aryl-oxy-β-diketiminate dianions on a multi-gram scale. The two ligands differ by their steric bulk and exhibit different coordination behaviors towards lanthanides and actinide ions, which were rationalized on geometric considerations. The reactivity of three of these new complexes has been investigated. A Ce(III) N-aryl-oxy-β-diketiminate complex exhibits interesting reduction properties, due to the shift of its oxidation potential to negative values by its coordination environment. A Th(IV) complex presents a vacant coordination site, which has been probed with different Lewis bases, emphasizing two spatial arrangements ruled by inter-ligand repulsion. It has been compared to its U(IV) analogue, which can be oxidized to a rare terminal mono-oxo uranium(VI) species. The latter was reversibly reduced to its U(V) and U(IV) derivatives, creating the first series of terminal mono-oxo uranium complexes with three successive oxidation states. These compounds represent an opportunity to better understand the influence of f-electrons on the inverse trans influence (ITI) in uranium oxo complexes. Preliminary DFT calculations have been carried out to explore geometric and energetic aspects at play in this interaction. (author) [fr

  15. Pedogennyje i litogennyje osobennosti mineralogičeskogo sostava černozema na krasnocvetnych porodach

    Czech Academy of Sciences Publication Activity Database

    Lesovaja, S. N.; Kapička, Aleš; Petrovský, Eduard; Aparin, B. F.

    2003-01-01

    Roč. 36, č. 12 (2003), s. 1482-1490 ISSN 0032-180X Grant - others:RFFI(RU) 01-04-48815 Institutional research plan: CEZ:AV0Z3012916 Keywords : mineralogical composition * chernozem * magnetic minerals Subject RIV: DE - Earth Magnetism, Geodesy, Geography

  16. Osobennosti razvitiya sakharnogo diabeta u bol'nykh tuberkulezom legkikh v Respublike Dagestan

    Directory of Open Access Journals (Sweden)

    S A Abusuev

    2008-12-01

    Full Text Available Цель. Выявить клинико-эпидемиологические особенности развития СД и туберкулеза легких при сочетанной патологии: возраст начала болезни; половой состав; соотношение городских и сельских жителей; распределение СД по степени тяжести; распределение туберкулеза по клиническим формам, бактериовыделению. Материалы и методы. Материалами исследования явились данные компьютерного полицевого регистра Республиканского противотуберкулезного диспансера на 11 702 вновь выявленных больных за 1999?2005 гг. и 143 истории болезни и амбулаторные карты больных Республиканского противотуберкулезного диспансера, туберкулезных больниц городов Буйнакска, Избербаша, Каспийска и Республиканского эндокринологического центра с сочетанием сахарного диабета и туберкулеза легких. Эти больные находились на учете в 2001?2006 гг. Для сравнения были использованы ранее опубликованные материалы по СД в Дагестане. Результаты. Из 143 больных СД и туберкулезом СД1 болели 18,88% (27 чел., СД 2 ? 81,12% (116 чел.. Среди больных СД2 в молодом возрасте заболели 25,00% (29 чел., в зрелом ? 52,59% (61 чел., в пожилом ? 21,55% (25 чел., в старческом ? 0,86% (1 чел.. Инфильтративный туберкулез был у 70,63% (101 чел., фиброзно-кавернозный ? у 11,19% (16 чел., очаговый ? у 5,60% (8 чел., диссеминированный ? у 4,19% (6 чел., туберкулома ? у 4,19% (6 чел., казеозная пневмония ? у 2,10% (3 чел., цирротический туберкулез ? у 1,40% (2 чел., туберкулезный плеврит ? у 0,70% (1 чел.. Выводы. Сочетание СД и туберкулеза характеризуется следующим: частое начало СД1 наблюдается в юношеском возрасте, СД2 ? в зрелом возрасте; наиболее частое начало туберкулеза у больных сахарным диабетом отмечается в зрелом и пожилом возрасте, в то время как среди всех вновь выявленных больных туберкулезом преобладают лица юношеского и молодого возраста; среди больных СД1 и туберкулезом преобладают мужчины, а среди больных СД2 и туберкулезом ? женщины; сочетанной патологией чаще страдают городские жители, причем как мужчины, так и женщины.

  17. Osobennosti kliniki i diagnostiki ishemicheskoy nefropatii u bol'nykh sakharnym diabetom 2 tipa

    Directory of Open Access Journals (Sweden)

    Inna Igorevna Klefortova

    2007-12-01

    Full Text Available Цель. Оценка распространенности особенностей клинического течения и прогностической значимости ИН у больных сахарным диабетом 2 типа. Материалы и методы. В скрининговое исследование были включены 157 пациентов (63 мужчины, 94 женщины с СД 2 в возрасте старше 50 лет. Всем пациентам проводилось общеклиническое обследование: клинический анализ крови, общий анализ мочи, биохимическое исследование крови, коагулограмма, оценка углеводного обмена (гликированный гемоглобин, альбуминурия, скорость клубочковой фильтрации (СКФ, ЭКГ, суточное мониторирование АД, ЭХОКГ, осмотр глазного дна. Всем пациентам была выполнена дуплексная ультрасонография ПА и брюшной аорты аппаратом. Для верификации диагноза ИН выполнялась магнитно резонансная ангиография (МРА ПА и брюшной аорты с внутривенным введением контрастного препарата. Результаты. Выявлено 58 (36,3% пациентов с СД 2 со стенозом ПА, из них: у 47 (28,7% пациентов ? односторонний, у 11 (7,6 % ? двусторонний. Оценивая возрастное распределение ИН, было отмечено, что чаще всего стеноз ПА определялся в возрастной группе от 50 до 59 лет ? 41,3%, в группе 60?69 лет этот показатель составил 30,7%, у пациентов старше 70 лет ? 40,9%. При сравнении значений уровня креатинина и СКФ до и после МРА и МСКТ статистически значимых различий получено не было. Оба метода визуализации позволили безопасно верифицировать диагноз у больных СД 2 с СКФ >30 мл/мин/1,73м2. Заключение. Дуплексная сонография ПА и брюшной аорты может служить методом скрининга ИН у больных СД 2. МРА и МСКТ являются безопасными методами верификации диагноза при условии соблюдения профилактики контрастиндуцированной нефропатии у больных СД 2. ИН является фактором риска прогрессирования кардиальной и почечной патологии у больных СД 2.

  18. Osobennosti khronicheskikh ran u bol'nykh sakharnym diabetom i puti ikh korrektsii

    Directory of Open Access Journals (Sweden)

    A Yu Tokmakova

    2007-03-01

    Full Text Available Хронические раневые дефекты (трофические язвы стоп часто встречающееся и специфичное для диабета поражение. Их определяют как эрозию кожи, распространяющуюся не только на эпидермис и дерму, но и проникающую в более глубоко расположенные ткани и характеризующуюся замедленной эпителизацией [13]. Распространенность хронических раневых дефектов нижних конечностей у пациентов с сахарным диабетом, по мнению различных авторов, составляет от 4 до 15% [16]. Локализация поражений на стопе зависит в основном от этиологических факторов. По данным эпидемиологических исследований у больных сахарным диабетом наиболее часто диагностируются раневые дефекты тыльной и подошвенной поверхностей пальцев, подошвенной поверхности в зоне проекции плюснефаланговых суставов и костей предплюсны. Последние характеризуются наиболее тяжелым течением и худшим клиническим прогнозом [14]. Большинство исследователей считает нейропатию, связанные с ней изменения периферической чувствительности и специфические изменения костных структур стопы наиболее значимым фактором в развитии хронических раневых дефектов мягких тканей нижних конечностей. Для того чтобы правильно выбрать тактику лечения хронических раневых дефектов у больных сахарным диабетом, необходимо учитывать особенности течения раневого процесса у данной категории пациентов.

  19. Osobennosti jenergeticheskoj strategii ES v Baltijskom regione [The features of EU energy strategy in the Baltic region

    Directory of Open Access Journals (Sweden)

    Kretinin Gannady

    2011-01-01

    Full Text Available This article analyses the issues of EU energy policy in the 1990s-the beginning of the 2000s in order to identify the features of energy supply and energy safety of the Baltic region countries. The research and practical significance of the work lies in the stepwise description of actions taken by EU leaders and EU member states in order to formulate a common European energy policy. The 2004 EU enlargement posed the problem of taking into account the features of energy supply of Eastern European countries and, especially, the Baltic States. The energy industries of Lithuania, Latvia, and Estonia, as well as other Eastern European and CIS countries, are closely related to the energy industry of the Russian Federation. Trying to allow for this circumstance, EU leaders and energy structures took a number of organizational measures aimed, on the one hand, at an increase in energy independence of new members of the EU and, on the other hand, at taking into account the recent trends in the energy market development. The research shows that most of the initiatives do not take into account the perspective and interests of Russia, which has a strong presence in the energy market. The analysis conducted will help the assessment of prospects of further development of the Baltic States' energy industry and its interaction with that of the Russian Federation.

  20. Influence of complexing on physicochemical properties of polymer-salt solutions. Vliyanie kompleksoobrazovaniya na fiziko-khimicheskie svojstva polimerno-solevykh rastvorov

    Energy Technology Data Exchange (ETDEWEB)

    Ostroushko, A A; Yushkova, S M; Koridze, N V; Skobkoreva, N V; Zhuravleva, L I; Palitskaya, T A; Antropova, S V; Ostroushko, I P [Ural' skij Gosudarstvennyj Univ., Sverdlovsk (Russian Federation) AN SSSR, Moscow (Russian Federation). Inst. Obshchej i Neorganicheskoj Khimii

    1993-06-01

    Using the methods of spectrophotometry, viscosimetry, conductometry the influence of salt-polymer complexing processes on physicochemical prperties of aqueous solutions of yttrium, barium, copper nitrates and formates with polyvinyl alcohol was studied. Change of dynamic viscosity, specific electric conductivity of solutions in the process of complexing was shown. Thermal effects of salt-polymer interaction were measured. It is shown that decrease of transition temperature of polymer to plastic state in films, temperature and effective activation energy of salt decomposition is also connected with complexing. Effective values of surface tension on the boundary with air are measured. Coefficients of cation diffusion in polymer-salt solutions are estimated.

  1. A study of the complex formation of bivalent lanthanides with tetraphenylborate-ion in organic solvents. Izuchenie kompleksoobrazovaniya dvukhvalentnykh lantanoidov s tetrafenilborat-ionom v organicheskikh rastvoritelyakh

    Energy Technology Data Exchange (ETDEWEB)

    Veleshko, I E; Mikheev, N B; Kulyukhin, S A

    1992-01-01

    Interaction of bivalent lanthanides with tetraphenylborate-ion (BPh[sub 4][sup -]) in solutions of CH[sub 3]CN and C[sub 2]H[sub 5]OH was studied by the methods of cocrystallization, conductometry and spectrophotometry.It is shown that no complexing between Ln[sup 2+] and BPh[sub 4][sup -] takes place in ethanol, wheras in CH[sub 3]CN formation of second sphere complexes of the composition [Ln(CH[sub 3]CN)[sub n

  2. Polarographic investigation of complexing kinetics of polyacrylate anions with cadmium ions. Polyarograficheskoe issledovanie kinetiki kompleksoobrazovaniya poliakrilat-anionov s ionami kadmiya

    Energy Technology Data Exchange (ETDEWEB)

    Avlyanov, Zh K; Kabanov, N M; Zezin, A B; Askarov, M A

    1990-01-01

    The processes which occur during the reduction of cadmium ions from polymer-metallic complexes (PMC) are studied for the purposes of polarographic investigation of complexing kinetics of polyacrylate anions (PAA) of different molecular masses with cadmium ions in KCl aqueous solutions. An expression is derived for establishing semiwave potential. PMC formation and dissociation reduction rate constants are calculated. It is shown that intramolecular reorderings required for the formation of a two-coordinate complex proceed much slower as compared to the diffusion of free ions.

  3. Investigation of REE perchlorates complexing with benzimidazole in aqua-dioxane media. Issledovanie kompleksoobrazovaniya perkhloratov RZEh s benzimidazolom v vodno-dioksanovoj srede

    Energy Technology Data Exchange (ETDEWEB)

    Akhrimenko, Z M; Panyushkin, V T; Ishbulatova, S K [Kubanskij Gosudarstvennyj Univ., Krasnodar (Russian Federation)

    1992-01-01

    Stability constant (K[sub 1]) of complexes of rare earth perchlorates with benzimidazole were determined by the method of pH-metric titration. Nonmonotonous change in lgK[sub 1] with rare earth ordinal number increase was revealed.

  4. Structural studies of f-element complexes with soft donor extractants

    International Nuclear Information System (INIS)

    Jensen, Mark P.; Bond, Andrew H.; Nash, Kenneth L.

    2000-01-01

    To better understand the unique features and structural implications of An-soft donor interactions, we used solvent extraction, extended x-ray absorption fine structure (Exafs), and optical spectroscopy to study both the lanthanide and actinide complexes of a series of dialkylphosphinic acid extractants, bis(2,4,4-trimethylpentyl)phosphinic acid, bis(2,4,4-trimethylpentyl)monothiophosphinic acid, and bis(2,4,4- trimethylpentyl)dithiophosphinic acid, which are the primary components of the commercial extractants Cyanex 272, Cyanex 302, and Cyanex 301

  5. Synthesis and assessment of imprinted polymers for the separation of f elements. Application to liquid chromatography

    International Nuclear Information System (INIS)

    Vigneau, Olivier

    2002-01-01

    Within the frame of the CEA's SPIN programme which aims at separate lanthanides (Ln) and actinides (An) in order to decrease the volume and activity of nuclear wastes to be stored, and after a presentation of lanthanides and actinides, of the main methods of inter-group and intra-group separation, this research thesis presents the principles and applications of the molecular print and ionic print which are then used to perform the Ln/Ln and Ln/an separation. The author discusses the choice and synthesis of selective complexing monomers which are used for the synthesis of imprinted polymers. The next chapter reports the synthesis of imprinted polymers, the assessment of their properties (selectivity and extraction power) in Ln/Ln competitive extraction in a batch reactor, and the optimization of synthesis conditions. Then, the author reports the assessment of properties of imprinted material in terms of ability to perform an inter-group Am 241 / Eu 152 separation in a batch reactor. The last part addresses Ln/Ln separation by High Performance Liquid Chromatography by using synthesised imprinted polymers as steady phase [fr

  6. Tripodal diglycol-amides as highly efficient extractants for f-elements

    Energy Technology Data Exchange (ETDEWEB)

    Janczewski, D.; Reinhoudt, D. N.; Verboom, W. [Univ Twente, Mesa Res Inst Nanotechnol, Lab Supramol Chem and Technol, NL-7500 AE Enschede, (Netherlands); Janczewski, D. [Inst Mat Res and Engn, Singapore 117602, (Singapore); Verboom, W. [Univ Twente, Mesa Res Inst Nanotechnol, Lab Mol Nanofabricat, NL-7500 AE Enschede, (Netherlands); Hill, C.; Allignol, C.; Duchesne, M. T. [CEA Valrho, DRCP/SCPS/LCSE, F-30207 Bagnols Sur Ceze, (France)

    2008-07-01

    A series of new ligands bearing three diglycol-amide functions pre-organized at the C-pivot and tri-alkyl-phenyl platforms was synthesized. They are very efficient extractants for Am{sup 3+} and Eu{sup 3+} with an up to five times relative extraction ability for Eu{sup 3+}. The distribution coefficients are up to 1000 times increased upon alkylation or arylation of the N-position of the diglycol-amide moieties. The tripodal diglycol-amides show a 1: 1 metal to ligand stoichiometry as proven with three independent methods for the complexation of the 3-pentyl N-substituted diglycol-amide ligand with Eu{sup 3+} (K = 2.5 x 10{sup 5} M{sup -1} in acetonitrile-water). A cage-like cryptand, containing three diglycol-amide units, was prepared using a Eu{sup 3+} templated synthesis. However, it does not exhibit improved extraction properties. (authors)

  7. Chemical analogy in the case of hydrolysis species of F-elements

    International Nuclear Information System (INIS)

    Hirotake Moriyama; Hajimu Yamana; Kenso Fujiwara

    2001-01-01

    In spite of much importance, some of the thermodynamic data of actinide elements are still lacking, and the chemical behaviour of these elements is often predicted by considering chemical analogy, that is by taking the known data of the same and similar group elements. It is thus quite important to establish the basis and conditions for applying the chemical analogy. In the present study, some topics are discussed which are related with the chemical analogy for the hydrolysis behaviour of actinide ions. Systematic trends of the thermodynamic data of actinide ions, namely the solubility products and hydrolysis constants, are discussed by considering the results of recent measurements and by considering possible contributions of non-electrostatic interactions of actinide ions in addition to those of ordinary electrostatic ones. (authors)

  8. Theoretical study of the electronic structure of f-element complexes by quantum chemical methods

    International Nuclear Information System (INIS)

    Vetere, V.

    2002-09-01

    This thesis is related to comparative studies of the chemical properties of molecular complexes containing lanthanide or actinide trivalent cations, in the context of the nuclear waste disposal. More precisely, our aim was a quantum chemical analysis of the metal-ligand bonding in such species. Various theoretical approaches were compared, for the inclusion of correlation (density functional theory, multiconfigurational methods) and of relativistic effects (relativistic scalar and 2-component Hamiltonians, relativistic pseudopotentials). The performance of these methods were checked by comparing computed structural properties to published experimental data, on small model systems: lanthanide and actinide tri-halides and on X 3 M-L species (X=F, Cl; M=La, Nd, U; L = NH 3 , acetonitrile, CO). We have thus shown the good performance of density functionals combined with a quasi-relativistic method, as well as of gradient-corrected functionals associated with relativistic pseudopotentials. In contrast, functionals including some part of exact exchange are less reliable to reproduce experimental trends, and we have given a possible explanation for this result . Then, a detailed analysis of the bonding has allowed us to interpret the discrepancies observed in the structural properties of uranium and lanthanides complexes, based on a covalent contribution to the bonding, in the case of uranium(III), which does not exist in the lanthanide(III) homologues. Finally, we have examined more sizeable systems, closer to experimental species, to analyse the influence of the coordination number, of the counter-ions and of the oxidation state of uranium, on the metal-ligand bonding. (author)

  9. Dialkyldithiophosphoric acids - chemical properties and 5f and 4f elements ions extraction

    International Nuclear Information System (INIS)

    Pattee, D.

    1987-09-01

    This work is a contribution to the study of the properties of the dialkyldithiophosphoric acids and of the extraction of the 4f and 5f ions from weakly acidic nitrate and phosphate media. Following a complete bibliographic study, synthesis and purification of the di-2-ethylhexyl-dithiophosphoric acid (HDEHDTP) is studied. It is identified with chemical methods and spectroscopic methods (I.R., N.M.R., V.P.C.); its by products, the di-2-ethylhexyl (monothio) phosphoric acids (HDEHTP, HDEHP) are also identified and characterized. Stability against hydrolysis and radiolysis is determined. The extractive properties are studied for the 4f and 5f ions. The presence of a sulfur donor atom in HDEHDTP makes it inefficient for the extraction of trivalent lanthanides and actinides but brings out a certain selectivity for americium. For HDEHTP, the presence of an oxygen donor atom rubs out any selectivity and the extraction constants are greater. Selectivity of HDEHDTP is increased by TBP (tri-n-butylphosphate) in synergistic mixtures. The mechanism of extraction of hexavalent uranium from phosphoric medium is elucidated. A model is developed by NMR for the micellisation of the sodium salts of HDEHDTP, HDEHTP and HDEHP, and extrapolated it to the trivalent rare earth salts of the acids. The structures are verified by light scattering and low angle X-ray diffraction [fr

  10. Thermodynamic approach of the poly-azine - f element ions interaction in aqueous conditions

    International Nuclear Information System (INIS)

    Miguirditchian, M.; Guillaumont, D.; Moisy, P.; Guillaneux, D.; Madic, C.

    2004-01-01

    2-Amino-4,6-di-(pyridine-2-yl)-1,3,5-triazine (Adptz) was considered as a model compound for selective aromatic nitrogen extractants (poly-azines) of minor actinides. Thermodynamic data ( ΔG 0 , ΔH 0 , ΔS 0 ) were systematically acquired for the complexation of lanthanide(III) ions as well as yttrium(III) and americium(III) in hydro-alcoholic medium. Two complementary experimental approaches were followed. Stability constants for the formation of the 1:1 complexes were evaluated from UV-visible spectrophotometry titration experiments, whereas enthalpies and entropies of reaction were obtained consistently from either temperature dependence experiments or micro-calorimetry. The interaction of Adptz with lanthanide(III) and yttrium(III) ions was found to be essentially ionic and dependent upon the hydration and size of the ion. As for americium(III) ion, stability constant and enthalpy of complexation was significantly larger. This was attributed to a partial electronic transfer from the ligand to empty orbitals of the cation. DFT calculations support this interpretation. (authors)

  11. Design and reactivity of mono- and polymetallic complexes of low valent f-elements

    International Nuclear Information System (INIS)

    Camp, Clement

    2013-01-01

    Beyond its importance in nuclear industry the redox chemistry uranium is attracting increasing interest because complexes of low-valent uranium can promote unusual reductive chemistry through unusual reaction pathways, including attractive examples of CO, CO 2 , N 2 , arenes and azides activation in mild condition. Due to the unique coordination and bonding properties of uranium, its compounds could provide an attractive alternative to transition metals for the catalytic transformation of small molecules. However, metal-based multi-electron processes remain uncommon in uranium chemistry especially in comparison with the d-block metals, the chemistry of low-valent uranium being dominated by single-electron transfers. In this context, the first aim of this project was to investigate the association of low-valent uranium to a non-innocent ligand acting as an independent electron reservoir at a same molecule. Accordingly, we interrogated the use of highly p-delocalized Schiff bases ligands for supporting low-valent uranium chemistry. This led to the isolation of electron-rich complexes which are stabilized by storing electrons on the ligands through the formation of C-C bonds. Interestingly, these C-C bonds can be cleaved by oxidizing agents and the electrons released to participate in multi-electron redox reactions. This process was observed within different Schiff-base ligand scaffolds, allowing a tuning of the properties of the compounds. The second part of this work was dedicated to the synthesis of novel trivalent uranium complexes supported by siloxy ligands and the study of their redox reactivity and coordination properties. Novel dinuclear highly-reactive low-valent uranium assemblies were developed. The study of their limited stability revealed that these compounds are spontaneously decomposing through the cleavage of tBu groups from the supporting ligands resulting in the formation of U(IV) species. In parallel, a mononuclear trivalent uranium complex was obtained, allowing to compare the reactivity of U(III) in different steric and electronic environments. Hence we became interested in studying the redox reactivity of these compounds with different substrates including CO 2 , CS 2 , azides and arenes. These investigations led to the stabilization of a rare CS 2 2- sandwich complex of uranium, and highlighted the ability of U(III) to promote reductive disproportionation of CO 2 to carbonate and CO. The reaction of these trivalent uranium siloxide species with organic and inorganic azides produced original uranium imidos and nitridos compounds with original topologies. Finally the capacity of these strongly reducing agents to transfer electrons to the toluene fragment lead to the isolation of a family of arenes inverted sandwich complexes. (author) [fr

  12. Syntheses and structures of three f-element selenite/hydroselenite compounds

    International Nuclear Information System (INIS)

    Burns, Wendy L.; Ibers, James A.

    2009-01-01

    The selenite/hydroselenite compounds Ce(SeO 3 )(HSeO 3 ), Tb(SeO 3 )(HSeO 3 ).2H 2 O, and Cs[U(SeO 3 )(HSeO 3 )].3H 2 O were synthesized by hydrothermal means at 453 K from the reaction of CeO 2 or Tb 4 O 7 or UO 2 with SeO 2 and CsCl (as a mineralizer). Ce(SeO 3 )(HSeO 3 ) crystallizes in the non-centrosymmetric orthorhombic space group Pca2 1 . The structure comprises a two-dimensional network of interconnected CeO 10 bicapped distorted square antiprisms and SeO 3 trigonal pyramids. Tb(SeO 3 )(HSeO 3 ).2H 2 O crystallizes in the non-centrosymmetric orthorhombic space group P2 1 2 1 2 1 . The structure features a two-dimensional layer of interconnected TbO 8 distorted square antiprisms and SeO 3 trigonal pyramids. Cs[U(SeO 3 )(HSeO 3 )].3H 2 O crystallizes in the centrosymmetric monoclinic space group P2 1 /n. The structure consists of two-dimensional layers of interconnected UO 7 pentagonal bipyramids and SeO 3 trigonal pyramids. The layers in all three structures are held together by hydrogen-bonding networks. - Graphical abstract: Structure of Ce[U(SeO 3 )(HSeO 3 )].3H 2 O (Cs, purple; U, black; Se, blue; O, red; O w , green; H, gray).

  13. Design and reactivity of mono- and polymetallic complexes of low valent f-elements

    OpenAIRE

    Camp , Clément

    2013-01-01

    Beyond its importance in nuclear industry the redox chemistry uranium is attracting increasinginterest because complexes of low-valent uranium can promote unusual reductive chemistrythrough unusual reaction pathways, including attractive examples of CO, CO2, N2, arenes andazides activation in mild condition. Due to the unique coordination and bonding properties ofuranium, its compounds could provide an attractive alternative to transition metals for thecatalytic transformation of small molecu...

  14. Russkie v Latvii: osobennosti sociokul'turnoj adaptacii i identichnosti [Russians in Latvia: Peculiarities of Socio-cultural Adaptation and Identity

    Directory of Open Access Journals (Sweden)

    Voronov Viktor

    2009-01-01

    Full Text Available The author identifies trends and variations of the socio-cultural identity and integration of Russians in Latvia. According to the author, since the middle 1990s, two trends have been recognized - first, the “ingrowing” of ethnic Russians into the life of independent Latvia, and second, forming their new identity. The article presents a number of factors hampering the integration of ethnic Russians into Latvian society. Variations and options of socio-cultural identity and integration (or assimilation of the Russian population of Latvia are shown.

  15. Features of method of employments on aerobics with the use of exercises of sporting orientation. [Osobennosti metodiki zaniatij po aerobike s ispol'zovaniem uprazhnenij sportivnoj napravlennosti

    Directory of Open Access Journals (Sweden)

    Lulina N.V.

    2011-11-01

    Full Text Available The features of method of leadthrough of employments are considered on aerobics. 24 girls of the first course took part in an experiment. Directions are offered perfection of outside the time limit forms of employments. A basic orientation of employments is a capture from the different types of sport and increase of level of physical preparedness of girls motive actions. Is proposed method of employments on aerobics with the use of imitation exercises from the different types of sport. It is rotined that with imaginary objects in hands it is possible to execute different exercises: javelin-throwing or kernel, throws of ball etc. It is set that during a slow imitation individuality of loading is regulated the volitional capabilities of man. In this case protective reflexes do not allow to overstrain a muscle.

  16. Processy konvergencii i divergencii v regionah Evropejskogo sojuza: osobennosti i kvalimetrija [Processes of convergence and divergence in the re-gions of the European Union: features and qualimetry

    Directory of Open Access Journals (Sweden)

    Voronov Viktor

    2013-01-01

    Full Text Available A higher level of unity and cohesion across the European Union member states is an important aspect of European integration though it has a rather ambiguous nature. The Law on the Common Market, which aims to increase the economic efficiency of the EU, became a subject of extensive discussions among researchers suggesting that its viability at the political and socio-economic levels depends on a fair distribution of gains among the countries and regions of the Community. These discussions resulted in a considerable increase in funding allocated for the development of the EU regions from the EU Structural Funds and the Cohesion Fund aiming to reduce regional disparities. The present analysis and the assessment of convergence processes (GDP per capita at purchasing power parity in the EU regions of NUTS-1, -2, -3 levels in 1995 -2009/2010 help demonstrate the efficiency of these efforts.

  17. K izučeniju kul'tury s keramikoj pražskogo tipa na territorii Moravii: formirovanije i osobennosti

    Czech Academy of Sciences Publication Activity Database

    Jelínková, Dagmar

    -, č. 5 (2015), s. 117-150 ISSN 1608-9057 Institutional support: RVO:68081758 Keywords : Prague-type pottery culture * Moravia * dating * Cultural relations to the east and South-East * Influence of the Merovingian sphere Subject RIV: AC - Archeology, Anthropology, Ethnology

  18. Metodologicheskie osobennosti upravlenija stoimost'ju kompanii, osushhestvljajushhej «zelenye» innovacii [The methodological features of managing the value of companies introducing "green" innovations

    Directory of Open Access Journals (Sweden)

    Kharin Alexander

    2012-01-01

    Full Text Available Although it is a common assumption that innovations are one of the most important factors of economic development, there is a need to review some provisions of innovation methodology so that new fundamental values are taken into account more fully. Most recent business models are based on the depletion of natural environment, whose potential has been almost exhausted. It is necessary to introduce new ideas that are of use for society and create values for companies. One way of achieving this goal is “green” (environmental innovations. The next decade is expected to see a rapid growth in environmental innovations. Their organization and management will require modern — and adequate to the objectives set —technologies. One of those is the quest for value methodology. To date, the quest for value methodology has given rise to several conceptual approaches, which can be used to evaluate the effectiveness of environmental innovations. This article discusses the advantages and disadvantages of major approaches. The author comes to a conclusion that that the modern theory and practice of corporate finance still lacks a generally accepted approach to assessing the value of companies that explicitly takes into account the impact of environmental factors on the cost. The article outlines the basic theoretical frameworks for the formation of such approach.

  19. Study of Sr sup 2+ and Eu sup 2+ complexing with 18-crown-6 in aqueous-ethanolic solutions. Izuchenie kompleksoobrazovaniya Sr sup 2+ i Eu sup 2+ s 18-kraun-6 v vodno-ehtanol'nykh rastvorakh

    Energy Technology Data Exchange (ETDEWEB)

    Kulyukhin, S A; Majorov, A V; Kamenskaya, A N; Mikheev, N B

    1989-01-01

    Using cocrystallization and conductometry methods Sr{sup 2+} and Eu{sup 2+} complexing with 18-crown-6 in aqueous-ethanolic solutions at (H{sub 2}O)=10 mol/l is studied. Stability constants of Sr{sup 2+} and Eu{sup 2+} complexes with 18-crown-6 in C{sub 2}H{sub 5}OH, for which lg{beta} is equal to (4.76{plus minus}0.12) and (4.72{plus minus}0.13) respectively, are determined. Comparison of the investigated elements features during complexing with 18-crown-6 in aqueous and aqueous-ethanolic solutions is carried out. It is shown that both in water and in C{sub 2}H{sub 5}OH -10 mol/l H{sub 2}O system under Sr{sup 2+} and Eu{sup 2+} complexing with 18-crown-6 the differences in properties of these elements are not detected.

  20. F-Element ion chelation in highly basic media. Annual progress report, October 1, 1996 - July 1, 1997

    International Nuclear Information System (INIS)

    Paine, R.T.

    1997-01-01

    'The specific fundamental chemical objectives of this project are to: (1) study the chemical speciation of Sr and Ln ions in basic media formed in aqueous solutions with and without classical chelation agents (e.g., EDTA, polyphosphates, and organic carboxylates); (2) prepare pyridine N-oxide phosphonate and phosphonoacetate chelators of the types 1--3 and characterize their ionization properties by titrimetric techniques; (3) study the interactions of 5--7 with soluble oxide-hydroxide metallate species and higher molecular weight sols, gels and precipitates containing Sr and Ln ions, as time permits, interactions with oxide-hydroxide metallates of U, Th, Ba, Al and Fe will also be studied; (4) study the interactions of newly designed phosphonate ligands with oxide-hydroxide metallate species; (5) transfer the fundamental coordination chemistry revealed here to research groups at LANL and PNNL that will utilize the results to improve tank waste treatment protocols.'

  1. The Thermodynamic Properties of the f-Elements and their Compounds. Part 2. The Lanthanide and Actinide Oxides

    Energy Technology Data Exchange (ETDEWEB)

    Konings, Rudy J. M., E-mail: rudy.konings@ec.europa.eu; Beneš, Ondrej; Kovács, Attila; Manara, Dario; Sedmidubský, David [European Commission, Joint Research Centre, Institute for Transuranium Elements, P.O. Box 2340, 76125 Karlsruhe (Germany); Gorokhov, Lev; Iorish, Vladimir S.; Yungman, Vladimir; Shenyavskaya, E.; Osina, E. [Joint Institute for High Temperatures, Russian Academy of Sciences, 13-2 Izhorskaya Street, Moscow 125412 (Russian Federation)

    2014-03-15

    A comprehensive review of the thermodynamic properties of the oxide compounds of the lanthanide and actinide elements is presented. The available literature data for the solid, liquid, and gaseous state have been analysed and recommended values are presented. In case experimental data are missing, estimates have been made based on the trends in the two series, which are extensively discussed.

  2. Single-ion 4f element magnetism: an ab-initio look at Ln(COT)2(-).

    Science.gov (United States)

    Gendron, Frédéric; Pritchard, Benjamin; Bolvin, Hélène; Autschbach, Jochen

    2015-12-14

    The electron densities associated with the Ln 4f shell, and spin and orbital magnetizations ('magnetic moment densities'), are investigated for the Ln(COT)2(-) series. The densities are obtained from ab-initio calculations including spin-orbit coupling. For Ln = Ce, Pr the magnetizations are also derived from crystal field models and shown to agree with the ab-initio results. Analysis of magnetizations from ab-initio calculations may be useful in assisting research on single molecule magnets.

  3. Influence of some f-elements on the properties of InP layers prepared by LPE

    Czech Academy of Sciences Publication Activity Database

    Procházková, Olga; Zavadil, Jiří; Žďánský, Karel; Novotný, Jan; Peřina, Vratislav

    1999-01-01

    Roč. 50, 2/s (1999), s. 20-23 ISSN 1335-3632. [Development of Materials Science in Research and Education - DMS -RE 1998 /8./. Zlenice, 08.09.1998-10.09.1998] R&D Projects: GA ČR GA102/96/1238; GA AV ČR KSK1010601 Projekt 7/96/K:4073 Institutional research plan: CEZ:AV0Z2067918 Keywords : III-V semiconductors * rare earth compounds * liquid phase epitaxial growth * crystal defects Subject RIV: CA - Inorganic Chemistry

  4. F-element metalated dipyrrins: synthesis and characterization of a family of uranyl bis(dipyrrinate) complexes.

    Science.gov (United States)

    Bolotaulo, Duer; Metta-Magaña, Alejandro; Fortier, Skye

    2017-03-07

    Using an improved, chromatography-free dipyrrin synthesis, the α,β-unsubstituted dipyrrins [RC(C 4 H 2 N) 2 H] (2) (R = tolyl (2toly l ), p-OMe-C 6 H 4 (2anis), mesityl (2mes), ferrocenyl (2Fc)) were isolated in good to excellent yields. Deprotonation of 2 with Na[N(SiMe 3 ) 2 ] gives the alkali metal salts [Na(DME) n ][RC(C 4 H 2 N) 2 ] (3) which reacts with UO 2 Cl 2 (THF) 3 to give the uranyl bis(dipyrrinates) UO 2 [RC(C 4 H 2 N) 2 ] 2 (L) (L = THF (4R-THF); DMAP (4R-DMAP)) (R = tolyl, p-OMe-C 6 H 4 , mesityl, ferrocenyl). The THF adducts, 4R-THF, are unstable in aromatic and nonpolar solvents and rapidly decompose to 2 and an intractable uranium-containing solid. On the other hand, the DMAP adducts, 4R-DMAP, are indefinitely stable in solution. The solid-state structures of 4R-THF and 4R-DMAP reveal distorted trigonal bipyramidal geometries. In the solid-state, the dipyrrinate ligands exhibit significant distortions including bowing and, in some instances, out-of-plane equatorial N-atom coordination, likely as a consequence of steric crowding and interligand repulsion. The complexes, 4R-DMAP, have been fully characterized by NMR, UV/Vis, and fluorescence spectroscopies, and their electrochemical properties have been investigated through cyclic voltammetry. The cyclic voltammograms of 4R-DMAP display several redox features but present a reversible wave at ca. -1.9 V (vs. Fc 0/+ ) attributable to a ligand centred reduction. Fluorescence measurements of all compounds reveal that only the mesityl derivatives 2mes, 3mes, and 4mes fluoresce with modest Stokes shift that ranges from ca. 30-70 nm, with 4mes displaying the greatest relative emission intensity.

  5. Amide mediated enhancement of sorption efficiency of trivalent f-elements on functionalized carbon nanotube: evidence of physiosorption

    International Nuclear Information System (INIS)

    Gupta, Nishesh K.; Sengupta, Arijit; Rane, Vinayak G.; Kadam, R.M.

    2017-01-01

    Amide Functionalized multi-walled carbon nanotube (CNT-DHA) was found to enhance the sorption efficiency of trivalent lanthanides and actinides from aqueous acidic solution. Langmuir, Freundlich, Dubinin-Radushkevich (D-R) and Temkin isotherm models were employed to understand the sorption mechanism revealing the predominance of Fruendlich isotherm. The sorption energy evaluated from D-R isotherm revealed the sorption process is physisorption, which was confirmed by the no shift in the IR frequency of amide functionality of carbon nanotube on sorption. The EPR spectra of the Gd"3"+ sorbed on carbon nanotube also showed no perturbation on the local environment of Gd"3"+ on sorption again revealing the physisorption. Analysis of the sorption kinetics through Lagergren's first order kinetics, intra particle diffusion model and pseudo second order kinetics revealed that the sorption kinetics followed pseudo second order kinetics for Am"3"+ and Eu"3"+ with rate constants 4.04E-05mg g"-"1 min"-"1 and 8.27E-05 mg g"-"1 min"-"1 respectively. The radiolytic stability of CNT-DHA was evaluated and found to be satisfactory. EDTA was found to strip the trivalent lanthanides and actinides almost quantitatively. (author)

  6. Complexation of f elements by tripodal ligands containing aromatic nitrogens. Application to the selective extraction of actinides(III)

    International Nuclear Information System (INIS)

    Wietzke, Raphael

    1999-01-01

    This work initiates a research project, whose aim is the actinides(lll)/lanthanides(III) separation by liquid-liquid extraction. We were interested in the study of the coordination chemistry of lanthanides(III) and uranium(III) (uranium(III) as model for the actinides(III)), with the aim to show differences between the two families and to better understand the coordination properties involved in the extraction process. We studied the lanthanide(III) and uranium(III) complexation with tripodal ligands containing aromatic nitrogens. Several tripodal ligands were synthesized varying the type and the number of the donor atoms. The lanthanide(III) complexes have been characterized in the solid state and in solution (by several techniques: "1H NMR, ESMS, luminescence, UV spectrophotometry, conductometry). Differences in the coordination were found depending on the nature of the donor atoms. The new ligands, tris(2-pyrazinylmethyl)amine (tpza) et tris(N,N-diethyl-2-carbamoyl-6- pyridylmethyl)amine (tpaa), have shown a selectivity for the actinides(III) with promising results in liquid-liquid extraction. The comparison between the lanthanum(III) and uranium(III) complexes with the ligand tpza showed differences in the bonding nature, which could be attributed to a covalent contribution to the metal-ligand bond. (author) [fr

  7. Methodical features of selection of radiation-resistant semiconductor devices on the base of initial informative parameters; Metodicheskie osobennosti otbora radiatsionno-stojkikh poluprovodnikovykh priborov po nachal`nym informativnym parametram

    Energy Technology Data Exchange (ETDEWEB)

    Zhukov, Yu N [and others

    1994-12-31

    A method for evaluating the statistic interrelation of informational parameter initial values with radiation resistance of semiconducting devices using the information content factor which is invariant relative to the election scope and confidence probability is proposed.

  8. Peculiarities of phenotype and genetic statuses of diabetes mellitus patients living on contaminated areas; Osobennosti fenotipicheskogo i geneticheskogo statusa lits s sakharnym diabetom 1 tipa, prozhivayushchikh na zagryaznennoj territorii

    Energy Technology Data Exchange (ETDEWEB)

    Mel' nov, S B; Morozik, V M; Mokhort, T V [International A. Sakharov environmental univ., Minsk (Belarus)

    2006-05-15

    Some peculiarities of cytogenetic status of the Diabetes Mellitus patients from areas with different level of ecology pressure were investigated. We found pronounced increase practically all types of aberrations. Comparative anthropology investigations showed real differences in status of children from mail group (citizens of radiation contaminated areas). (authors)

  9. Atomnaja jenergetika Pribaltiki: istorija vozniknovenija i politiko-jekonomicheskie osobennosti razvitija [Nuclear power in the Baltic Sea region: the history of emergence and the political and economic features of its development

    Directory of Open Access Journals (Sweden)

    Kretinin Gannady

    2013-01-01

    Full Text Available This article focuses on the development of peaceful nuclear power. The author draws attention to the fact that nuclear power is a rather young branch of national economy. However, over recent decades, it has already seen rises and falls, and a number of states have had tragic experiences of nuclear emergencies. Nevertheless, many countries — including the three Baltic States of Estonia, Latvia and Lithuania — express a strong interest in development, generation, and application of nuclear power. In the Baltic States, nuclear power dates back to the Soviet times, but its development was suspended pursuant to the EU regulations (the Ignalina NPP. Lithuania, Latvia, and Estonia have been striving for energy independence from Russia — the principal supplier of energy carriers to these countries. For a long time, the three Baltic States have been proclaiming their unanimity on the general European path of development. However, the reality proved to be different. The touchstone for achieving common goals was the idea of constructing a new NPP at the site of the closed Ignalina NPP. The author concludes that the joint construction of a new NPP is quite questionable. When it comes to politics, each of the three Baltic States is ready to build its own NPP. Thus, the development of nuclear power in the Baltic Sea region requires joint coordinated actions independent of any bloc-inspired interests of the states involved. Moreover, this success may prove sustainable if the actions are based on innovative decisions and modern technologies.

  10. Synthesis and properties of bis(pentamethylcyclopentadienyl) actinide hydrocarbyls and hydrides. A new class of highly reactive f-element organometallic compounds

    International Nuclear Information System (INIS)

    Fagan, P.J.; Manriquez, J.M.; Maatta, E.A.; Seyam, A.M.; Marks, T.J.

    1981-01-01

    The synthesis and chemical and physcochemical properties of Th and U bis(pentamethylcyclopentadienyl) chlorides, hydrocarbyls, chlorohydrocarbyls, and hydrides are reported. The reaction of the precursor compounds M[eta 5 -(CH 3 ) 5 C 5 ] 2 Cl 2 with 2 equiv of lithium reagent RLi produces M[eta 5 -(CH 3 ) 5 ] 2 R 2 compounds where R = CH 3 , CH 2 Si(CH 3 ) 3 , CH 2 C(CH 3 ) 3 , CH 2 C 6 H 5 , and C 6 H 5 (M = Th) and R = CH 3 , CH 2 Si(CH 3 ) 3 , CH 2 C 6 H 5 , and C 6 H 5 (M = U) in good yield. With 1 equiv of lithium reagent, M[eta 5 -(CH 3 ) 5 C 5 ] 2 (R)Cl compounds where R = CH 2 C(CH 3 ) 3 , CH 2 Si(CH 3 ) 3 , CH 2 C 6 H 5 , and C 6 H 5 (M = Th) and R = CH 2 C(CH 3 ) 3 CH 2 Si(C 3 ) 3 , CH 2 C 6 H 5 , and C 6 H 5 , and C 6 H 5 (M = U) are formed in high yield. The M[eta 5 -(CH 3 ) 5 C 52 (C 3 )Cl compounds can be synthesized by redistribution between the corresponding dimethyl and dichloro complexes. The new organoactinides were thoroughly characterized by elemental analysis, 1 H NMR and vibrational spectroscopy, and in many cases cryoscopic molecular weight measurements. The hydrocarbyls and chlorohydrocarbyls generally exhibit high thermal stability. However, the diphenyl compounds react readily with C 6 D 6 to yield, via a benzyne complex, the corresponding M(C 6 D 5 ) 2 compounds. The Th bis(neopentyl) complex reacts with benzene to produce the corresponding diphenyl complex. Competition experiments at -78 0 C indicate that the Th complexes are more reactive than those of U. The M[eta 5 -(CH 3 ) 5

  11. Metal-metal bonds involving the f elements. 4. Molecular orbital studies of metal-metal and metal-ligand interactions in dinuclear uranium(V) systems

    International Nuclear Information System (INIS)

    Cayton, R.H.; Novo-Gradac, K.J.; Bursten, B.E.

    1991-01-01

    The electronic structures of a series of dinuclear uranium(V) complexes have been investigated using Xα-SW molecular orbital calculations including quasirelativistic corrections. Complexes of the formula U 2 H 10 and U 2 (OH) 10 were used to model the metal-ligand σ and π interactions, respectively, in the known species U 2 (O-i-Pr) 10 . Two basic geometries were investigated: a vertex-sharing bioctahedron with only terminal ligands (D 4h symmetry) and an edge-sharing bioctahedron containing two bridging ligands (D 2h symmetry). The latter geometry, which is that of U 2 (O-i-Pr) 10 , was also examined at U-U bonding and nonbonding distances. The calculations indicate that the U-U interactions are significantly perturbed when H is replaced by OH, owing to strong donation from the OH pπ orbitals into selected U 5f orbitals. The result is a lack of any appreciable U-U interaction for U 2 (OH) 10 in either the D 4h or D 2h geometry. In addition, the overall OH π donation to the U 5f levels is enhanced in the D 2h geometry. The electronic structure of a hypothetical U(V) dimer, Cp 2 U 2 O 4 , was also examined in both bridged and unsupported geometries. The unbridged geometry, like that for U 2 (OH) 10 , suffered from a destabilization of the U-U σ orbital due to ligand π donation and revealed no net U-U bonding. However, the geometry exhibiting two bridging oxo ligands maintains the U-U σ-bonding MO as its lowest energy U 5f orbital. 21 refs., 8 figs., 8 tabs

  12. What a difference a 5f element makes: trivalent and tetravalent uranium halide complexes supported by one and two bis[2-(diisopropylphosphino)-4-methylphenyl]amido (PNP) ligands.

    Science.gov (United States)

    Cantat, Thibault; Scott, Brian L; Morris, David E; Kiplinger, Jaqueline L

    2009-03-02

    The coordination behavior of the bis[2-(diisopropylphosphino)-4-methylphenyl]amido ligand (PNP) toward UI3(THF)4 and UCl4 has been investigated to access new uranium(III) and uranium(IV) halide complexes supported by one and two PNP ligands. The reaction between (PNP)K (6) and 1 equiv of UI3(THF)4 afforded the trivalent halide complex (PNP)UI2(4-tBu-pyridine)2 (7) in the presence of 4-tert-butylpyridine. The same reaction carried out with UCl4 and no donor ligand gave [(PNP)UCl3]2 (8), in which the uranium coordination sphere in the (PNP)UCl3 unit is completed by a bridging chloride ligand. When UCl4 is reacted with 1 equiv (PNP)K (6) in the presence of THF, trimethylphosphine oxide (TMPO), or triphenylphosphineoxide (TPPO), the tetravalent halide complexes (PNP)UCl3(THF) (9), (PNP)UCl3(TMPO)2 (10), and (PNP)UCl3(TPPO) (11), respectively, are formed in excellent yields. The bis(PNP) complexes of uranium(III), (PNP)2UI (12), and uranium(IV), (PNP)2UCl2 (13), were easily isolated from the analogous reactions between 2 equiv of 6 and UI3(THF)4 or UCl4, respectively. Complexes 12 and 13 represent the first examples of complexes featuring two PNP ligands coordinated to a single metal center. Complexes 7-13 have been characterized by single-crystal X-ray diffraction and 1H and 31P NMR spectroscopy. The X-ray structures demonstrate the ability of the PNP ligand to adopt new coordination modes upon coordination to uranium. The PNP ligand can adopt both pseudo-meridional and pseudo-facial geometries when it is kappa3-(P,N,P) coordinated, depending on the steric demand at the uranium metal center. Additionally, its hemilabile character was demonstrated with an unusual kappa2-(P,N) coordination mode that is maintained in both the solid-state and in solution. Comparison of the structures of the mono(PNP) and bis(PNP) complexes 7, 9, 11-13 with their respective C5Me5 analogues 1-4 undoubtedly show that a more sterically congested environment is provided by the PNP ligand. The electronic influence of replacing the C5Me5 ligands with PNP was investigated using electronic absorption spectroscopy and electrochemistry. For 12 and 13, a chemically reversible wave corresponding to the UIV/UIII redox transformation comparable to that for 3 and 4 was observed. However, a 350 mV shift of this couple to more negative potentials was observed on substitution of the bis(C5Me5) by the bis(PNP) framework, therefore pointing to a greater electronic density at the metal center in the PNP complexes. The UV-visible region of the electronic spectra for the mono(PNP) and bis(PNP) complexes appear to be dominated by PNP ligand-based transitions that are shifted to higher energy in the uranium complexes than in the simple ligand anion (6) spectrum, for both the UVI and UIII oxidation states. The near IR region in complexes 1-4 and 7, 9, 11-13 is dominated by f-f transitions derived from the 5f3 and 5f2 valence electronic configuration of the metal center. Though complexes of both ligand sets exhibit similar intensities in their f-f bands, a somewhat larger ligand-field splitting was observed for the PNP system, consistent with its higher electron donating ability.

  13. Complexes in solution of o-phenanthroline with the ions of 4f and 5f elements at valencies II, III, V, VI

    International Nuclear Information System (INIS)

    Le Marois, Gilles.

    1980-06-01

    Slight differences between the complexation in aqueous solution of 4f and 5f series ions are revealed by the use of a soft, aromatic and chelating ligand of the o-phenanthroline type. Trivalent actinide ions are extrated selectively in the presence of a carboxylic acid. This extraction takes place at high pH and does not require large quantities of salts in aqueous solution, which increase the volume of radioactive wastes for storage. Only the first two o-phenanthroline complexes of these ions are obtained in aqueous solution. Determination of the constants of formation of such complexes shows the stronger affinity of the ligand for actinide ions. An inversion of the usual order of complexation of the different actinide valencies is also observed: pentavalent ions are most complexed than trivalent, o-phenanthroline stabilises actinide ions preferentially because they are more liable to form bonds with delocalised electrons. Finally a slight stabilisation of europium at valency II shows the participation of electrons by back bonding of the metal, due to the strong conjugation of the ligand π electrons [fr

  14. High and low oxidation states and special bonding situations. An investigation of f-elements, xenon and fluorine by matrix-isolation spectroscopy and quantum-chemical calculations

    Energy Technology Data Exchange (ETDEWEB)

    Vent-Schmidt, Thomas

    2015-11-30

    During this thesis, the matrix-isolation technique in conjuction with quantum-chemical calculations has been employed in order to synthesize and characterize new compounds. The focus of the study were new species of the actinide and lanthanide series, but the photochemistry of XeO{sub 4} and the polyfluorides were also investigated. Based on the experience of laser ablated uranium and thorium atoms with H{sub 2} and F{sub 2} the reaction of these actinide atoms with HF has been investigated. The main products in these experiments are HThF and HUF which contain an actinide metal in the rather scarce +II oxidation state. In addition, the deuterated compounds have also been prepared and the isotopic shifts support the assignment. The higher hydride fluorides of thorium such as HThF{sub 3}, H{sub 2}ThF{sub 2} and H{sub 3}ThF have also been observed, whereas there is only little evidence for higher uranium hydride fluorides. The different behavior of the two metals under similar reaction conditions has been investigated theoretically. Besides the hydride fluorides, the reaction of the actinide atoms with HF gives also rise to the low valent fluorides and hydrides such as AnH and AnF (An = U, Th). These compounds have already been identified in experiments using fluorine or hydrogen as reagent, but a more reliable assignment can be made in these experiments due to the lower concentration of H or F. In addition, ThF{sub 2} has been observed in these experiments and there is evidence for the unknown difluoride of uranium, which will be addressed in a future paper. Experiments with laser ablated uranium and thorium atoms were extended to the reaction of these metals with H{sub 2}Se. Previous experiments using H{sub 2}O and H{sub 2}S instead of H{sub 2}Se yielded H{sub 2}AnX (An = U, Th; X = O, S) compounds which show evidence for an actinide-chalcogenide multiple bond. The new synthesized species H{sub 2}ThSe and H{sub 2}USe are characterized by their symmetric and asymmetric H-An-H stretching frequencies. Unfortunately the An-Se stretching mode was not observed. The assignment is supported by experiments with deuterated H{sub 2}Se and by electronic structure calculations. The Kohn-Sham orbitals show a polarized triple bond for the An-Se bonds which is supported by a NBO analysis. However, we do note that the description of the bonding can be done in different ways and that it might depend on the applied method. The results obtained for the H{sub 2}AnSe molecules are comparable to the H{sub 2}AnS compounds, but a comparison with the H{sub 2}AnTe species would be interesting. The investigation of the lanthanides is focussed on fluorides with high oxidation states on the metal center. In a first project, the Pr/F{sub 2} system is investigated experimentally and theoretically, with the focus on the question if there might exists a Pr(V) fluoride. The electronic structure calculations predict the pentafluoride, PrF{sub 5}, to be stable under cryogenic conditions. However, there is only little experimental evidence for its formation. Besides the investigation of the pentafluoride, IR bands for the tetrafluoride are reported for the first time herein and the known matrix IR bands of PrF{sub 3} are extended by values for the neon matrix. In addition, there is evidence for the formation of the low valent PrF and PrF{sub 2} species. Using the experience obtained from the Pr/F{sub 2} system, experiments were extended to other lanthanides in order to find possible new LnF{sub 4} species. Besides the known tetrafluorides CeF{sub 4}, PrF{sub 4} and TbF{sub 4}, NdF{sub 4} and DyF{sub 4} have been synthesized and characterized for the fist time in neon and argon matrices. The results are confirmed by experiments in neat fluorine matrixes and by quantum-chemical calculations. These calculations show that the synthesized LnF{sub 4} compounds are in the +IV oxidation state with only little backbonding from F orbitals into empty 5d metal orbitals. The calculated Ln-F bond dissociation energy in these species is high enough that these compounds will be stable under cryogenic conditions. SmF{sub 4} and HoF{sub 4} are not observed although HoF{sub 4} might be stable according to the calculations. In all of the above mentioned experiments using F{sub 2} as reagent a so far unknown band at 850.7 cm{sup -1} has been observed in neon matrixes. Several attempts to experimentally identify the carrier of this bands are reported herein. In conjunction with quantumchemical methods the band can be attributed to a V-shaped [F{sub 5}]{sup -} anion which solves an outstanding question in our group we dealed with for already five years. In addition, the Cs{sup +}[F{sub 3}]{sup -} ion pair complex is further characterized in neon matrixes and the electronic structure is evaluated using state-of-the-art coupled cluster techniques. Using the experience with neat fluorine matrixes the chemical reactivity of the unstable Xe(VIII) oxide, XeO{sub 4}, was tested in fluorine doped neon, argon and krypton matrixes as well as in neat fluorine. However, the reactivity tend out to be low and no oxyfluoride or fluoride formation is observed. On photolysis with a 365 nm UVLED the new xenon (VIII) oxide, (η{sup 2}-O{sub 2})XeO{sub 3}, can be obtained and our results are confirmed by experiments using isotopic substituted 18O-enriched material as well as by quantum-chemical structure calculations. The photochemical process has been investigated theoretically and gives further insights in the photochemistry of XeO4 and the reaction channel to (η{sup 2}-O{sub 2})XeO{sub 3}. Further experiments to investigate the reaction of XeO{sub 4} with XeF{sub 6} would be interesting but are beyond the scope of this thesis.

  15. Theoretical description of metal-ligand bonding within f-element complexes: A successful and necessary interplay between theory and experiment

    International Nuclear Information System (INIS)

    Maldivi, P.; Petit, L.; Vetere, V.; Petit, L.; Adamo, C.

    2007-01-01

    The quantum chemical study presented here shows various aspects of the bonding of lanthanide (La 3+ , Gd 3+ ) and actinide (U 3+ , Am 3+ , Cm 3+ ) ions with N-heterocyclic ligands (poly-azines, BTP: bis(1,2,4-triazinyl)-2,6-pyridine). Several families of complexes, differing by their coordination sphere, have been examined. Clearly, the lanthanide complexes always show a purely ionic bonding. The behaviour of U(III) is also well defined with a more or less strong back bonding interaction whatever the complex is. In contrast, the heavy actinides (Am 3+ and Cm 3+ ) are changeable, with a weak covalent character, going from donation to back donation, depending on the coordination sphere of the complex. (authors)

  16. Can a pentamethylcyclopentadienyl ligand act as a proton-relay in f-element chemistry? Insights from a joint experimental/theoretical study.

    Science.gov (United States)

    Kefalidis, Christos E; Perrin, Lionel; Burns, Carol J; Berg, David J; Maron, Laurent; Andersen, Richard A

    2015-02-14

    Isomerisation of buta-1,2-diene to but-2-yne by (Me(5)C(5))(2)Yb is a thermodynamically favourable reaction, with the Δ(r)G° estimated from experimental data at 298 K to be -3.0 kcal mol(-1). It proceeds in hydrocarbon solvents with a pseudo first-order rate constant of 6.4 × 10(-6) s(-1) and 7.4 × 10(-5) s(-1) in C(6)D(12) and C(6)D(6), respectively, at 20 °C. This 1,3-hydrogen shift is formally forbidden by symmetry and has to occur by an alternative pathway. The proposed mechanism for buta-1,2-diene to but-2-yne isomerisation by (Me(5)C(5))(2)Yb involves coordination of methylallene (buta-1,2-diene) to (Me(5)C(5))(2)Yb, and deprotonation of methylallene by one of the Me(5)C(5) ligands followed by protonation of the terminal methylallenyl carbon to yield the known coordination compound (Me(5)C(5))(2)Yb(η(2)-MeC[triple bond, length as m-dash]CMe). Computationally, this mechanism is not initiated by a single electron transfer step, and the ytterbium retains its oxidation state (II) throughout the reactivity. Experimentally, the influence of the metal centre is discussed by comparison with the reaction of (Me(5)C(5))(2)Ca towards buta-1,2-diene, and (Me(5)C(5))(2)Yb with ethylene. The mechanism by which the Me(5)C(5) acts as a proton-relay within the coordination sphere of a metal also rationalises the reactivity of (i) (Me(5)C(5))(2)Eu(OEt(2)) with phenylacetylene, (ii) (Me(5)C(5))(2)Yb(OEt(2)) with phenylphosphine and (iii) (Me(5)C(5))(2)U(NPh)(2) with H(2) to yield (Me(5)C(5))(2)U(HNPh)(2). In the latter case, the computed mechanism is the heterolytic activation of H(2) by (Me(5)C(5))(2)U(NPh)(2) to yield (Me(5)C(5))(2)U(H)(HNPh)(NPh), followed by a hydrogen transfer from uranium back to the imido nitrogen atom using one Me(5)C(5) ligand as a proton-relay. The overall mechanism by which hydrogen shifts using a pentamethylcyclopentadienyl ligand as a proton-relay is named Carambole in reference to carom billiards.

  17. Theoretical study of the electronic structure of f-element complexes by quantum chemical methods; Analyse de la structure electronique des complexes contenant des elements F par des methodes de la chimie quantique

    Energy Technology Data Exchange (ETDEWEB)

    Vetere, V

    2002-09-15

    This thesis is related to comparative studies of the chemical properties of molecular complexes containing lanthanide or actinide trivalent cations, in the context of the nuclear waste disposal. More precisely, our aim was a quantum chemical analysis of the metal-ligand bonding in such species. Various theoretical approaches were compared, for the inclusion of correlation (density functional theory, multiconfigurational methods) and of relativistic effects (relativistic scalar and 2-component Hamiltonians, relativistic pseudopotentials). The performance of these methods were checked by comparing computed structural properties to published experimental data, on small model systems: lanthanide and actinide tri-halides and on X{sub 3}M-L species (X=F, Cl; M=La, Nd, U; L = NH{sub 3}, acetonitrile, CO). We have thus shown the good performance of density functionals combined with a quasi-relativistic method, as well as of gradient-corrected functionals associated with relativistic pseudopotentials. In contrast, functionals including some part of exact exchange are less reliable to reproduce experimental trends, and we have given a possible explanation for this result . Then, a detailed analysis of the bonding has allowed us to interpret the discrepancies observed in the structural properties of uranium and lanthanides complexes, based on a covalent contribution to the bonding, in the case of uranium(III), which does not exist in the lanthanide(III) homologues. Finally, we have examined more sizeable systems, closer to experimental species, to analyse the influence of the coordination number, of the counter-ions and of the oxidation state of uranium, on the metal-ligand bonding. (author)

  18. Unprecedented reduction of the uranyl ion [UO2]2+ into a polyoxo uranium(IV) cluster: synthesis and crystal structure of the first f-element oxide with a M6(micro3-O)8 core.

    Science.gov (United States)

    Berthet, Jean-Claude; Thuéry, Pierre; Ephritikhine, Michel

    2005-07-21

    The smooth comproportionation reaction of the U(VI) and U(III) complexes UO2(OTf)2 and U(OTf)3, afforded the hexanuclear U(IV) oxide cluster [U6(micro3-O)8(micro2-OTf)8(py)8], a rare example of a metal oxide with a M6(micro3-O)8 core.

  19. Characteristics of the Biological Effects and the RBE of High Energy Protons; Caracteristiques des Effets Biologiques et EBR des Protons de Haute Energie; Osobennosti biologicheskogo dejstviya i obeh protonov vysokikh ehnergii; Caracteristicas de los Efectos Biologicos y de la EBR de los Protones de Elevada Energia

    Energy Technology Data Exchange (ETDEWEB)

    Grigor' ev, Ju. G.; Darenskaja, N. G.; Domshlak, M. M.; Lebedinskij, A. V.; Nefedov, Ju. G.; Ryzhov, N. I.

    1964-03-15

    The characteristics of the biological effects of high-energy protons (120, 240 and 510 MeV) were studied in experiments on mice, rats and dogs. It was shown that together with a certain resemblance or identity in radiation damage due to the effects of X-rays and protons, there were certain differences in the case of proton irradiation. In the proton irradiation of dogs the haemorrhagic syndrome was more pronounced. Haemorrhage appeared earlier in the animals and was more abundant. A difference was found in proton RBE levels for small animals (rats, mice) and large animals (dogs). This difference is quite large and equals respectively 0.7 and 1.0 * 1.15. Some considerations are presented in the report on the cause of these differences. (author) [French] Les auteurs ont etudie les caracteristiques des effets biologiques des protons de haute energie (120, 240 et 510 MeV) au cours d'experiences sur des souris, des rats et des chiens. Ils montrent que si les dommages causes par les rayons X et les protons presentent une certaine ressemblance ou des caracteres identiques, on observe des differences dans le cas de l'irradiation par les protons. Chez les chiens exposes aux protons, le syndrome hemorragique etait plus prononce. L'hemorragie s'est manifestee plus tot chez ces animaux et etait plus abondante. Les auteurs ont decele une difference dans l*EBRdes protons pour les petits animaux (rats, souris) et pour les grands animaux (chiens). Cette difference etait importante: 0,7 dans le premier cas et de 1,0 a 1,15 dans le second cas. On trouve dans le memoire quelques considerations sur la cause de ces differences. (author) [Spanish] Los autores estudiaron las caracteristicas de los efectos biologicos de los protones de elevada energia (120, 240 y 510 MeV) mediante experimentos con ratones, ratas y perros. Comprobaron que a pesar de ciertas semejanzas en las radiolesiones causadas por los rayos X y los protones, los efectos de estos ultimos acusan algunas diferencias. El sindrome hemorragico provocado en el perro por la irradiacion protonica es mas pronunciado. La hemorragia se presenta al cabo de un tiempo mas breve y es mas abundante. Verificaron asimismo que la EBR de los protones es diferente segun se trate de animales pequeflos (ratas o ratones) o de animales grandes (perros). La diferencia es apreciable, ya que los valores respectivos son 0,7 para los primeros y 1,0 o 1,15 para los segundos. En la memoria se examinan las posibles causas de estas diferencias. (author) [Russian] Harakteristiki biologicheskogo dejstvija protonov vysokih jenergij (120, 210 i 510Mjev) izuchalis' v jeksperimentah na myshah, krysah i sobakah. Bylo pokazano, chto narjadu s nekotorym shodstvom ili identichnost'ju radiacionnogo porazhenija pri dejstvii rentgenovskih luchej i protonov imelsja rjad razlichij. Pri protonnom obluchenii sobak byl bolee otchetlivo vyrazhen gemorrogicheskij sindrom. Krovoizlijanija pojavljalis' u zhivotnyh ran'she i byli b olee obil'nymi. Obnaruzhena raznica v urovnjah OBJe protonov dlja melkih (krysy, myshi) i krupnyh zhivotnyh (sobaki). Jeta raznica javljaetsja dovol'no znachitel'noj i ravnjaetsja so otvetstvenno 0,7 i 1,0 - 1,15. V doklade privodjatsja nekotorye soobrazhenija otnositel'no prichiny jetih razlichij. (author)

  20. Osobennosti vybora institucional'nogo puti razvitija v Vostochnoj Evrope XVI—XVII vekov: Moskovskoe gosudarstvo i Rech' Pospolitaja [The features of choosing an institutional development trajectory in Eastern Europe in the 16th—17th centuries: Moscovy and the Polish — Lithuanian Commonwealth

    Directory of Open Access Journals (Sweden)

    Vdovin Mikhail

    2011-01-01

    Full Text Available Recent decades have witnessed an increase in the number of works dedicated to the analysis of effects of historical events on the choice of institutions and further economic and social development of regions. This article employs the new institutional economic theory approach to consider the choices regarding title to land and serfdom in Moscovy and the Polish — Lithuanian Commonwealth (earlier the Grand Duchy of Lithuania in the 16th—17th centuries. The author emphasizes the factors, which affected the choice of institutional development trajectory, and considers the influence exerted by these institutes on the political and military development of these states. This article shows how the contingent property rights in Moscovy turned out to be competitive in the conditions of a considerable contribution of decentralization factors to defence capacity and, opposite to the situation in the Polish — Lithuanian Commonwealth, ensured the formation of large and efficient troops. This work contributes to the research on the property rights and Russian economic history.

  1. Specific features of the domain structure of (Gd sub 1-x Nd sub x ) sub 2 (MoO sub 4 ) sub 3 crystals. Osobennosti domennoj struktury kristallov (Gd sub 1-x Nd sub x ) sub 2 (MoO sub 4 ) sub 3

    Energy Technology Data Exchange (ETDEWEB)

    Bryzgalov, A N; Slepchenko, B M; Virachev, B P [Cherepovetskij Gosudarstvennyj Pedagogicheskij Inst., Cherepovets (USSR)

    1989-11-01

    Formation of the domain structures by sample transfer into thermodynamically metastable state using a simultaneous effect of electric field and temperature change is investigated in Gd{sub 1.7}Nd{sub 0.3}(MoO{sub 4}){sub 3} monocrystals (GMO). Some new results obtained under investigations into GMO domain structure using neodymium by means of hydrothermal etching and polarization-optical method are presented.

  2. Neodymium and uranium borohydride complexes, precursors to cationic derivatives: comparison of 4f and 5f element complexes; Complexes borohydrures du neodyme et de l'uranium, precurseurs de derives cationiques: comparaison de complexes des elements 4f et 5f

    Energy Technology Data Exchange (ETDEWEB)

    Cendrowski-Guillaume, S.M. [Bordeaux-1 Univ., Lab. de Chimie des Polymeres Organiques, CNRS (UMR 5629), ENSCPB, 33 - Pessac (France); Le Gland, G.; Lance, M.; Nierlich, M.; Ephritikhine, M. [CEA Saclay, Dept. de Recherche sur l' Etat Condense, les Atomes et les Molecules, 91 - Gif sur Yvette (France)

    2002-02-01

    Nd(BH{sub 4}){sub 3}(THF){sub 3}, 1, reacted with KCp{sup *}, KP{sup *} and K{sub 2}COT (Cp{sup *} = {eta}-C{sub 5}Me{sub 5}, P{sup *} = {eta}-PC{sub 4}Me{sub 4}, COT = {eta}-C{sub 8}H{sub 8}) to form (Cp{sup *})Nd(BH{sub 4}){sub 2}(THF){sub 2}, 2, [K(THF)][(P{sup *}){sub 2}Nd(BH{sub 4}){sub 2}], 3 and (COT)Nd(BH{sub 4})(THF){sub 2}, 4a, respectively. The mixed ring complexes (COT)Nd(Cp{sup *})(THF), 6, and [(COT)Nd(P{sup *})(THF)], 7a, the alkoxide [(COT)Nd(OEt)(THF)]{sub 2}, 8, and the thiolates [Na][(COT)Nd-(S{sup t}Bu){sub 2}], 11, and [Na(THF){sub 2}][(COT)Nd((COT)Nd){sub 2}(S{sup t}Bu){sub 3}], 12, were similarly synthesised from 4a by reaction with the alkali metal salt of the respective ligand. Protonolysis of the metal-borohydride bonds in 4a or (COT)U(BH{sub 4}){sub 2}(THF), with NEt{sub 3}HBPh{sub 4} in THF afforded the cations [(COT)Nd(THF){sub 4}][BPh{sub 4}), 5, [(COT)U(BH{sub 4})(THF){sub 2}][BPh{sub 4}], 13, and [(COT)U(HMPA){sub 3}][BPh{sub 4}]{sub 2}, 14. These cations allowed the preparation of (COT)U(P{sup *})(HMPA){sub 2}, 15, [(COT)U(P{sup *})(HMPA){sub 2}][BPh{sub 4}], 16, and [(COT)U(HMPA){sub 3}][BPh{sub 4}], 17. The X-ray crystal structures of [(COT)M(HMPA){sub 3}[BPh{sub 4}], M = Nd, 18, U, 17, have been determined, allowing comparison of Nd(III) and U(III) derivatives. (authors)

  3. U.S. Department of Energy Office of Science Heavy Elements Program. Final Report

    International Nuclear Information System (INIS)

    Clark. S. B.; Ewing, R.

    2005-01-01

    In our first funding cycle, much time was spent developing protocols for characterizing and working with samples containing transuranium isotopes and obtaining preliminary experimental data on non-f-element systems

  4. Unusual high-temperature behavior of neptunium and plutonium systems

    International Nuclear Information System (INIS)

    Brewer, L.

    1991-01-01

    The initial Manhattan Project effort to predict the properties of transuranium elements was based on the assumption that the lanthanides would serve as models. However, since then, many unexpected differences have been found. With the extensive work on the electronic configurations of the gaseous atoms, it is now possible to understand the reasons for the different behavior of the 5f elements compared to the 4f elements. In this paper a review of these differences are presented along with examples of other unexpected behavior such as the very strong generalized Lewis acid-base interactions of the 5f elements with the platinum-group metals that provide techniques for preparation of pure metal samples. The thermodynamic properties of the transuranium metals and some of the compounds will be reviewed

  5. Actinide phosphonate complexes in aqueous solutions

    International Nuclear Information System (INIS)

    Nash, K.L.

    1993-01-01

    Complexes formed by actinides with carboxylic acids, polycarboxylic acids, and aminopolycarboxylic acids play a central role in both the basic and process chemistry of the actinides. Recent studies of f-element complexes with phosphonic acid ligands indicate that new ligands incorporating doubly ionizable phosphonate groups (-PO 3 H 2 ) have many properties which are unique chemically, and promise more efficient separation processes for waste cleanup and environmental restoration. Simple diphosphonate ligands form much stronger complexes than isostructural carboxylates, often exhibiting higher solubility as well. In this manuscript recent studies of the thermodynamics and kinetics of f-element complexation by 1,1 and 1,2 diphosphonic acid ligands are described

  6. Almost everywhere convergence over cubes of multiple trigonometric Fourier series

    International Nuclear Information System (INIS)

    Antonov, N Yu

    2004-01-01

    Under certain conditions on a function φ:[0,+∞)→[0,+∞) we prove a theorem asserting that the convergence almost everywhere of trigonometric Fourier series for all functions of class φ(L) [-π,π) implies the convergence over cubes of the multiple Fourier series and all its conjugates for an arbitrary function f element of φ(L)(log + L) d-1 ) [-π,π) d , d element of N. It follows from this and an earlier result of the author on the convergence almost everywhere of Fourier series of functions of one variable and class L(log + L)(log + log + log + L)) [-π,π) that if f element of L(log + L) d (log + log + log + L)) [-π,π) d , d element of N, then the Fourier series of f and all its conjugates converge over cubes almost everywhere

  7. Fermions on spacetimes of spatially closed hypersurfaces

    International Nuclear Information System (INIS)

    Dariescu, Marina-Aura; Dariescu, Ciprian

    2009-01-01

    Using a convenient compact time-like coordinate f element of [0, 1], characterizing the whole big bang-big crunch spacetime history cyclicly evolving with a 2π conformal period, we write down the Dirac-type equation in a FRW matter-dominated Universe. It turns out that, by accepting the idea of existence of an alternative time gauge, as for example in the projected Universe, one is able to derive closed form solutions, for physically meaningful cases.

  8. The physics and chemistry of heavy Fermions

    International Nuclear Information System (INIS)

    Fisk, Z.; Sarrao, J.L.

    1994-01-01

    The heavy Fermions are a subset of the f-element intermetallics straddling the magnetic/non-magnetic boundary. Their low temperature properties are characterized by an electronic energy scale of order 1--10 K. Among the low temperature ground states observed in heavy Fermion compounds are exotic superconductors and magnets, as well as unusual semiconductors. We review here the current experimental and theoretical understanding of these systems

  9. COMPLEXES POLYMETALLIQUES DE LANTHANIDES (III) POUR LE DEVELOPPEMENT DE NOUVEAUX MATERIAUX LUMINESCENTS

    OpenAIRE

    Marchal , Claire

    2008-01-01

    The incorporation of f elements in highly organized polymetallic complexes is of great interest in supramolecularchemistry and allows the combination of their nanoscopic size with the magnetic or optical properties of the metal ions. However due to the difficulty in controlling the coordination environment of these ions, the assembly of lanthanide-based polynuclear architectures has lagged behind that of other systems. These factors make the rational design for the construction of supramolecu...

  10. Development of Geiger-Mueller counters for operation at high temperatures; Mise au point de compteurs Geiger-Mueller fonctionnant a haute temperature; Razrabotka schetchikov Gejgera-Myullera, rabotayushchikh pri povyshennoj temperature; Contadores Geiger-Mueller que funcionan a temperaturas elevadas

    Energy Technology Data Exchange (ETDEWEB)

    Draghicescu, M [Institut de Physique Atomique, Bucarest (Romania)

    1962-04-15

    Counters of this type are necessary for radioactive logging at great depths; they have to operate normally at temperatures up to 180{sup o}C. In order to preserve their characteristics under such conditions, the work function of the cathode has been improved by a special treatment. Tests have been made on counters with graphite, copper and wolfram cathodes in a glass envelope. The method is simple, and can easily be employed in industry. (author) [French] De tels compteurs sont necessaires pour le sondage radioactif aux grandes profondeurs; ils doivent fonctionner dans des conditions normales jusqu'a la temperature de 180{sup o}C. Afin qu'ils puissent conserver leurs caracteristiques jusqu'a cette temperature, on a agi sur le travail de sortie de la cathode par un traitement adequat. On a fait l'essai sur des compteurs avec cathode de graphite, de cuivre ou de tungstene, dans un ballon de verre. La methode proposee est simple et peut etre appliquee facilement dans l'industrie. (author) [Spanish] Se requiere este tipo de contador para la determinacion de la radiactividad a grandes profundidades; debe ser capaz de funcionar normalmente a temperaturas hasta de 180{sup o}C. A fin de que sus caracteristicas se conserven inalteradas hasta tales temperaturas, se ha modificado la funcion de trabajo del catodo mediante un tratamiento adecuando. Se han ensayado contadores con catodo de grafito, de cobre o de wolframio en un balon de vidrio. El metodo propuesto es simple y puede aplicarse facilmente en la industria. (author) [Russian] Podobnye schetchiki neobkhodimy dlya radioaktivnogo karottazha na bol'shikh glubinakh; oni dolzhny funktsionirovat' v normal'nykh usloviyakh pri temperature do 180{sup o}C. Nakonets, dlya togo, chtoby oni mogli sokhranyat' svoi osobennosti pri ehtoj temperature, bylo obrashcheno vnimanie na rabotu katodnogo vykhoda pri pomoshchi sootvetstvuyushchej obrabotki. Byl proveden opyt na schetchikakh s grafitovym, mednym ili vol'framovym katodom v

  11. Synthesis of molecular complexes for small molecule activation

    International Nuclear Information System (INIS)

    Andrez, Julie

    2016-01-01

    The redox chemistry of f-elements is drawing the attention of inorganic chemists due to their unusual reaction pathways. Notably low-valent f-element complexes have been shown to be able to activate small molecules such as CO_2 and N_2 in mild conditions. Compared to d-block metals, f-elements present a coordination chemistry dominated by electrostatic interactions and steric constraints. Molecular complexes of f-elements could thus provide new catalytic routes to transform small molecules into valuable chemicals. However the redox chemistry of low valent f-elements is dominated by single-electron transfers while the reductions of CO_2 and N_2 require multi-electronic processes. Accordingly the first approach of this PhD work was the use of redox active ligands as electron reservoir to support f-element centres increasing the electron number available for reduction events. The coordination of uranium with tridentate Schiff base ligand was investigated and led to isolation of a dinuclear electron-rich species able to undertake up to eight-electron reduction combining the redox activity of the ligands and the uranium centres. In order to obtain electron-rich compounds potentially able to polarize the C=O bond of CO_2, the synthesis of hetero-bimetallic species supported by salophen Schiff base ligand was also studied. In a second approach we have used bulky ligands with strong donor-character to tune the reducing abilities of low valent f-elements. In this case a bimolecular electron-transfer process is often observed. The reactivity of the U(III) siloxid complex [U(OSi(OtBu)_3)_4K] was further investigated. Notably, reaction with Ph_3PS led to the formation of a terminal U(IV) sulfide complex with multiple U-S bond which was analysed by DFT studies to better understand the bonding nature. Preliminary studies on the role of the counter-cation (M) in the system [U(OSi(OtBu)_3)_4M] on the outcome of the reactivity with CS_2 and CO_2 have also been performed. The

  12. Static and dynamic modelling of lanthanide and actinide cations in solution

    International Nuclear Information System (INIS)

    Marjolin, A.

    2012-01-01

    We propose a theoretical approach, based on both quantum analyses (energy decomposition analysis and topological analysis of the chemical bond) and classical molecular dynamics, for the study of f-element complexes. First, we introduce the different QM methods adapted to the study of f-elements and use them for geometry optimization and interaction energy calculations of the model system [M-(OH 2 )] m+ where M is a lanthanide or actinide cation. We then perform energy decomposition analysis to quantify the physical nature of the metal-ligand interaction in terms of the different contributions. Furthermore, the different energy contributions will be used as reference curves for the parameterization of the polarizable force fields AMOEBA and SIBFA. Next, starting from the optimized geometries, we establish the reference diabatic dissociation curves at high level of theory so as to take into account the multi-reference nature of the systems. These dissociation curves will also be used for parameterization of the AMOEBA potential. We then propose a three step validation protocol as well as a first application, it being the computation of Gibbs hydration free energies for the f-element cations. We also propose an extension of the SIBFA force field to trivalent lanthanide ions and tetravalent actinide ions. Last, we use the topological analysis approaches of ELF and NCI to investigate the nature of the different interactions in Gadolinium(III) model and real systems. The aim of the whole study was to develop and apply different theoretical approaches so as to be able to discriminate between lanthanide and actinide cations. Indeed, despite their similar chemical behavior, they still feature a selective character that we wish to be able to both explain and predict. (author) [fr

  13. Oxidation-reduction properties of americium, curium, berkelium, californium, einsteinium and fermium, and thermodynamic consequences for the 5f series

    International Nuclear Information System (INIS)

    Samhoun, K.

    1976-01-01

    The amalgamation of 5f elements from Am to Fm has been studied by using 241 Am, 244 Cm, 249 Bk, 249 Cf, 252 Cf, 253 Es, 254 Es, 252 Fm and 255 Fm with two electrochemical methods, radiocoulometry and radiopolarography, perfectly adapted to investigate extremely diluted solutions when the concentration of electroactive species is as low as 10 -16 M. The theory of radiocoulometry has been developed in the general cases of reversible and irreversible electrode process. It has been used to interpret the experimental data on the kinetic curves of amalgamation, and to estimate the standard rate constant of the electrode process in complexing medium (citric). On the other hand the radiopolarographic method has been applied to study the mechanism of reduction at the dropping mercury electrode of cations M 3+ in aqueous medium to the metal M with formation of amalgam. The results are exploited into two directions: 1- Acquisition of some data concerning the oxidation-reduction properties of elements from Am to Fm. Therefore the standard electrode E 0 [M(III-0)] potentials for Bk, Cf and Es, and the standard electrode E 0 [M(II-0)] potential for Fm are estimated and the relative stability of each oxidation state (from II to VII) of 5f elements is discussed; 2- Acquisition of unknown thermodynamic data on transcalifornium elements. Correlations between 4f and 5f elements are precised and some divergences appear for the second half of 4f and 5f series (i.e. for 65 [fr

  14. Cluster electric spectroscopy of colloid chemical oxyhydrate systems

    CERN Document Server

    Sucharev, Yu I

    2015-01-01

    This monograph deals with the shape of Liesegang operator and its respective phase diagrams of spontaneous surges and analyzed properties of cluster attractors. It describes the influence of pulsation noise or self-organization current of gel systems in a magnetic field on singularities of optic parameters of yttrium oxyhydrate, as well as on kinetic curves of changes in optic density of oxyhydrate systems, sorptive properties of d- and f-elements, and the structural organization of their colloids. This monograph is meant for postgraduate students, magisters, researchers, and those interested

  15. Controlling Actinide Hydration in Mixed Solvent Systems: Towards Tunable Solvent Systems to Close the Fuel Cycle

    International Nuclear Information System (INIS)

    Clark, Sue B.

    2016-01-01

    The goal of this project has been to define the extent of hydration the f-elements and other cations in mixed solvent electrolyte systems. Methanol-water and other mixed solvent systems have been studied, where the solvent dielectric constant was varied systematically. Thermodynamic and spectroscopic studies provide details concerning the energetics of complexation and other reactions of these cations. This information has also been used to advance new understanding of the behavior of these cations in a variety of systems, ranging from environmental studies, chromatographic approaches, and ionization processes for mass spectrometry.

  16. Design, synthesis and evaluation of carbamoyl-methyl-phosphine sulfide (CMPS)-based chelates for separation of lanthanides and actinides

    Energy Technology Data Exchange (ETDEWEB)

    Matlokaa, K.; Saha, A.K.; Srinivasan, P.; Scott, M.J. [Florida Univ., Dept. of Chemistry, FL (United States)

    2007-10-15

    C{sub 3}-symmetric tri-phenoxy-methane platforms were substituted with carbamoyl-methyl-phosphine sulfide arms and these tris-CMPS compounds were evaluated as extractants for f-element metal ions from 1 M nitric acid solution. Their properties were compared to the carbamoyl-methyl-phosphine oxide derivatives on the same tri-phenoxy-methane platform (tris-CMPO). The terbium complex of tris-CMPS was crystallized and examined via X-ray structural analysis to provide valuable insight into the binding properties of the soft tripodal chelate. (authors)

  17. Preorganized and Immobilized Ligands for Metal Ion Separations

    Energy Technology Data Exchange (ETDEWEB)

    Paine, Robert T. [Univ. of New Mexico, Albuquerque, NM (United States)

    2015-07-01

    The research project, in the period 2003-2015, was focused on the discovery of fundamental new principles in f-element ion coordination chemistry and the application of the new knowledge to the development of advanced detection/separations reagents and methods for these ions. The findings relate to the Nation's efforts to safely and efficiently process nuclear materials. In addition, the project provided training for young scientists needed to maintain the Nation's preeminence in nuclear science.

  18. Electronic structure of the light actinides

    International Nuclear Information System (INIS)

    Dunlap, B.D.

    1976-01-01

    In the last few years, considerable advances have been made in our understanding of the properties of the light actinides. Although these are 5f transition elements formally equivalent to the lanthanide (4f) elements, these materials show a much more varied behavior due to the larger spatial extent and ionizability of the 5f electrons. A review is given of some areas of current interest, especially where hyperfine measurements have played an active role. These include studies of a variety of magnetic phenomena, systematics of isomer shift measurements, and studies of paramagnetic relaxation

  19. Electrochemical synthesis of transition element complexes with carboxyl- and carbonyl-containing ligands

    International Nuclear Information System (INIS)

    Frolov, V.Yu.; Bolotin, S.N.; Panyushkin, V.T.

    2005-01-01

    Complexes of d- and f-elements (E = Cu, Ni, Zn, Nd, Tb, Pr, Gd, Er) with carboxyl- and carbonyl-containing ligands were synthesized by the electrochemical method. The products were characterized by elemental analysis, thermal gravimetric analysis and IR spectra. The influence exerted by a number of factors on the process course was studied. The dependence of the electro synthesis parameters on the composition of the forming compounds was established. A new method for anodic synthesis of these compounds was developed [ru

  20. Controlling Actinide Hydration in Mixed Solvent Systems: Towards Tunable Solvent Systems to Close the Fuel Cycle

    Energy Technology Data Exchange (ETDEWEB)

    Clark, Sue B. [Washington State Univ., Pullman, WA (United States). Dept. of Chemistry

    2016-10-31

    The goal of this project has been to define the extent of hydration the f-elements and other cations in mixed solvent electrolyte systems. Methanol-water and other mixed solvent systems have been studied, where the solvent dielectric constant was varied systematically. Thermodynamic and spectroscopic studies provide details concerning the energetics of complexation and other reactions of these cations. This information has also been used to advance new understanding of the behavior of these cations in a variety of systems, ranging from environmental studies, chromatographic approaches, and ionization processes for mass spectrometry.

  1. Nonlinearity of colloid systems oxyhydrate systems

    CERN Document Server

    Sucharev, Yuri I

    2008-01-01

    The present monograph is the first systematic study of the non-linear characteristic of gel oxy-hydrate systems involving d- and f- elements. These are the oxyhydrates of rare-earth elements and oxides - hydroxides of d- elements (zirconium, niobium, titanium, etc.) The non-linearity of these gel systems introduces fundamental peculiarities into their structure and, consequently, their properties. The polymer-conformational diversity of energetically congenial gel fragments, which continu-ously transform under the effect of, for instance, system dissipation heat, is central to the au-thor's hy

  2. A suggested periodic table up to Z≤ 172, based on Dirac-Fock calculations on atoms and ions.

    Science.gov (United States)

    Pyykkö, Pekka

    2011-01-07

    Extended Average Level (EAL) Dirac-Fock calculations on atoms and ions agree with earlier work in that a rough shell-filling order for the elements 119-172 is 8s Periodic Table develops further that of Fricke, Greiner and Waber [Theor. Chim. Acta 1971, 21, 235] by formally assigning the elements 121-164 to (nlj) slots on the basis of the electron configurations of their ions. Simple estimates are made for likely maximum oxidation states, i, of these elements M in their MX(i) compounds, such as i = 6 for UF(6). Particularly high i are predicted for the 6f elements.

  3. Macrocyclic extractants for separating Am(III)/Ln(III)

    International Nuclear Information System (INIS)

    Ludwig, R.; Nguyen, T.K.D.; Kunogi, K.; Tachimori, Shoichi

    1999-01-01

    The extraction of trivalent f-elements by calix(n)arene-type macrocyclic ligands increases in the order n=4, 8, 6 corresponding to the balance between cavity size, molecular flexibility, and number of donor atoms. Introduction of mixed functionalities into calix(6)arenes, e.g. carboxylic acid and amide groups, results in better extractability of actinides compared with lanthanides. For calix(4)arenes, such a different extractability could not be observed. Furthermore, the effects of solvent composition with respect to a modifier and of the aqueous phase composition were investigated. (author)

  4. Compatibilities of YBa2Cu3O(9-delta) type phase in quintenary systems Y-Ba-Cu-O-X (impurity)

    Science.gov (United States)

    Karen, P.; Braaten, O.; Fjellvag, H.; Kjekshus, A.

    1991-01-01

    Isothermal phase diagrams at various oxygen pressures were studied by powder diffraction and chemical analytical methods. The components, Y, Ba, Cu, and O (specifically O2, O2-, and O2 sup 2-) are treated, together with C (specifically CO2 and CO2 sup 2-), alkaline metals, Mg, alkaline earths, Sc, 3-d and 4-f elements. Effects of the substitutions at the structural sites of YBa2Cu3O(9-delta) on T sub c are discussed with respect to changes in crystallochemical characteristics of the substituted phase and to the nature of the substituents.

  5. Compatibilities of YBa2Cu3O(9-delta)-type phase in quintenary systems Y-Ba-Cu-O-X (impurity)

    International Nuclear Information System (INIS)

    Karen, P.; Braaten, O.; Fjellvag, H.; Kjekshus, A.

    1991-01-01

    Isothermal phase diagrams at various oxygen pressures were studied by powder diffraction and chemical analytical methods. The components, Y, Ba, Cu, and O (specifically O2, O2-, and O2 sup 2-) are treated, together with C (specifically CO2 and CO2 sup 2-), alkaline metals, Mg, alkaline earths, Sc, 3-d and 4-f elements. Effects of the substitutions at the structural sites of YBa2Cu3O(9-delta) on T sub c are discussed with respect to changes in crystallochemical characteristics of the substituted phase and to the nature of the substituents

  6. Economic Aspects of Radiation Treatment; Considerations Economiques sur le Traitement par Irradiation; Ehkonomicheskie aspekty obrabotki produktov metodom oblucheniya; Consideraciones Economicas Sobre el Tratamiento por Irradiacion

    Energy Technology Data Exchange (ETDEWEB)

    Leveque, P. [Centre d' Etudes Nucleaires de Saclay (France)

    1966-11-15

    pudieron sacar varias conclusiones sobre el costo del tratamiento por medio de fuentes radiactivas y maquinas. Es conveniente, tres aflos despues, revisar las hipotesis fundamentales y, sobre todo, tener en cuenta el abaratamiento de los radioelementos, en particular, del {sup 137}Cs. Esto influye a la vez sobre el precio del kilovatio instalado y del kilovatio-hora de energfa producido. La experiencia adquirida en estos tres ultimos aflos permite precisar los rendimientos y factores de carga observados en instalaciones actualmente en servicio. Es cierto que en la mayorfa de los casos estas consisten en instalaciones de tratamiento de accesorios medicos, pero los problemas son analogos. (author) [Russian] V mae 1963 goda vo vremja raboty Konferencii po promyshlennomu primeneniju moshhnyh istochnikov izluchenija, organizovannoj MAGATJe, razvernulas' bol'shaja diskussija po voprosu sebestoimosti. V rezul'tate obmena mnenijami mozhno sdelat' nekotorye ocenki stoimosti obrabotki radioaktivnymi istochnikami i ustrojstvami. Zhelatel'no po istechenii treh let peresmotret' osnovnye gipotezy i uchest' snizhenie stoimosti radiojelementov, i v osobennosti cezija-137. Stoimost' radiojelementov okazyvaet vlijanie srazu na stoimost' 1 kvt ustanovlennoj moshhnosti i kilovatt/chasa proizvodimoj jelektrojenergii. V svete poluchennogo v techenie poslednih treh let opyta imeetsja vozmozhnost' utochnit' proizvoditel'nost' i kojefficient nagruzki dejstvujushhih v nastojashhee vremja ustanovok; Rech' idet v bol'shinstve sluchaev ob obrabotke vspomogatel'nogo medicinskogo oborudovanija, no vse jeti problemy sravnimy. (author)

  7. Some Questions on the Fixation of Radioisotopes in Connexion with the Problem of their Safe Burial; Quelques Aspects de la Fixation des Isotopes Radioactifs en Rapport avec le Probleme de leur Elimination dans le Sol; 041d 0414 ; Algunos Aspectos de la Fijacion de los Isotopos Radiactivos en Relacion con los Problemas de su Evacuacion sin Riesgos en el Suelo

    Energy Technology Data Exchange (ETDEWEB)

    Zimakov, P. V.; Kulichenko, V. V.

    1960-07-01

    isotopos procedentes de la fision, consiste en encerrarlos en bloques de vidrio fundido. Exponen los principios fisicoquimicos de la transformacion de los desechos liquidos radiactivos en bloques solidos. La memoria contiene termogramas de este proceso y un analisis de sus caracteristicas. Se indican las condiciones de fusion de las masas de vidrio, especialmente las que favorecen el desplazamiento de los aerosoles radiactivos. Se presentan algunos resultados del estudio de la composicion quimica de los isotopos de fision radiactivos en el interior de la masa solida en relacion con la eliminacion de su radiactividad mediante el lavado. Por ultimo, se dan algunos resultados del calculo de las temperturas a que es posible recalentar los bloques radiactivos segun sus caracteristicas. (author) [Russian] Doklad ishodit iz polozhenija, chto nailuchshej formoj zahoronenija oskolochnyh izotopov javljajutsja steklovidnye plavlenye bloki, vkljuchajushhie v svoej strukture jeti oskolki. Izlagajutsja fiziko-himicheskie osnovy prevrashhenija zhidkih radioaktivnyh othodov v tverdye bloki. Privodjatsja termogrammy jetogo processa i analizirujutsja ee otdel'nye osobennosti. Ukazyvajutsja uslovija plavlenija steklovidnoj massy, osobenno sposobstvujushhie poletu radioaktivnyh ajerozolej. Privodjatsja nekotorye rezul'taty izuchenija himicheskogo sostojanija radioaktivnyh oskolkov v tverdoj masse v svjazi s vymyvaniem radioaktivnosti iz nee. V zakljuchenie privodjatsja rezul'taty podscheta temperatur, do kotoryh mogut nagrevat'sja radioaktivnye bloki v zavisimosti ot ih harakteristik. (author)

  8. Some Possibilities of Radiation Polymerization from the Gaseous Phase on Solid Bases; Possibilites de polymerisation radiochimique en phase gazeuse sur des lits de matiere solide; O nekotorykh vozmozhnostyakh radiatsionnoj polimerizatsii iz gazovoj fazy na tverdykh podlozhkakh; Perspectivas de la radiopolimerizacion en fase gaseosa sobre lechos de sustancias solidas

    Energy Technology Data Exchange (ETDEWEB)

    Tsetlin, B. L.

    1963-11-15

    composants; la fibre servant de lit et la fibre ''greffee'' peuvent, dans des conditions appropriees, presenter chacune son propre ensemble de proprietes mecaniques. (author) [Spanish] de vapores del monomero respectivo se caracteriza por los siguientes aspectos: los centros activos que inician la polimerizacion solo se forman en la superficie del lecho, obstaculizando el transporte de la cadena cinetica al monomero y las nuevas cadenas polimericas se desarrollan por influencia unilateral de las fuerzas moleculares en la superficie solida. Estas particularidades del proceso en fase gaseosa mejoran las perspectivas que ofrece el metodo de polimerizacion injertada. Asi, es factible extender la aplicacion del mismo a lechos inorganicos y emplearlo para la sintesis de compuestos organo-minerales. Por otra parte, si se emplean como lechos fibras sinteticas estiradas, las macromoleculas orientadas de estas fibras dirigen el desarrollo de las nuevas cadenas polimericas de modo que el polimero injertado se obtiene directamente en estado orientado. Como consecuencia, se forman fibras combinadas de dos componentes; las fibras del lecho y las fibras ''injertadas'' pueden, en condiciones apropiadas, ofrecer la suma de las propiedades mecanicas propias de cada tipo. (author) [Russian] Svoeobrazie sinteza privitykh polimerov putem oblucheniya tverdykh ''podlozhek'' v prisutstvii parov polimeriehuyushchikhsya monomerov sostoit v tom, chto aktivnye tsentry, initsiiruyushchie polimerizatsiyu, generiruyutsya prakticheski tol'ko na podlozhke, peredacha kineticheskoj tsepi monomeru zatrudnena, i novye polimernye tsepi rastut v usloviyakh odnostoronnego vliyaniya molekulyarnykh sil tverdoj poverkhnosti. Ehti osobennosti gazofaznogo protsessa rasshiryayut vozmozhnosti metoda privitoj polimerizatsii. Metod mozhet byt' rasprostranen v ehtom sluchae i na neorganicheskie podlozhki i ispol'zovan dlya sinteza mineral'no-organicheskikh produktov. S drugoj storony, pri ispol'zovanii v kachestve podlozhek

  9. Synthesis, crystallographic and magnetic properties of protactinium pnictides

    International Nuclear Information System (INIS)

    Hery, Yves.

    1979-03-01

    From a theoretical point of view, protactinium lies in a very important place in the periodic system for it seems to be the first element of the actinide series where the 5f state is occupied. We have studied protactinium pnictides, particularly arsenides and antimonides. PaAs 2 , Pa 3 As 4 , PaSb 2 and Pa 3 Sb 4 were synthetized and their crystallographic properties were determined and discussed. We have measured the magnetic susceptibilities of PaC, PaAs 2 and PaSb 2 . Protactinium exhibits a dual character. In its monocarbide, which is a weakly diamagnet, it behaves as a transition element while in the temperature independent paramagnets PaAs 2 and PaSb 2 , it behaves like a 'f' element. This 'f' element character increases with increasing metal-metal distances. Furthermore the radial expansion of the protactinium 5f orbital seems to be more important than the Uranium one, and consequently the corresponding protactinium 5f electrons are less localized. In addition, some protactinium chalcogenides (βPaS 2 , γPaSe 2 and PaOSe) have been identified [fr

  10. On the suitability of lanthanides as actinide analogs

    International Nuclear Information System (INIS)

    Raymond, Kenneth; Szigethy, Geza

    2008-01-01

    With the current level of actinide materials used in civilian power generation and the need for safe and efficient methods for the chemical separation of these species from their daughter products and for long-term storage requirements, a detailed understanding of actinide chemistry is of great importance. Due to the unique bonding properties of the f-elements, the lanthanides are commonly used as structural and chemical models for the actinides, but differences in the bonding between these 4f and 5f elements has become a question of immediate applicability to separations technology. This brief overview of actinide coordination chemistry in the Raymond group at UC Berkeley/LBNL examines the validity of using lanthanide analogs as structural models for the actinides, with particular attention paid to single crystal X-ray diffraction structures. Although lanthanides are commonly accepted as reasonable analogs for the actinides, these comparisons suggest the careful study of actinide materials independent of their lanthanide analogs to be of utmost importance to present and future efforts in nuclear industries. (authors)

  11. The pressure behaviour of actinides via synchrotron radiation

    International Nuclear Information System (INIS)

    Haire, R.G.; Heathman, S.; Le Bihan, T.; Lindbaum, A.

    2002-01-01

    Various aspects of performing high-pressure studies with radioactive f-elements using synchrotrons as sources of X-rays are discussed. For ultra-high pressures, intense well-focused beams of 10 to 30 microns in diameter and a single wavelength of 0.3 to 0.7 angstrom are desired for angle dispersive diffraction measurements. Special considerations are necessary for the studies of transuranium elements under pressure at synchrotron facilities. Normally, with these actinides the pressure cells are prepared off-site and shipped to the synchrotron for study. Approved containment techniques must be provided to assure there is not a potential for the release of sample material. The goal of these high-pressure studies is to explore the fundamental science occurring as pressure is applied to the actinide samples. One of the primary effects of pressure is to reduce interatomic distances, and the goal is to ascertain the changes in bonding and electronic nature of the system that result as atoms and electronic orbitals are forced closer together. Concepts of the science being pursued with these f-elements are outlined. A brief discussion of the behaviour of americium metal under pressure performed recently at the ESRF is provided as an example of the high-pressure research being performed with synchrotron radiation. Also discussed here is the important role synchrotrons play and the techniques/procedures employed in high-pressure studies with actinides. (authors)

  12. Extraction of Am (III) and Nd (III): comparison of TODGA and TEHDGA

    International Nuclear Information System (INIS)

    Gujar, R.B.; Murali, M.S.; Ansari, S.A.; Manchanda, V.K.

    2009-01-01

    Belonging to the class of extractants, diglycolamides which are recently explored and promising for actinide partitioning, two reagents (N, N, N', N'-tetraoctyl diglycolamide) TODGA and its isomerically substituted counterpart, (N, N, N', N'- tetraethylhexyl diglycolamide) TEHDGA after addition of suitable phase modifiers, Dihexyoctanamide and isodecanol respectively in dodecane have been compared in their extraction abilities for Am (III) and Nd (III) from nitric acid as well as simulated high-level waste solutions (SHLW) equivalent to HLW arising from PHWR fuel reprocessing. Both 0.1M TODGA + 0.5M DHOA and 0.2M TEHDGA + 30% isodecanol in dodecane display high distribution ratios for the trivalent metal ions of f-elements. Similarities and differences in their extraction are discussed. (author)

  13. A Heterobimetallic Complex With an Unsupported Uranium(III)-Aluminum(I) Bond: (CpSiMe3)3U-AlCp* (Cp* = C5Me5)

    Energy Technology Data Exchange (ETDEWEB)

    Minasian, Stefan; Krinsky Ph.D., Jamin; Williams, Valerie; Arnold Ph.D., John

    2008-07-23

    The discovery of molecular metal-metal bonds has been of fundamental importance to the understanding of chemical bonding. For the actinides, examples of unsupported metal-metal bonds are relatively uncommon, consisting of Cp{sub 3}U-SnPh{sub 3}, and several actinide-transition metal complexes. Traditionally, bonding in the f-elements has been described as electrostatic; however, elucidating the degree of covalency is a subject of recent research. In carbon monoxide complexes of the trivalent uranium metallocenes, decreased {nu}{sub CO} values relative to free CO suggest that the U(III) atom acts as a {pi}-donor. Ephritikhine and coworkers have demonstrated that {pi}-accepting ligands can differentiate trivalent lanthanide and actinide ions, an effect that renders this chemistry of interest in the context of nuclear waste separation technology.

  14. Polysulfide coordination clusters of the lanthanides

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Ying-Zhao; Bestgen, Sebastian; Gamer, Michael T.; Roesky, Peter W. [Institute of Inorganic Chemistry, Karlsruhe Institute of Technology, Karlsruhe (Germany); Konchenko, Sergey N. [Institute of Inorganic Chemistry, Karlsruhe Institute of Technology, Karlsruhe (Germany); Nikolaev Institute of Inorganic Chemistry, SB RAS, Novosibirsk (Russian Federation); Novosibirsk State University (Russian Federation)

    2017-10-16

    The reaction of [(DippForm){sub 2}Ln(thf){sub 2}] with an excess of elemental sulfur in toluene resulted in the formation of the trinuclear polysulfide coordination clusters [(DippForm){sub 3}Ln{sub 3}S{sub 12}] (Ln=Sm, Yb; DippForm=N,N'-bis(2,6-diisopropylphenyl)formamidinate). These are the first f element coordination clusters (Ln{sub n}S{sub x}) with a larger polysulfide unit (n and x>2). The formation of the coordination clusters can be rationalized by the reductive cleavage of S{sub 8} with divalent lanthanides. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  15. The electronic structure of the lanthanides and actinides, a comparison

    International Nuclear Information System (INIS)

    Edelstein, N.M.

    1998-01-01

    Full text: Optical spectra of the two f-element series (the lanthanides and actinides) are comparable in many respects. For the trivalent ions isolated in single crystals, both series exhibit rich, narrow line spectra. These data can be analysed in terms of a parametric model based on a free-ion Hamiltonian plus the addition of a crystal field Hamiltonian. For most systems the agreement between the calculated and experimental energy levels is quite good. In the actinide series there appears to be a correlation between the magnitude of the crystal field and the inadequacy of the fits. The early actinides exhibit multiple oxidation states for which there is no precedent in the lanthanide series. The parametric model mentioned earlier has been utilized for some tetravalent actinide systems with reasonably good results. A selective survey of results describing the similarities and differences of various lanthanide and actinide systems will be given

  16. Preparation and characterization of uranium-iron triple-bonded UFe(CO){sub 3}{sup -} and OUFe(CO){sub 3}{sup -} complexes

    Energy Technology Data Exchange (ETDEWEB)

    Chi, Chaoxian; Meng, Luyan; Luo, Mingbiao [School of Chemistry, Biological and Materials Sciences, State Key Laboratory Breeding Base of Nuclear Resources and Environment, East China University of Technology, Nanchang (China); Wang, Jia-Qi; Li, Wan-Lu; Li, Jun [Department of Chemistry and Key Laboratory of Organic Optoelectronics and Molecular Engineering of Ministry of Education, Tsinghua University, Beijing (China); Qu, Hui; Zhou, Mingfei [Department of Chemistry, Collaborative Innovation Center of Chemistry for Energy Materials, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai (China)

    2017-06-06

    We report the preparation of UFe(CO){sub 3}{sup -} and OUFe(CO){sub 3}{sup -} complexes using a laser-vaporization supersonic ion source in the gas phase. These compounds were mass-selected and characterized by infrared photodissociation spectroscopy and state-of-the-art quantum chemical studies. There are unprecedented triple bonds between U 6d/5f and Fe 3d orbitals, featuring one covalent σ bond and two Fe-to-U dative π bonds in both complexes. The uranium and iron elements are found to exist in unique formal U(I or III) and Fe(-II) oxidation states, respectively. These findings suggest that there may exist a whole family of stable df-d multiple-bonded f-element-transition-metal compounds that have not been fully recognized to date. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  17. Reaction chemistry of cerium

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-01-01

    It is truly ironic that a synthetic organic chemist likely has far greater knowledge of the reaction chemistry of cerium(IV) than an inorganic colleague. Cerium(IV) reagents have long since been employed as oxidants in effecting a wide variety of organic transformations. Conversely, prior to the late 1980s, the number of well characterized cerium(IV) complexes did not extend past a handful of known species. Though in many other areas, interest in the molecular chemistry of the 4f-elements has undergone an explosive growth over the last twenty years, the chemistry of cerium(IV) has for the most part been overlooked. This report describes reactions of cerium complexes and structure.

  18. Fundamental aspects of actinide-zirconium pyrochlore oxides: Systematic comparison of the Pu, Am, Cm, Bk and Cf systems

    International Nuclear Information System (INIS)

    Haire, R.G.; Raison, P.E.

    2000-01-01

    Zirconium- and hafnium-based oxide materials have gained attraction for various nuclear applications. These materials have features in common with one of the early, well-publicized inorganic ceramics for immobilizing nuclear waste. Our interests have addressed the fundamental structural and chemical properties of these oxide systems. We pursued both the crystal chemical constraints of the oxide matrices, as well as the importance of the chemistry of the f-elements. By incorporating five actinide elements in our studies, we were able to compare systematically the materials science of these materials with the fundamental chemistry and electronic configurations of these actinides employed. It is expected that this basic information will be useful technologically in the realm of tailor-made materials for different applications

  19. Crystallographic and Spectroscopic Characterization of Americium Complexes Containing the Bis[(phosphino)methyl]pyridine-1-oxide (NOPOPO) Ligand Platform

    Energy Technology Data Exchange (ETDEWEB)

    Corbey, Jordan F. [Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Rapko, Brian M. [Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Wang, Zheming [Pacific Northwest National Laboratory, Richland, Washington 99354, United States; McNamara, Bruce K. [Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Surbella, Robert G. [Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Pellegrini, Kristi L. [Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Schwantes, Jon M. [Pacific Northwest National Laboratory, Richland, Washington 99354, United States

    2018-02-06

    Abstract The crystal structures of americium species containing a common multi-functional phosphine oxide ligand, reported for its ability to extract f elements from acidic solutions, namely 2,6-[Ph2P(O)CH2]2C5H3-NO, L, have finally been determined after over three decades of separations studies involving these species and their surrogates. The molecular compounds Am(L)(NO3)3, Am 1:1, and [Am(L)2(NO3)][NO3]2, Am 2:1, along with their neodymium and europium analogs were synthesized and characterized using single-crystal X-ray crystallography, attenuated total reflectance Fourier transform infrared (ATR) spectroscopy and luminescence spectroscopy to provide a comprehensive comparison with new and known analogous complexes.

  20. New insights into phosphate based materials for the immobilisation of actinides

    Energy Technology Data Exchange (ETDEWEB)

    Neumeier, Stefan; Ji, Yaqi; Kowalski, Piotr M.; Kegler, Philip; Schlenz, Hartmut; Bosbach, Dirk; Deissmann, Guido [Forschungszentrum Juelich GmbH (Germany). Inst. fuer Energie und Klimaforschung (IEK), Nukleare Entsorgung und Reaktorsicherheit (IEK-6); JARA High-Performance Computing, Aachen (Germany); Arinicheva, Yulia [Forschungszentrum Juelich GmbH (Germany). Inst. fuer Energie und Klimaforschung (IEK), Nukleare Entsorgung und Reaktorsicherheit (IEK-6); JARA High-Performance Computing, Aachen (Germany); Forschungszentrum Juelich (Germany). Institut fuer Energie- und Klimaforschung (IEK), Werkstoffsynthese und Herstellungsverfahren (IEK-1); Heuser, Julia M. [Forschungszentrum Juelich GmbH (Germany). Inst. fuer Energie und Klimaforschung (IEK), Nukleare Entsorgung und Reaktorsicherheit (IEK-6); JARA High-Performance Computing, Aachen (Germany); Karlsruhe Institute of Technology (Germany). Inst. of Applied Materials (IAM)

    2017-07-01

    This paper focuses on major phosphate-based ceramic materials relevant for the immobilisation of Pu, minor actinides, fission and activation products. Key points addressed include the recent progress regarding synthesis methods, the formation of solid solutions by structural incorporation of actinides or their non-radioactive surrogates and waste form fabrication by advanced sintering techniques. Particular attention is paid to the properties that govern the long-term stability of the waste forms under conditions relevant to geological disposal. The paper highlights the benefits gained from synergies of state-of-the-art experimental approaches and advanced atomistic modeling tools for addressing properties and stability of f-element-bearing phosphate materials. In conclusion, this article provides a perspective on the recent advancements in the understanding of phosphate based ceramics and their properties with respect to their application as nuclear waste forms.

  1. Normal coordinate treatment and Raman intensity analysis of yttrium vanadate and calcium tungstate crystal

    Energy Technology Data Exchange (ETDEWEB)

    Budha Addepalli, V; Kumar, S P; Padma, V A; Rajeswara Rao, N [Osmania Univ., Hyderabad (India). Dept. of Physics

    1976-09-01

    Raman scattering tensors of crystalline YVO/sub 4/ and CaWO/sub 4/ are derived. Using the spectra of YVO/sub 4/, the intensities are substituted in the formulae. They are used to determine the polarizability derivatives of V-O bond. Substituting them back into the intensity formulae, a number of equations involving the L elements are obtained. Supplementing them with the matrix equation LL' = G, and using L'FL = ..gamma.., a-l the F-elements are determined. It is observed that the force constants relating to the translations of the group YVO/sub 4/ are quite high, explaining the high melting point of the crystal.

  2. The structure determination of uranocene and the first COT lanthanide complexes

    International Nuclear Information System (INIS)

    Raymond, Kenneth N.

    2015-01-01

    This paper results from my introductory talk at the symposium 'Frontiers of Organo-f-Element Chemistry'. Although my active research in organo-actinide and -lanthanide chemistry ended early in my career, it led to an interest in actinide coordination chemistry that continues to this day; I am a member of the actinide research group of the Chemical Sciences Division of the Lawrence Berkeley National Laboratory. My remarks will be somewhat personal and are intended to provide a perspective on the history of this field, but I hope to connect it to what has become a new and very active area of research; this class of compounds is now associated with what are essentially quantum confined multiconfigurational molecules. (authors)

  3. Twisted classical Poincare algebras

    International Nuclear Information System (INIS)

    Lukierski, J.; Ruegg, H.; Tolstoy, V.N.; Nowicki, A.

    1993-11-01

    We consider the twisting of Hopf structure for classical enveloping algebra U(g), where g is the inhomogeneous rotations algebra, with explicite formulae given for D=4 Poincare algebra (g=P 4 ). The comultiplications of twisted U F (P 4 ) are obtained by conjugating primitive classical coproducts by F element of U(c)xU(c), where c denotes any Abelian subalgebra of P 4 , and the universal R-matrices for U F (P 4 ) are triangular. As an example we show that the quantum deformation of Poincare algebra recently proposed by Chaichian and Demiczev is a twisted classical Poincare algebra. The interpretation of twisted Poincare algebra as describing relativistic symmetries with clustered 2-particle states is proposed. (orig.)

  4. Double-double effect and coordination number

    International Nuclear Information System (INIS)

    Mioduski, T.

    1992-01-01

    The original method of interpretation together with its theoretical foundations is developed, making it possible to use location and direction of the double-double (tetrad) effect within the Ln and An series to determine the coordination number (CN) complexes of the f-block elements. The method is applied for potentiometric and radiometric equilibrium studies. It has been pointed and that the decisive factor for the direction of the double-double effect in the case of the Gibbs energy variations is a difference in the CN of the f-element ion between the reaction product complex and that for the reaction substrate the ''regular'' effect for a given tetrad is accompanied by decrease in the CN while the ''reverse'' effect by increase in the CN. (author). 122 refs, 5 tabs, 8 figs

  5. Lanthanide and actinide inorganic complexes in natural waters. TRLFS and ESI-MS studies

    Energy Technology Data Exchange (ETDEWEB)

    Vercouter, T.; Amekraz, B.; Moulin, C.; Vitorge, P

    2004-07-01

    Aqueous complexes of M(III) f-element ions with the inorganic ligands CO{sub 3}{sup 2-} and SO{sub 4}{sup 2-} have been investigated using the highly-sensitive speciation techniques TRLFS and ESI-MS. The Eu(CO{sub 3}){sub i}{sup 3-2i} (i=1-3) species have been characterized by TRLFS, and the stoichiometry of the limiting complex Eu(CO{sub 3}){sub 3}{sup 3-} have been confirmed by solubility measurements of NaEu(CO{sub 3}){sub 2}(s) at high ionic strength. Temperature effect on Cm(III) carbonate complexes is evidenced by the TRLFS technique. Investigation on sulphate complexation has been done at various ionic strengths by TRLFS on Eu(III) and by ESI-MS on La(III). New thermodynamic data are obtained by both techniques, which are consistent with literature data. (authors)

  6. Development of Halide and Oxy-Halides for Isotopic Separations

    Energy Technology Data Exchange (ETDEWEB)

    Martin, Leigh R. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Johnson, Aaron T. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Pfeiffer, Jana [Idaho National Lab. (INL), Idaho Falls, ID (United States); Finck, Martha R. [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2014-10-01

    The goal of this project was to synthesize a volatile form of Np for introduction into mass spectrometers at INL. Volatile solids of the 5f elements are typically those of the halides (e.g. UF6), however fluorine is highly corrosive to the sensitive internal components of the mass separator, and the other volatile halides exist as several different stable isotopes in nature. However, iodide is both mono-isotopic and volatile, and as such presents an avenue for creation of a form of Np suitable for introduction into the mass separator. To accomplish this goal, the technical work in the project sought to establish a novel synthetic route for the conversion NpO2+ (dissolved in nitric acid) to NpI3 and NpI4.

  7. f-state luminescence of lanthanide and actinide ions in solution

    International Nuclear Information System (INIS)

    Beitz, J.V.

    1993-01-01

    Detailed studies of the luminescence of aquated Am 3+ are presented in the context of prior lanthanide and actinide ion work. The luminescing state of aquated Am 3+ is confirmed to be 5 D l based on observed emission and excitation spectra. The luminescence lifetime of Am 3+ in H 2 O solution is (22 ± 3) ns and (155 ± 4) ns in D 2 O solution at 295 K. Judd-Ofelt transition intensity theory qualitatively describes the observed Am 3+ relative integrated fluorescence intensities. Recent luminescence studies on complexed trivalent f-element ions in solution are reviewed as to the similarities and differences between lanthanide ion 4f state and actinide ion 5f state properties

  8. Complexation of trivalent cationic lanthanides by N.O donor ligands: physico-chemical studies of the association and selectivity in solution

    International Nuclear Information System (INIS)

    Bravard, F.

    2004-01-01

    The aim of this work is to study the complexation of f-elements in solution by ligands incorporating N-heterocyclic donors. These ligands display interesting properties for the selective separation of An(III)/Ln(III) have been studied to obtain a better understanding of the coordination properties with f-elements and to develop more selective extractants. The hepta-dentate ligand tpaam shows an affinity for Ln(III) similar to the tetradentate ligand tpa in water even when the three additional amide groups are bonded to the metal. Even though the complexation with tpa is exothermic, that with tpaam is endothermic with a more positive entropy. The dehydration of the cation disfavours the formation of Ln(III) complexes with ligands containing weak donors. The analysis of the solution paramagnetic relaxation times of the tpaam complexes is in agreement with data in the solid-state. There is little difference between the formation constants of the Ln 3+ complexes with different ligands (tpaam, tpzen, tpa and tpza) as determined by UV-vis spectrophotometry in anhydrous acetonitrile. The limitations encountered during this study are intrinsic to the ligands studied. The preliminary study of two tetrapodal ligands containing acid and pyridine groups (L py )or pyrazine (L pz ) show the formation of 1:1 complexes in water. Analysis of the formation constants of the corresponding Gd(III) complexes shows that replacement of a pyridine group by pyrazine result in a loss of stability of 1.6 logarithmic units. (author) [fr

  9. Controlling Hexavalent Americium – A Centerpiece to a Compact Nuclear Fuel Cycle

    Energy Technology Data Exchange (ETDEWEB)

    Shafer/Braley, Jenifer; Nash, Kenneth L; Lumetta, Gregg; McCann, Kevin; Sinkov, Sergey I

    2014-10-01

    Closing the nuclear fuel cycle could be simplified by recovering the actinides U through Am as a group. This could be achieved by converting U, Np, Pu and Am to the hexavalent state. Uranium, Np and Pu are readily oxidized to the hexavalent state. Generation of hexavalent Am in acidic solutions is more difficult, as the standard reduction potential of the Am(VI) /Am(III) couple (+1.68 V in 1 M HClO4) is well outside of the electrochemical stability window of water. While the oxidation and separation of Am has been demonstrated under laboratory conditions, several issues could plague scale up and implementation of this separation with used fuel. Two primary concerns are considered. The first issue concerns the stability of the oxidized Am. The second involves the undesirable co-extraction of tetravalent f-elements with the hexavalent actinides. To address the first concern regarding Am redox instability, Am reduction will be monitored under a variety of different conditions to establish the means of improving the stability of Am(VI) in the organic phase. Identifying the components contributing most significantly to its reduction will allow thoughtful modification of the process. To address the second concern, we propose to apply branched chain extractants to separate hexavalent actinides from tetravalent f-elements. Both branched monoamide and organophosphorus extractants have demonstrated significant selectivity for UO22+ versus Th4+, with separation factors generally on the order of 100. The efforts of this two-pronged research program should represent a significant step forward in the development of aqueous separations approaches designed to recover the U-Am actinides based on the availability of the hexavalent oxidation state. For the purposes of this proposal, separations based on this approach will be called SAn(VI) separations, indicating the Separation of An(VI).

  10. The Role of Non-Destructive Testing in Test-Reactor Operation at the National Reactor Testing Station; Role des Essais Non Destructifs dans l'Exploitation des Reacteurs d'Essai au Centre National d'Essais de Reacteurs; Rol' nedestruktivnykh ispytanij pri ehkspluatatsii ispytatel'nykh reaktorov na natsional'noj stantsii po ispytaniyam reaktorov; Papel de los Metodos No Destructivos en la Explotacion de los Reactores de la National Reactor Testing Station

    Energy Technology Data Exchange (ETDEWEB)

    Francis, W. C.; Brown, E. S.; Burdick, E. E.; Gibson, G. W.; Tingey, F. H. [Phillips Petroleum Company, Atomic Energy Division, Idaho Falls, Idaho (United States)

    1965-10-15

    corrientes de Foucault. Otras tecnicas que han demostrado su utilidad son la inspeccion por penetracion de liquidos, los ensayos con nitrogeno liquido para detector grietas superficiales, los ensayos de recocido termico para determinar ampollas, y la exploracion gamma de placas irradiadas. Muestras de elementos combustibles tomadas estadisticamente se ensayan por metodos hidraulicos para confirmar su integridad estructural, especialmente la estabilidad de la union entre la placa combustible y la placa lateraL Constantemente se intenta mejorar las tecnicas actuales y perfeccionar nuevos procedimientos de inspeccion de caracter no destructivo. (author) [Russian] Bol'shie kapitalovlozhenija (bolee 100 mln. doll. ) v jadernye opytnye reaktory pri Nacional'noj labo- ratorii po ispytaniju reaktorov i neobhodimost' jekspluatirovat' ih bezopasno trebujut vyso- kokachestvennogo kontrolja za reaktorami i opytnymi komponentami v osobennosti za topli- vom i upravljajushhimi sterzhnjami. Pojetomu nedestruktivnye ispytanija igrajut ochen' vazhnuju rol' v opredelenii kachestva jetih komponentov do togo , kak oni ispol'zujutsja na opytnyh reaktorah. Hotja mnogie iz jetih opytov provodjatsja po horosho otrabotannym programmam, tem ne menee bylo razrabotano mnogo unikal'nyh sposobov i shiroko ispol'zuetsja obychnoe oborudovanie. Dolgoe vremja ispol'zovalis' ul'trazvukovye metody v celjah obnaruzhenija rakovin, nediffuzioznosti teplovydeljajushhih jelementov i vnutrennih treshhin. V poslednee vremja jeta rabota byla rasprostranena na avtomaticheskoe skennirovanie krivyh plastin i dlja o b - sledovanija obluchennyh toplivnyh plastin v kanalah dlja hranenija. Ves'ma interesnaja rabota byla provedena v dele primenenija ul'trazvuka dlja obnaruzhenija razryva hrupkih aktivnyh zon, kotoryj mozhet vozniknut' v prcesse izgotovlenija. Metod gamma-skennirovanija dlja opredelenija soderzhanija urana-235 v toplivnyh jele- mentah okazalsja nastol'ko nadezhnym, chto on javljaetsja osnovoj dlja podscheta

  11. Radiant-Heat Spray Calcination Studies; Calcination par Pulverisation et Chauffage Radiant; 0418 0421 0421 041b 0415 0414 041e 0412 0410 041d 0418 042f 041d 0410 041a 0410 041b 042c 0426 0418 041d 0410 0422 041e 0420 0410 0425 0424 041e 0420 0421 0423 041d 041e 0427 041d 041e 0413 041e 0422 0418 041f 0410 0421 041d 0410 0413 0420 0415 0412 0410 041d 0418 0415 041c 0422 0415 041f 041b 041e 0412 042b 041c 0418 0417 041b 0423 0427 0415 041d 0418 0415 041c ; Estudios de Calcinacion por Pulverizacion y Calentamiento Radiante

    Energy Technology Data Exchange (ETDEWEB)

    Allemann, R. T.; Moore, R. L.; Upson, U. L. [Hanford Laboratories General Electric Co., Richland, WA (United States)

    1963-02-15

    sustitucion de la tobera, calentamiento por induccion del crisol, detectorde radiactividad de] crisol, sistema de tratamiento de los gases de escape (comprendidos el condensador, el depurador y los filtros) tomamuestras de gases de escape, tomamuestras de liquidos, sistema de lavado, instrumentos de precision y metodos de control. Les autores examinan la experiencia adquirida con el funcionamiento de las instalaciones de calcinacion y el equipo auxiliar. Los resultados experimentales expuestos ponen de manifiesto la eficacia de la descontaminacion de los gases de escape, asi como el comportamiento de los principales constituyentes quimicos y de determinados productos de fision. (author) [Russian] Daetsja opisanie processa forsunochnogo kal'cinirovanija s nagrevaniem teplovym izlucheniem dlja otverzhdenija zhidkih othodov, a-takzhe obsuzhdaetsja konstrukcija forsunochnogo kal'cinatora proizvoditel'nost'ju 3,7 l/chas; jetot apparat vkljuchaet nebol'shoj tigel' dlja plavanija, kotoryj mozhet byt' samostojatel'no ispol'zovan v kachestve tigel'noj obzhigatel'noj pechi. Apparat byl skonstruirovan dlja togo, chtoby proverit' vozmozhnost' osushhestvlenija processov kal'cinirovanija na promyshlennoj ustanovke po pererabotke othodov ''Pureks-processa'' so sledujushhih tochek zrenija: osushhestvlenie processa v kachestve edinoj operacii, obrabotka vydeljaemyh gazov, povedenie produktov delenija, harakternye osobennosti kondensata i kal'cinirovannyh othodov. Vsja sistema byla skonstruirovana takim obrazom, chtoby ona pomestilas' v zashhitnuju kameru ploshhad'ju 2,26 h 4,57 m i vysotoj 4,57M', oborudovannuju manipuljatorom. Obsuzhdajutsja sledujushhie voprosy: jelektricheskij nagrevatel' obzhigatel'noj kolonny dlja forsunochnogo kal'cinirovanija; termicheskaja izoljacija kolonny; soplo forsunki; metod zameny sopla; indukcionnyj podogrev plavil'nogo tiglja; detektor radioaktivnosti dlja tiglja; sistema obrabotki vyhodjashhih gazov, vkljuchaja kondensor, skrubber i fil'try; probootbornoe

  12. Half-Life Studies of Radiocaesium in Humans; Etudes sur la Periode de Radiocesium chez l'Homme; 0418 0421 0421 041b 0415 0414 ; Estudio sobre el Periodo Biologico del Radiocesio en el Hombre

    Energy Technology Data Exchange (ETDEWEB)

    Naversten, Y.; Liden, K. [Radiation Physics Department, University of Lund (Sweden)

    1964-11-15

    estos estudios, sobre todo en lo que respecta a la velocidad de eliminacion del cesio, es decir, al periodo biologico y a su variacion segun el sexo y la edad. Por lo general, los periodos biologicos determinados experimentalmente oscilan entre 30 y 90 d. (author) [Russian] Izuchalas zaderzhka cezija-137 u ljudej pri razlichnyh obstojatel'stvah. Dvum vzroslym muzhchinam vvodili vnutrivenno malye kolichestva cezija-137. Pacienty nahodilis' pod nabljudeniem 300 dnej, v techenie kotoryh proizvodilis' chastye izmerenija radio aktivnosti vsego organizma.i sbor vydelenij v nachal'nom periode. Stepen' zaderzhki izotopa snizhalas' kak summa dvuh jeksponencial'nyh velichin. Naibolee medlenno izmenjajushhajasja velichina snizhalas' s periodom poluvyvedenija okolo 75 dnej. Olin iz pacientov poluchal cezij-137 vnutr' 2 goda spustja,prichem nabljudalsja tot zhe tip vydelenija, kak i posle vnutrivennogo vvedenija. Skorost' vydelenija cezija-137 izuchalas' takzhe drugim sposobom u bol'shoj gruppy muzhchin, zhenshhin i detej putem sravnenija dannyh issledovanija diety. Pri obsledovanii gruppy iz 10 dobrovol'cev, izmenivshih svoju dietu, okazalos' vozmozhnym rasschitat' srednjuju skorost' vydelenija na osnovanii izmerenija radioaktivnosti vsego organizma s intervalom v 6 nedel'. Vydelenija opredeljali takzhe u 2-h chelovek posle priema vnutr' cezija-137. Predstavleny podrobnye dannye jetih issledovanij, v osobennosti v otnoshenii skorosti vydelenija cezija, t.e. perioda ego poluvyvedenija i ego variacij v zavisimosti ot pola i vozrasta. V srednem byli polucheny sroki poluvyvedenija ot 30 do 90 dnej. (author)

  13. Scanning in Thyroid Cancer; Exploration des tumeurs de la thyroide; Ispol'zovanie radioizotopov pri issledovanii raka shchitovidnoj zhelezy; Exploracion de los tumores tiroideos

    Energy Technology Data Exchange (ETDEWEB)

    Bauer, Franz K [Radioisotope Centre, University of Southern California School of Medicine, Los Angeles, CA (United States)

    1959-07-01

    methode qui permette de suivre l'evolution de la maladie. (author) [Spanish] La exploracion de los tumores de la tiroides reviste interes para: 1. El diagnostico preoperatorio de los nodulos tiroideos; 2. La localization de metastasis del cancer de tiroides; 3. El tratamiento de los enfermos tiroidectomizados, con metastasis del cancer de la tiroides. El autor describe el aspecto de los nodulos tiroideos en el centelleograma y proporciona algunos resultados preliminares obtenidos con el empleo del fosforo radiactivo y con el recuento externo de los nodulos < inactivos > mediante un contador Geiger-Mueller. El autor describe asimismo la localizacion de las metastasis del cancer de la tiroides, destacando, especialmente, el empleo de la hormona tirotropica. Ese metodo ha permitido comprobar que las tres cuartas partes de los enfermos que padecen de tumores metastaticos de la tiroides tienen metastasis activas. Estudia detalladamente la tecnica de la ablation de los restos glandulares que suelen quedar despues de la tiroidectomia total, asi como el tratamiento de las metastasis. La exploracion de las metastasis constituye el mejor medio para observar la evolucion de la enfermedad. (author) [Russian] Primenenie radioizotopov v issledovanii raka shchitovidnoj zhelezy rekomenduetsya v sleduyushchikh sluchayakh: 1. Predoperatsionny j diagnoz uzelkovogo utolshcheniya shchitovidnoj zhelezy; 2. Lokalizatsiya metastazov raka shchitovidnoj zhelezy; 3. Lechenie bol'nykh s udalennoj shchitovidnoj zhelezoj, no s metastazami, obrazovann{sup m}i rakom ehtoj zhelezy; Opisyvaetsya vliyanie uzelkovykh utolshchenij shchitovidnoj zhelezy na etsiitigrammu. Soobshchaetsya o nekotorykh predvaritel'nykh rezul'tatakh opredeleniya < kholodnykh > utolshchenij pri pomoshchi radioaktivnog o fosfora i naruzhnogo primeneniya schetchika Gejgera-Myullera. Opisyvaetsya lokalizatsiya metastazov raka shchitovidnoj zhelezy i v osobennosti ispol'zovanie dlya ehtoj Deli gormona perednej doli gipofiza. S pomoshch

  14. Use of radioactive tracers in studying the transport of solids in watercourses; Emploi de traceurs radioactifs pour l'etude du transport solide dans les cours d'eau; Ispol'zovanie radioaktivnykh indikatorov dlya izucheniya peremeshcheniya tverdykh chastits v vodnykh potokakh; Empleo de indicadores radiactivos para el estudio del transporte de solidos en las corrientes de agua

    Energy Technology Data Exchange (ETDEWEB)

    Courtois, G [Centre d' Etudes Nucleaires de Saclay (France); Jaeery, P; Heuzel, M [Laboratoire National d' Hydraulique de Chatou (France)

    1962-01-15

    izucheniya vozmozhnostej usovershenstvovaniya metoda radioaktivnykh indikatorov, v osobennosti dlya polucheniya kolichestvennykh dannykh. (author)

  15. Thermal Shock Tests on UO{sub 2} Small Spheres; Essais de choc thermique sur des elements spheriques de UO{sub 2}; Ispytaniya nebol'shikh sharikov iz UO{sub 2} teplovykh udarom; Ensayo de pequenas esferas de UO{sub 2} por choque.termico

    Energy Technology Data Exchange (ETDEWEB)

    Perona, G.; Brutto, E.; Galbusera, U.; Palladino, G.; Sesini, R. [Centro Informazioni Studi Esperienze, Milan (Italy)

    1963-11-15

    exponen los resultados obtenidos. La aplicacion de este metodo presenta, al parecer, considerable interes, sobre todo en lo que concierne a las investigaciones encaminadas a mejorar las caracteristicas de las esferas de UO{sub 2} por medio de aditivos. En e fecto, permite verificar el efecto global con una sola medicion. (author) [Russian] Ispol'zuya malye pariki iz UO{sub 2} v kachestve yadernogo topliva v reaktore, gde oni nakhodyatsya v soprikosnovenii s teplonositelem, neobkhodimo znat' maksimal'nuyu pri rabochem rezhime reaktora velichinu termicheskikh napryazhenij, kotorye mogut vyderzhivat' bez povrezhdeniya ehti shariki. Esli izvestny fizicheskie svojstva materiala, to mozhno rasschitat' ehti napryazheniya pri rabochem rezhime. Odnako vvidu mnogochislennosti podlezhashchikh uchetu faktorov i neizbezhnoj doli neopredelennosti kazhdogo iz nikh predstavlyaetsya predpochtitel'nym provesti neposredstvennye ispytaniya ehtikh sharikov, podvergnuv ikh tem zhe napryazheniyam, kakie oni ispytyvayut v reaktore. V nastoyashchej rabote byl izuchen metod teplovogo udara v primenenii k malym sharikam i ukazyvayutsya usloviya, pri kotorykh ehtot metod pozvolyaet proizvesti napryazheniya, neposredstvenno sravnimye s temi, kotorye sushchestvuyut v reaktore. V sluchae malykh sharikov zatrudnenie zaklyuchaetsya v osushchestvlenii okhlazhdeniya, pozvolyayushchego dostigat' ochen' bol'shikh znachenij koehffitsienta poverkhnostnoj teploperedachi. Opisyvayutsya ehksperimental'nye metody i soobshchayutsya poluchennye rezul'taty. Primenenie ehtogo' metoda, po-vidimomu., predstavlyaet bol'shoj interes, v osobennosti v oblasti tekhnologicheskikh izyskanij s tsel'yu uluchsheniya svojstv malykh sharikov iz UO{sub 2} putem vklyucheniya dobavochnykh komponentov. Fakticheski,ehtot metod daet vozmozhnost' pri pomoshchi odnogo tol'ko izmereniya kontrolirovat' izuchaemoe vozdejstvie. (author)

  16. Tissue Metabolism of Tritium-Labelled Thyroid Hormones and Thyronine; Sur le Metabolisme Cellulaire d'Hormones Thyroiediennes Marquees par le Tritium; 0422 043a 0430 043d 0435 0432 044b 0439 043c 0414 ; Metabolismo de las Hormonas Tiroideas y de la Tironina Marcadas con {sup 3}H en los Tejidos

    Energy Technology Data Exchange (ETDEWEB)

    Roche, J.; Nunez, J.; Jacquemin, Cl. [Laboratoire de Biochimie Generale et Comparee, College de France, Paris (France)

    1962-02-15

    tironina v kachestve estestvennogo produkta shhitovidnyh gormnov podtverzhdaet issledovanie ego tkanevogo metabolizma; mechennyj tri- tiem tironin v 3 i 5 byl poluchen v laboratornyh uslovijah (in-vitro) putem razrezov pochki i myshcy. Harakternye osobennosti opredeljalis' zhidkoscintil- -ljacionnym radiohromatografom radioavtografiej : 1. Tirozin, obrazovanie kotorogo svidetel'stvuet o razryve svjazujushhego (difeniletornogo) mosta tironina. 2. 3' s gidroksitironinom i 3 i 4 s bigidroksifenilalaninom, nalichie koto- ryh illjustriruet uchastie processa d'gidroksilacii v katabolizme ciklov. 3. Tiroacetichnye i rgidroksifenilaceticheskie kisloty, pojavdenie kotoryh otvechaet obshhej sheme ponizhenija al'fa- amidirovannyh kislot. (author)

  17. Application of Tritiated Compounds to the Midge Chironomus and some Aspects of the Metabolism of Salivary Gland Chromosomes; Emploi de Composes Trities pour l'Etude du Chironome et de Certains Aspects du Metabolisme des Chromosomes des Glandes Salivaires; 041f 0440 0438 043c 0414 ; Aplicacion de Compuestos Tritiados a la Mosca Cbironomus y Algunos Aspectos del Metabolismo en los Cromosomas de las Glandulas Salivares

    Energy Technology Data Exchange (ETDEWEB)

    Pelling, C. [Max-Planck-Institut fuer Biologie, Tuebingen, Federal Republic of Germany (Germany)

    1962-02-15

    vysokoj stepen'ju razdelenija. Sintez DNK (timidin), sintez RNK (uridin) i proteinovyj sintez v kletke mozhno prosledit' putem opredelenija vremeni i priblizitel'- nogo kolichestva pogloshhenija. V protivopolozhnost' proteinovomu sintezu sintez-DNK i sintez RNK javlja- jutsja ogranichennymi dlja hromosom. Sushhestvennaja fiziologicheskaja aktivnost' hromosom, vidimo, predstavlena sintezom RNK, kotoryj imeet mesto pri opre- delennyh otchetlivyh mestopolozhenijah (nukleoljarnye obrazovateli, kol'ca 'Balbiani' odutlovatosti i drugie hromosomye svjazi). I doklade rassmatrivajutsja nekotorye osobennosti sinteza NIK. (author)

  18. Hydrothermal syntheses, structural, Raman, and luminescence studies of Cm[M(CN)2]3.3H2O and Pr[M(CN)2]3.3H2O (M=Ag, Au)

    International Nuclear Information System (INIS)

    Assefa, Zerihun; Haire, Richard G.; Sykora, Richard E.

    2008-01-01

    We have prepared Cm[Au(CN) 2 ] 3 .3H 2 O and Cm[Ag(CN) 2 ] 3 .3H 2 O as a part of our continuing investigations into the chemistry of the 5f-elements' dicyanometallates. Single crystals of Cm[Au(CN) 2 ] 3 .3H 2 O were obtained from the reaction of CmCl 3 and KAu(CN) 2 under mild hydrothermal conditions. Due to similarities in size, the related praseodymium compounds were also synthesized and characterized for comparison with the actinide systems. The compounds crystallize in the hexagonal space group P6 3 /mcm, where the curium and the transition metals interconnect through cyanide bridging. Crystallographic data (Mo Kα, λ=0.71073 A): Cm[Au(CN) 2 ] 3 .3H 2 O (1), a=6.6614(5) A, c=18.3135(13) A, V=703.77(9), Z=2; Pr[Au(CN) 2 ] 3 .3H 2 O (3), a=6.6662(8) A, c=18.497(3) A, V=711.83(17), Z=2; Pr[Ag(CN) 2 ] 3 .3H 2 O (4), a=6.7186(8) A, c=18.678(2) A, V=730.18(14), Z=2. The Cm 3+ and/or Pr 3+ ions are coordinated to six N-bound CN - groups resulting in a trigonal prismatic arrangement. Three oxygen atoms of coordinated water molecules tricap the trigonal prismatic arrangement providing a coordination number of nine for the f-elements. The curium ions in both compounds exhibit a strong red emission corresponding to the 6 D 7/2 → 8 S 7/2 transition. This transition is observed at 16,780 cm -1 , with shoulders at 17,080 and 16,840 cm -1 for the Ag complex, while the emission is red shifted by ∼100 cm -1 in the corresponding gold complex. The Pr systems also provide well-resolved emissions upon f-f excitation. - Graphical abstract: Coordination polymeric compounds between a trans-plutonium element, curium and transition metal ions, gold(I) and silver(I), were prepared using the hydrothermal synthetic procedure. The curium ion and the transition metals are interconnected through cyanide bridging. The Cm ion has a tricapped trigonal prismatic coordination environment with coordination number of nine. Detail photoluminescence studies of the complexes are also reported

  19. Pointing Out Main Factors from Design, Construction and Operating Experience of Existing Nuclear Plants for Assisting in Shaping Future Nuclear Power Programmes; Les principaux criteres degages de l'etude, de la construction et de l'exploitation des centrales nucleaires existantes et leur interet pour l'elaboration des futurs programmes d'energie d'origine nucleaire; Ukazanie osnovnykh faktorov proektirovaniya, stroitel'stva i opyta ehkspluatatsii sushchestvuyutsikh atomnykh ehlektrostantsij, chto dolzhno pomoch' pri sostavlenii budushchikh programm atomnoj ehnergetiki; Principales consideraciones relativas al diseno, construccion y explotacion de centrales nucleares, encaminadas a facilitar la preparacion de programas futuros de energia nucleoelectrica

    Energy Technology Data Exchange (ETDEWEB)

    Dalla Volta, F. [Comitato Nazionale per l' Energia Nucleare, Rome (Italy)

    1963-10-15

    de tipo bien conocido, la memoria estudia en que medida estas instalaciones pueden construirse sin dificultades y satisfacer la demanda de la red; tambien en este aspecto se refiere al creciente papel que cabe atribuir en Italia a la energia nucleoelectrica. Por ultimo, la memoria re calca hasta que punto el acopio y la interpretacion de los datos relativos a las tres centrales nucleares que ahora comienzan a funcionar en Italia facilitarian el proyecto de instalaciones futuras. Alude a la posibilidad de establecer desde ya ciclos de combustible mas extensos. (author) [Russian] Rassmatrivayutsya naibolee vazhnye tekhnicheskie i ehkonomicheskie faktory, kotorye vyyavilis' pri proektirovanii, stroitel'stve i ehkspluatatsii pervykh promyshlennykh atomnykh ehlektrostantsij i kotorye mogut byt' ochen' poleznymi pri sozdanii v budushchem novykh atomnykh ehlektrostantsij, uchityvaya osoben-nosti uslovij v Italii. Nyneshnee sostoyanie tekhnologii proizvodstva i ee postoyannoe razvitie v khode osushchestvleniya proektov pokazali sushchestvovanie opredelennoj tendentsii k snizheniyu kak stoimosti toplivnogo tsikla, tak i stoimosti komponentov stantsii. Ehtomu takzhe blagopriyatstvuyut vozrastayushchaya tendentsiya k uvelicheniyu razmerov ehlektrostantsii i tot fakt, chto analiz ehnergeticheskogo prognoza ehnergosistemy govorit o nalichii blagopriyatnykh uslovij dlya stroitel'stva ehlektrostantsij bol'shej moshchnosti na yadernom toplive vmesto stantsij na obychnom toplive, iskhodya iz predskazannykh izmenenij v stoimosti proizvodstva ehnergii, obuslovlennykh uvelicheniem kolichestva atomnykh ehlektrostantsij. Rassmatrivayutsya osnovnye faktory, kotorye dolrsny byt' uchteny v budushchem pri planirovanii ehlektrostantsij s uchetom takzhe grafikov stroitel'stva i ispytaniya. Opredelennyj upor sdelan na problemu protivoavarijnoj obolochki s uchetom takzhe spetsificheskikh uslovij Italii v otnoshenii nekotorykh aspektov ehtoj problemy; v rezul'tate udobnogo razmeshcheniya

  20. Studies on the Influence of Tritium Radiation on Anaerobic Bacteria from the Bovine Rumen; Influence de l'Irradiation par le Tritium sur les Bacteries Anaerobies du Rumen des Bovins; 0418 0441 0414 ; Estudios sobre los Efectos de las Radiaciones del Tritio en las Bacterias Anaerobias de la Panza de los Bovinos

    Energy Technology Data Exchange (ETDEWEB)

    Brueggemann, J.; Giesecke, D. [Institute of Physiology and Animal Nutrition, University of Munich, Munich, Federal Republic of Germany (Germany)

    1962-02-15

    logarifmicheskim porjadkom snizhenija. Predpolagaetsja, chto vtorichnye produkty obluchenija, v osobennosti N{sub 2}O{sub 2} obuslavlivajut dejstvie T{sub 2}O na te mikroorganizmy, v kotoryh net jenzimov. Dlja takogo obosnovanija sleduet poluchit' podtverzhdajushhie rezul'taty. (author)

  1. Industrial Ultrasonic Inspection of Stainless-Steel Claddings for the EL4 Reactor; Controle Industriel par Ultrasons des Gaines en Acier Inoxydable du Reacteur EL4; Promyshlennyj kontrol' obolochechnykh trub iz nerzhaveyushchej stali reaktora dlya EL4 s pomoshch'yu ul'trazvukovogo metoda; Metodos Ultrasonicos para Control Industrial de las Vainas de Acero Inoxidable del Reactor EL4

    Energy Technology Data Exchange (ETDEWEB)

    Prot, A. C.; Foulquoer, H. E.; Peyrot, J. P. [Centre d' Etudes Nucleaires de Saclay (France)

    1965-09-15

    'nosti reaktorov. Podtverzhdaetsja, chto vybor metoda, kotoryj sleduet primenjat' i razrabatyvat', javljaetsja trudnym. Privodjatsja osnovnye momenty. Posle togo, kak v rezul'tate laboratornyh rabot sdelan vybor, voznikajut dve novye problemy: D) vnedrenie v promyshlennost' neobhodimost' ucheta dopustimogo kachestva v opredelennyj moment metodami izgotovlenija v svjazi s ustanovlennymi bolee ili menee proizvol'nym obrazom normami dlja priema. Jeto, v dejstvitel'nosti, obuslavlivaetsja neobhodimost'ju v statisticheskom issledovanii komplektov trub razlichnogo izgotovlenija i ih klassifikacii po otnosheniju k bolee ili menee strogim normam. Vidno, chto kolichestvo podlezhashhih kontrolju trub znachitel'no prevyshaet pervonachal'no namechennoe. Jeto vedet k izucheniju avtomaticheskogo kontrol'nogo mehanizma, sposobnogo udovletvorit' odnovremenno i trebovanijam tempa, i trebovanijam, vytekajushhim iz vybrannogo tipa kontrolja: poslednie obychno svodjatsja k mehanicheskomu kontrolju i nuzhdajutsja v osobenno tshhatel'no razrabotannoj konstrukcii. Sovokupnost' jetih soobrazhenij privela k razrabotke ustrojstva, temp raboty kotorogo uzhe sejchas mozhet bez truda pokryt' potrebnosti vsego cikla proizvodstva toplivnyh jelementov. Vozmozhnosti jetogo ustrojstva tesno svjazany s harakteristikami podobrannogo oborudovanija navedenija i kontrolja, v osobennosti so svojstvami jelektroniki priborov kontrolja po ul'trazvuku i so svojstvami ispol'zuemyh preobrazovatelej. K tomu zhe iz jetogo issledovanija javstvuet, chto standartnoe oborudovanie daleko ne sootvetstvuet probleme i chto uzhe sejchas sleduet predusmotret' osoboe ustrojstvo dlja dannogo tipa kontrolja. (author)

  2. Desirable New Geologic Research in Support of Radioactive Waste Disposal as Indicated by Hanford Experience; Nouvelles Recherches Geologiques Souhaitables au Sujet de l'Elimination des Dechets Radioactifs, Selon les Indications Fournies par l'Experience de Hanford; 041f 0420 041e 0412 0415 0414 ; Nuevas Investigaciones Geologicas que Convendria Hacer para Facilitar la Evacuacion de Desechos Radiactivos Siguiendo las Indicaciones Proporcionadas por las Experiencias Efectuadas en Hanford

    Energy Technology Data Exchange (ETDEWEB)

    Brown, Randall E. [Hanford Laboratories, Hanford Atomic Products Operation, General Electric Company, Richland, WA (United States)

    1960-07-01

    estudios de los geologos, hidrologos, geoquimicos y matematicos ha contribuido mucho a asegurar la evacuacion sin riesgos de los desechos en el subsuelo de Hanford. No obstante, todavia queda mucho camino por recorrer. (author) [Russian] Ves process udalenija radioaktivnyh othodov zavisit ot geologicheskoj struktury okruzhajushhej sredy. No udalenie v jetu sredu ne javljaetsja okonchatel'nym, poskol'ku nikakoj material ne javljaetsja sovershenno nepronicaemym, nenas'ncajushhimsja ili nekorrozijnym s tochki zrenija geologicheskogo vremeni. Opyt v Hjenforde po udaleniju radioaktivnyh othodov podcherkivaet neobhodimost' sopostavlenija geologicheskih osobennostej, sushhestvujushhih v rajone udalenija otohodov i v blizhajshem rajone, gde vozmozhno obluchenie naselenija. Problemy, voznikshie v Hjenforde v svjazi s udaleniem radioaktivnyh othodov, vkljuchajut: 1. kolichestvennuju netochnost' geologii, 2. nedostatok izotopnyh, gomogennyh geologicheskih struktur, 3. opredelenie kolichestvennogo znachenija otklonenija geologicheskih i gidrologicheskih osobennostej ot normal'nogo polozhenija i 4. opredelenie i izmerenie parametrov, predstavljajushhih interes. Privodjatsja primery dlja illjustracii vysheukazannyh sluchaev. Bylo otryto 557 kolodcev obshhej glubinoj 33000 metrov, no dannye, poluchennye v rezul'tate jetoj bol'shoj raboty, nedostatochno tochny. Cennost' standartnyh akvifer- nyh ispytanij v rabochih uslovijah ogranichena, poskol'ku neobhodimye vvodnye dannye slishkom obobshhajutsja. Izuchenie ionnogo obmena daet kolichestvennye znachenija, kotorye predstavljajut neposredstvennyj interes i pomogajut istolkovat' geologicheskie osobennosti. Gidrologicheskie issledovanija, uvjazannye s rabotoj po himii pochvy i imejushhimisja geologicheskimi dannymi, okazyvajut pomoshh' v ob'jasnenii processa dvizhenija gruntovyh vod. Udalenie radioaktivnyh othodov v grunt ne javljaetsja ni panaceej, ni chem- to inym, chego sleduet bojat'sja. Obobshhenie dannyh, poluchennyh v rezul

  3. The Containment of Radioactive Wastes in Deep Geologic Formations; L'Elimination des Dechets Radioactifs dans les Formations Geologiques Profondes; 0423 0414 0414 ; Evacuacion de Desechos Radiactivos en Formaciones Geologicas Profundas

    Energy Technology Data Exchange (ETDEWEB)

    Kaufman, W. J. [University of California, Berkeley (United States)

    1960-07-01

    , chto v takom sluchae glubokie geologicheskie obrazovanija mogut javit'sja mestami dlja bezopasnogo i renta- bil'nogo zahoronenija othodov. V obrazovanijah peschanika mozhno hranit' v bol'shom kolichestve othody s vysokoj aktivnost'ju. Kak obshhee svojstvo zhidkostej, vsegda stremjashhihsja zapolnit' pustoty, tak i osobennosti ionnogo obmena v othodah blagoprijatstvujut shirokomu ispol'zovaniju takih emkostej dlja hranenija othodov. Sistema udalenija othodov, v kotoroj ispol'zujutsja glubokie geologicheskie obrazovanija, kak schitajut, sostoit iz sistemy vpusknyh skvazhin dlja vvedenija othodov i razgruzochnyh skvazhin, kotorye sluzhat dlja kontrolja i regulirovanija potoka othodov s cel'ju obespechit' naibolee racional'noe ispol'zovanie emkosti. Nuzhnye svedenija dlja proektirovki takoj sistemy vkljuchajut dannye po dispersionnym svojstvam, obrazovaniju dannoj geologicheskoj formacii, osobennostjam ionnogo obmena sredy, a takzhe po himicheskim i radiohimicheskim svojstvam othodov. V tehnicheskoj polevoj stancii universiteta v techenie dvuh let dejstvuet opytnaja dvuhskvazhennaja vpusknaja sistema. (author)

  4. Environmental Implications of Radioactive Waste Disposal as Related to Stream Environments; Incidences du Milieu sur l'Elimination des Dechets Radioactifs dans le Voisinage des Cours d'Eau; 0412 041b 0418 042f 0414 ; Efectos de la Evacuacion de Desechos Radiactivos en las Corrientes Fluviales

    Energy Technology Data Exchange (ETDEWEB)

    Straub, Conrad P.; Goldin, Abraham S.; Friend, Albert G.; Taft, Robert A. [Sanitary Engineering Center, US Department of Health, Education and Welfare, Cincinnati, OH (United States)

    1960-07-01

    'zovat'sja dlja mnozhestva celej, naprimer, ih vody ispol'zujutsja dlja pit'ja, dlja promyshlennyh celej, dlja provedenija otdyha, rybolovstva, irrigacii i navigacii, dejstvie sbrosa othodov na kazhduju iz perechislennyh celej dolzhno byt' tshhatel'no izucheno. Nastojashhij kriterij ne obespechivaet polnyh dannyh dlja opredelenija dopustimogo, urovnja radioaktivnyh veshhestv do teh por, poka ne budet imet'sja informacija o kolichestvah special'nyh radioaktivnyh izotopov, uzhe imejushhihsja v rekah, i kakovo polozhenie s temi zhe samymi izotopami v uslovijah rechnogo techenija. Dopustimoe prisutstvie radioizotopov dolzhno izmenjat'sja v sootvetstvii s vysheukazannoj informaciej i, v osobennosti, s uchetom, kak ispol'zuetsja voda vniz po techeniju rek. Sleduet ustanovit', gde mozhno razreshit' na dannom techenii reki neskol'ko istochnikov udalenija othodov i raspredelenie maksimal'nogo kolichestva special'nyh radioaktivnyh izotopov v. sootvetstvii s toj opasnost'ju, kotoraja mozhet ugrozhat' naseleniju ot pol'zovanija vodoj rek vdol' ego techenija, uchityvaja vse istochniki popadanija othodov. Dano opisanie neskol'kih predlozhennyh podhodov k razresheniju problemy, kak postupat' s othodami pri sbrasyvanii ih vniz po techeniju rek i rassmatrivajutsja nekotorye trudnye momenty, svjazannye s primeneniem kazhdogo podhoda k jetoj probleme. (author)

  5. The Combined Use of Autoradiographic and Electron Microscopic Techniques for Studies on Ultra-Thin Sections of Tritium-Labelled Cells of the Intestinal Epithelium; Emploi Combine de l'Autoradiographie et du Microscope Electronique pour L'Etude de Coupes Ultra-Fines de Cellules Tritiees de l'Epithelium Intestinal; 0421 043e 0432 043c 0435 0414 ; Empleo Combinado de Tecnicas de Autorradiografia y de MicroscopiA Electronica para Estudiar Cortes Ultrafinos de Celulas Tritiadas del Epitelio Intestinal

    Energy Technology Data Exchange (ETDEWEB)

    Hampton, J. C. [Division of Experimental Biology, Baylor University College of Medicine, TX (United States); Quastler, H. [Brookhaven National Laboratory, Upton, Long Island, NY (United States)

    1962-02-15

    tomado las micrografias electronicas adecuadas y aplicar una capa de emulsion suficientemente gruesa como para obtener una autorradiografia, pero, al mismo tiempo, bastante delgada como para permitir un nuevo examen de la muestra en el microscopio electronico y obtener micrografias electronicas de las autorradiografias de las celulas examinadas previamente. La emulsion autorradiografica se aplico en la siguiente forma: se formo primeramente una pelicula delgada sumergiendo un pequeno ojal de alambre en una emulsion liquida y trasladando la pelicula mediante el recurso de pasar el ojal sobre la muestra montado sobre un soporte, fijado a su vez en el extremo de una clavija de material plastico. El control adecuado se puede lograr tomando una seccion de media miera de espesor despues de cada operacion de corte, montandola sobre una placa de vidrio y aplicando luego las tecnicas autorradiograficas usuales. Debido a la fragilidad de los cortes ultrafinos, la proporcion de autorradiografias satisfactorias es bastante reducida. A pesar de este inconveniente, se espera que una vez perfeccionada la tecnica y adquirido experiencia en su manejo, este metodo permitira comprender mejor procesos que se verifican en las celulas vitales. (author) [Russian] Osvoennaja v nastojashhee vremja vozmozhnost' dostizhenija vysokoj razreshajushhej sposobnosti v izuchenii kletochnyh srezov pri pomoshhi jelektronnogo mikro- skopa otkryvaet puti k nabljudeniju za nekotorymi mezhkletochnymi javlenjami, vedushhimi k sintezu proteinov. Osobennosti pogloshhenija tritirovannogo timi- dina dezoksiribonukleinovoj kislotoj obrazujut sistemu, otkryvajushhuju vozmozhnost' tochnogo nabljudenija za vremenem ee proniknovenija i mestom ee sos- redotochenija v kletke. V dokladyvaemoj zdes' rabote pokazyvaetsja, chto sverh- tonkie srezy mechenyh kletochek mozhno izuchit' pri pomoshhi jelektronnogo mikroskopa, a zatem, posle poluchenija nuzhnoj mikrografii, vynut' obrazec, pokryt' ego plenkoj jemul'sii dostatochno

  6. Case Study in Internal Audit of Nuclear Material; Etude d'un Systeme de Verification Comptable Interne des Matieres Nucleaires; Izuchenie primera organizatsii vnutrennego ucheta yadernykh materialov na predpriyatii; Estudio de la Fiscalizacion Interna de los Materiales Nucleares

    Energy Technology Data Exchange (ETDEWEB)

    Kops, S. [United States Atomic Energy Commission, Argonne, IL (United States)

    1966-02-15

    diversos grupos dentro de la organizacion; se discute, ademas, la cuestion de la distribucion de las informaciones. (author) [Russian] Kratko obsuzhdajutsja obshhaja potrebnost' v organizacii vnutrennej proverki nalichija jadernyh materialov na predprijatii i osnovnye principy administrativno- hozjajst vennogou ch eta. Pri opredelenii potrebnosti v organizacii obychnogo vnutrennego ucheta glavnymi faktorami javljajutsja: razmer predprijatija, ego slozhnost' i stepen' centrali- zacii ili decentralizacii. Obsuzhdajutsja i protivopostavljajutsja vnutrennemu uchetu obych- nogo tipa bolee special'nye trebovanija i osobennosti vnutrennego ucheta, prisushhie predpri- jatiju, raspolagajushhemu radioaktivnymi istochnikami ili special'nymi rasshhepljajushhimisja materialami (jadernymi materialami). Vvidu vysokoj denezhnoj stoimosti i strategicheskoj vazhnosti materialov dokazyvaetsja neobhodimost' organizacii osoboj vnutrennej proverki. Podrobno obsuzhdaetsja planirovanie organizacii vnutrennej proverki na proizvodst- vennom predprijatii. Pomimo vedenija uchetnyh dokumentov i fakticheskoj proverki nalichija materialov, podlezhashhih proverke i vyjavleniju, ob{sup j}asnjajutsja soobrazhenija, lezhashhie v osno- ve ustanovlenija srokov obsledovanij. Obsuzhdajutsja takzhe kvalifikacii i kategorii specia- listov, kotorye dolzhny byt' privlecheny k vypolneniju funkcij vnutrennej proverki. Obsuzhdaetsja konkretnyj statisticheskij plan vybora ob{sup e}ktov dlja ispytanij i prob. Podrobno opisyvaetsja primenenie takih planov k fakticheskomu provedeniju vnutrennej proverki. Obsuzhdajutsja vozmozhnye othody ot obshheprinjatyh norm i vozmozhnye podhody k resheniju problemy. Hotja na mnogih promyshlennyh predprijatijah obychnogo tipa i sushhest- vujut razlichnye metody proverki nalichija materialov bezfizicheskogo ih obsledovanija, dokazyvaetsja neobhodimost' fizicheskogo obsledovanija nalichija jadernyh materialov. Opisyvajutsja razlichnye sposoby predstavlenija otchetovorezul'tatah vnutrennej

  7. Recent development in clusters of rare earths and actinides. Chemistry and materials

    International Nuclear Information System (INIS)

    Zheng, Zhiping

    2017-01-01

    This book contains the following eight contributions: 1. Lanthanide Hydroxide Cluster Complexes via Ligand-Controlled Hydrolysis of the Lanthanide Ions (Zhonghao Zhang, Yanan Zhang, and Zhiping Zheng); 2. Synthesis and Structures of Lanthanide-Transition Metal Clusters (Xiu-Ying Zheng, Xiang-Jian Kong, and La-Sheng Long); 3. Hydrothermal Synthesis of Lanthanide and Lanthanide-Transition-Metal Cluster Organic Frameworks via Synergistic Coordination Strategy (Jian-Wen Cheng and Guo-Yu Yang); 4. Oxo Clusters of 5f Elements (Sarah Hickam and Peter C.); 5. Construction and Luminescence Properties of 4f and d-4f Clusters with Salen-Type Schiff Base Ligands (Xiaoping Yang, Shiqing Wang, Chengri Wang, Shaoming Huang, and Richard A.); 6. 4f-Clusters for Cryogenic Magnetic Cooling (Yan-Cong Chen, Jun-Liang Liu, and Ming-Liang Tong); 7. Lanthanide Clusters Toward Single-Molecule Magnets (Tian Han, You-Song Ding, and Yan-Zhen Zheng); 8. Molecular Rare Earth Hydride Clusters (Takanori Shima and Zhaomin Hou).

  8. Analysis of the crystal lattice instability for cage–cluster systems using the superatom model

    Energy Technology Data Exchange (ETDEWEB)

    Serebrennikov, D. A., E-mail: dserebrennikov@innopark.kantiana.ru, E-mail: dimafania@mail.ru; Clementyev, E. S. [I. Kant Baltic Federal University, “Functional Nanomaterials” Scientific–Educational Center (Russian Federation); Alekseev, P. A. [“Kurchatov Institute” National Research Center (Russian Federation)

    2016-09-15

    We have investigated the lattice dynamics for a number of rare-earth hexaborides based on the superatom model within which the boron octahedron is substituted by one superatom with a mass equal to the mass of six boron atoms. Phenomenological models have been constructed for the acoustic and lowenergy optical phonon modes in RB{sub 6} (R = La, Gd, Tb, Dy) compounds. Using DyB{sub 6} as an example, we have studied the anomalous softening of longitudinal acoustic phonons in several crystallographic directions, an effect that is also typical of GdB{sub 6} and TbB{sub 6}. The softening of the acoustic branches is shown to be achieved through the introduction of negative interatomic force constants between rare-earth ions. We discuss the structural instability of hexaborides based on 4f elements, the role of valence instability in the lattice dynamics, and the influence of the number of f electrons on the degree of softening of phonon modes.

  9. Solid state physics and actinide spectroscopy with ThBr4 and ThCl4

    International Nuclear Information System (INIS)

    Genet, M.

    1984-01-01

    From the solid state physics to the optical spectroscopy of 5 f elements, we have described in details how ThBr 4 and ThCl 4 are acting an important role in the applied and basic research field. The possible applications are based on the scintillation properties of these crystals while the fundamental aspect is related to their special incommensurate structure which modulates the host properties of these matrices at low temperature. This very small perturbation of bromine atom positions have optical consequences on the absorption and emission of the actinide studied ions which are interpreted in function of the modulated structure parameters determined by inelastic and elastic neutron scattering and by Raman spectroscopy. The structural model proposed shows, for the first time, how the optical properties of the investigated ion are influenced by the sinusoidal displacements of the bromine atoms, leading to an energy continuum in the absorption and reducing the site symmetry from Dsub(2d) to a multisite of D 2 symmetry

  10. Insertion of an SVA element, a nonautonomous retrotransposon, in PMS2 intron 7 as a novel cause of Lynch syndrome.

    Science.gov (United States)

    van der Klift, Heleen M; Tops, Carli M; Hes, Frederik J; Devilee, Peter; Wijnen, Juul T

    2012-07-01

    Heterozygous germline mutations in the mismatch repair gene PMS2 predispose carriers for Lynch syndrome, an autosomal dominant predisposition to cancer. Here, we present a LINE-1-mediated retrotranspositional insertion in PMS2 as a novel mutation type for Lynch syndrome. This insertion, detected with Southern blot analysis in the genomic DNA of the patient, is characterized as a 2.2 kb long 5' truncated SVA_F element. The insertion is not detectable by current diagnostic testing limited to MLPA and direct Sanger sequencing on genomic DNA. The molecular nature of this insertion could only be resolved in RNA from cultured lymphocytes in which nonsense-mediated RNA decay was inhibited. Our report illustrates the technical problems encountered in the detection of this mutation type. Especially large heterozygous insertions will remain unnoticed because of preferential amplification of the smaller wild-type allele in genomic DNA, and are probably underreported in the mutation spectra of autosomal dominant disorders. © 2012 Wiley Periodicals, Inc.

  11. Citric complexes of trivalent cerium and berkelium

    International Nuclear Information System (INIS)

    Boulhassa, S.

    1977-01-01

    The extraction by thenoyltrifluoroacetone (TTA) in benzene of trivalent cerium, berkelium and californium, at the indicator scale, hydrolysis and complexation by citric acid of these cations are studied. The radionuclides used were 144 Ce, 249 Bk and 249 Cf respectively γ, β and α emitters. The solvent extraction technique of the elements by TTA in benzene from a perchloric medium at the ionic stength 0.1 was employed. The distribution coefficients D were measured by the γ, β or α radiometry. Cerium and berkelium, which have a comparable redox behavior, show in solution a relatively stable valency IV. Therefore the study by solvent extraction of their trivalent form required the standing up of complete reducing conditions of these elements and their stabilization in solution at the valency III. The thermodynamic data obtained for berkelium and californium contribute to understand the chemistry of these elements and permit to complete the third 'tetrad branch' of 5f elements from Cm 3+ to Es 3+ . This tetrad effect is a manifestation of thermodynamic consequence of the 'nephelauxetic effect'. As for Ce(III), the data confirm the pronounced acid property and may be show no neglected ligand effect for f 1 configuration [fr

  12. Group theory for magnetic structure determination: Recent developments and quadrupolar ordering analysis

    Energy Technology Data Exchange (ETDEWEB)

    Sikora, W. [Faculty of Physics and Applied Computer Science, AGH-University of Science and Technology, al.Mickiewicza 30, 30-059 Cracow (Poland)]. E-mail: sikora@novell.ftj.agh.edu.pl; Pytlik, L. [Faculty of Physics and Applied Computer Science, AGH-University of Science and Technology, al.Mickiewicza 30, 30-059 Cracow (Poland); Bialas, F. [Nowy Sacz School of Busines-National Louis University, 33-300 Nowy Sacz (Poland); Malinowski, J. [Faculty of Physics and Applied Computer Science, AGH-University of Science and Technology, al.Mickiewicza 30, 30-059 Cracow (Poland)

    2007-09-13

    In this paper, the recent developments in practical applications of symmetry analysis are described. The theoretical basis shortly described in Section 1 has been implemented in several computer applications, one of which is the program 'MODY-win', developed by the authors of the paper. The program calculates the so-called basis vectors of irreducible representations of a given symmetry group, which can be used for calculation of possible ordering modes. Its practical application is demonstrated on some examples, presenting the recent aspects of using the symmetry analysis to description of various types of ordering encountered in solids. The scalar-type ordering (occupation probability) is discussed shortly for occupation of interstitial sites by hydrogen atoms in inter-metallic compounds. The description of vector ordering is demonstrated on the magnetic ordering modes, with special attention focused on the freedom that is left in the structure after imposing all the symmetry constraints. In practice, the final ordering mode usually contains some free parameters that cannot be determined from the symmetry itself. The last application presented in the paper is the description of quadrupolar ordering, recently found in some compounds of 4f (5f) elements. For the latter case, an additional advantage is demonstrated by calculation of possible displacements of neighboring atoms after the establishment of non-zero quadrupolar order parameter on the central atom.

  13. Samarium Polystibides Derived from Highly Activated Nanoscale Antimony.

    Science.gov (United States)

    Schoo, Christoph; Bestgen, Sebastian; Egeberg, Alexander; Klementyeva, Svetlana; Feldmann, Claus; Konchenko, Sergey N; Roesky, Peter W

    2018-05-14

    Zintl ions in molecular compounds are of fundamental interest for basic research and application. Two reactive antimony sources are presented that allow direct access to molecular polystibide compounds. These are Sb amalgam (Sb/Hg) and ultrasmall Sb 0 nanoparticles (d=6.6±0.8 nm), which were used independently as precursors for the synthesis of the largest f-element polystibide, [(Cp* 2 Sm) 4 Sb 8 ]. Whereas the reaction of the nanoparticles with [Cp* 2 Sm] directly led to [(Cp* 2 Sm) 4 Sb 8 ], Sm/Sb/Hg intermediates were isolated when using Sb/Hg as the precursor. These Sm/Sb/Hg intermediates [{(Cp* 2 Sm) 2 Sb} 2 (μ-Hg)] and [{(Cp* 2 Sm) 3 (μ 4 ,η 1:2:2:2 -Sb 4 )} 2 Hg] were synthetically trapped and structurally characterized, giving insight in the formation mechanism of polystibide compounds. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Spectroscopic studies of the transplutonium elements

    International Nuclear Information System (INIS)

    Carnall, W.T.; Conway, J.G.

    1983-01-01

    The challenging opportunity to develop insights into both atomic structure and the effects of bonding in compounds makes the study of actinide spectroscopy a particularly fruitful and exciting area of scientific endeavor. It is also the interpretation of f-element spectra that has stimulated the development of the most sophisticated theoretical modeling attempted for any elements in the periodic table. The unique nature of the spectra and the wealth of fine detail revealed make possible sensitive tests of both physical models and the results of Hartree-Fock type ab initio calculations. This paper focuses on the unique character of heavy actinide spectroscopy. It discusses how it differs from that of the lighter member of the series and what are the special properties that are manifested. Following the introduction, the paper covers the following: (1) the role of systematic studies and the relationships of heavy-actinide spectroscopy to ongoing spectroscopic investigations of the lighter members of the series; (2) atomic (free-ion) spectra which covers the present status of spectroscopic studies with transplutonium elements, and future needs and directions in atomic spectroscopy; (3) the spectra of actinide compounds which covers the present status and future directions of spectroscopic studies with compounds of the transplutonium elements; and other spectroscopies. 1 figure, 2 tables

  15. Handbook on the physics and chemistry of the actinides. V. 3

    International Nuclear Information System (INIS)

    Freeman, A.J.; Keller, C.

    1985-01-01

    It is the purpose of the Handbook to describe in detail the present understanding of the actinides by means of comprehensive, critical, broad and up to date reviews covering both physics and chemistry of these exotic elements. Volume 3 is the first of two volumes to cover the more chemical, physico-chemical, structural and environmental aspects of the actinide elements. Leading scientists from Europe, USA and P.R. China present critical reviews on important aspects of the behaviour of this radioactive group of elements. In contrast to most other elements radioactivity has, to a degree, a profound influence on the chemical behaviour of the actinides. The unusual behaviour of the 5f-elements - delocalization of the electrons for the light actinides versus localization for the heavier ones - makes them an outstanding tool for the scientist, which can be seen by the variety of oxidation states ranging from +1 to +7. Special laboratory techniques must be developed to deal with the problem of the transcurium elements only being available in small amounts (nanograms to micrograms) or only in the tracer scale. Special emphasis is also placed on the fate of actinides released in the environment, e.g. their reaction to carbonate and organic complexing agents in aquatic systems. In contrast to volumes 1 and 2 which deal mainly with the less radioactive actinides, this volume and the forthcoming volume 4 cover all actinides, in particular those which can be prepared in weighable quantities (up to fermium, element 100). refs.; figs.; tabs

  16. Numerical Simulation of Magnetic Field Effect on Cryocooler Regenerators: Temperature Distribution

    Directory of Open Access Journals (Sweden)

    Rajendra Kumar

    2017-01-01

    Full Text Available Regenerative types of cryogenic refrigerators (or cryocoolers employ magnetic intermetallic compounds of 3d and 4f elements to work well below 10 K. This paper presents the analysis of temperature distribution in regenerators of such cryocoolers under the influence of magnetic fields of 1 T, 3 T, and 4.3 T. Commercial code of finite element analysis (FEA package, ANSYS (APDL 14.5, is used to investigate the temperature distribution under above-mentioned fields. Er3Ni is selected as regenerator material and the criteria for its selection are discussed in detail. The cold end temperature is varied from 4.2 K to 10 K and hot end temperature is fixed at 20 K. The values obtained from FEA clearly show that the ineffectiveness of Er3Ni is at 8 K and 10 K at 3 T and 4.3 T.

  17. The radiochemistry, a multi-disciplinary science for the 21. century

    International Nuclear Information System (INIS)

    David, F.

    1999-04-01

    The basic radiochemistry occupies an avant-garde place in inorganic chemistry. It covers a very vast multi-disciplinary field, important for about 40% of the periodic table. It allows understanding better the periodic classification and it is directly connected with various disciplines: metal physical chemistry, solid compounds, solutions, thermodynamics, etc. The applications are also multi-disciplinary, mainly in nuclear industries but also in analysis, geology, biochemistry, medicine, archaeology, astrophysics. This report is a short variant of the document delivered in 1988 for CNRS. It treats neither all the aspects of radiochemistry or the priorities in this field but points out the main directions of this discipline and the fields of research which should be studied in more details. The content is as follows: - Introduction; - I. Definition and radiochemistry's domain of action; - II. The actinides constitute a particularly interesting series of the periodic table; - III. Research on actinides to be developed; III.1 Metals; III.2 Solid compounds; III.3 Gas compounds; III.4 Chemistry in solution (water ions, oxidation degrees, thermodynamic properties, chemical species in solution, non-aqueous media, chemical kinetics, chemistry at the atom scale); IV. Other radioelements; IV.1 The trans-actinide elements; IV.2 The long-lived fission products; V. Radiochemical methods; VI. Study of the 4f and 5f elements is interesting from the point of view of physico-chemical theories; VII. The heavy elements are implied in the nuclear power production; VII.1 Reprocessing the nuclear fuels; VII.2 Waste management; VIII. Conclusions

  18. Reduction of a cerium(III) siloxide complex to afford a quadruple-decker arene-bridged cerium(II) sandwich

    Energy Technology Data Exchange (ETDEWEB)

    Kelly, Rory P.; Scopelliti, Rosario; Mazzanti, Marinella [Institut des Sciences et Ingenierie Chimiques, Ecole Polytechnique Federale de Lausanne (EPFL), Lausanne (Switzerland); Maron, Laurent [Laboratoire de Physique et Chimie des Nano-objets, Institut National des Sciences Appliquees, Toulouse (France)

    2017-12-04

    Organometallic multi-decker sandwich complexes containing f-elements remain rare, despite their attractive magnetic and electronic properties. The reduction of the Ce{sup III} siloxide complex, [KCeL{sub 4}] (1; L=OSi(OtBu){sub 3}), with excess potassium in a THF/toluene mixture afforded a quadruple-decker arene-bridged complex, [K(2.2.2-crypt)]{sub 2}[{(KL_3Ce)(μ-η"6:η"6-C_7H_8)}{sub 2}Ce] (3). The structure of 3 features a [Ce(C{sub 7}H{sub 8}){sub 2}] sandwich capped by [KL{sub 3}Ce] moieties with a linear arrangement of the Ce ions. Structural parameters, UV/Vis/NIR data, and DFT studies indicate the presence of Ce{sup II} ions involved in δ bonding between the Ce cations and toluene dianions. Complex 3 is a rare lanthanide multi-decker complex and the first containing non-classical divalent lanthanide ions. Moreover, oxidation of 1 by AgOTf (OTf=O{sub 3}SCF{sub 3}) yielded the Ce{sup IV} complex, [CeL{sub 4}] (2), showing that siloxide ligands can stabilize Ce in three oxidation states. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  19. E1A-dependent trans-activation of the human MYC promoter is mediated by the E2F factor

    International Nuclear Information System (INIS)

    Hiebert, S.W.; Lipp, M.; Nevins, J.R.

    1989-01-01

    E2F is a cellular transcription factor that binds to two sites in the adenovirus E2 promoter. Previous experiments have implicated E2F in the E1A-dependent transactivation of the E2 gene since levels of active E2F increase markedly during adenovirus infection in parallel with the increase in E2 transcription, and an E2F binding site can confer E1A inducibility to a heterologous promoter. Here the authors show that E2F binds to two sequence elements within the P2 promoter of the human MYC gene which are within a region that is critical for promoter activity. The MYC promoter can be trans-activated in an E1A-dependent manner and site-directed mutagenesis demonstrates that these E2F elements are essential for trans-activation. Finally, they also find that adenovirus infection of quiescent cells results in a stimulation of the endogenous MYC gene. They conclude that the activation of the E2F factor, which is likely responsible for the activation of viral E2 transcription, is also responsible for the E1A-dependent induction of MYC transcription

  20. Recent development in clusters of rare earths and actinides. Chemistry and materials

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Zhiping (ed.) [Arizona Univ., Tucson, AZ (United States). Dept. of Chemistry and Biochemistry

    2017-02-01

    This book contains the following eight contributions: 1. Lanthanide Hydroxide Cluster Complexes via Ligand-Controlled Hydrolysis of the Lanthanide Ions (Zhonghao Zhang, Yanan Zhang, and Zhiping Zheng); 2. Synthesis and Structures of Lanthanide-Transition Metal Clusters (Xiu-Ying Zheng, Xiang-Jian Kong, and La-Sheng Long); 3. Hydrothermal Synthesis of Lanthanide and Lanthanide-Transition-Metal Cluster Organic Frameworks via Synergistic Coordination Strategy (Jian-Wen Cheng and Guo-Yu Yang); 4. Oxo Clusters of 5f Elements (Sarah Hickam and Peter C.); 5. Construction and Luminescence Properties of 4f and d-4f Clusters with Salen-Type Schiff Base Ligands (Xiaoping Yang, Shiqing Wang, Chengri Wang, Shaoming Huang, and Richard A.); 6. 4f-Clusters for Cryogenic Magnetic Cooling (Yan-Cong Chen, Jun-Liang Liu, and Ming-Liang Tong); 7. Lanthanide Clusters Toward Single-Molecule Magnets (Tian Han, You-Song Ding, and Yan-Zhen Zheng); 8. Molecular Rare Earth Hydride Clusters (Takanori Shima and Zhaomin Hou).

  1. Organometallic neptunium(III) complexes

    Science.gov (United States)

    Dutkiewicz, Michał S.; Farnaby, Joy H.; Apostolidis, Christos; Colineau, Eric; Walter, Olaf; Magnani, Nicola; Gardiner, Michael G.; Love, Jason B.; Kaltsoyannis, Nikolas; Caciuffo, Roberto; Arnold, Polly L.

    2016-08-01

    Studies of transuranic organometallic complexes provide a particularly valuable insight into covalent contributions to the metal-ligand bonding, in which the subtle differences between the transuranium actinide ions and their lighter lanthanide counterparts are of fundamental importance for the effective remediation of nuclear waste. Unlike the organometallic chemistry of uranium, which has focused strongly on UIII and has seen some spectacular advances, that of the transuranics is significantly technically more challenging and has remained dormant. In the case of neptunium, it is limited mainly to NpIV. Here we report the synthesis of three new NpIII organometallic compounds and the characterization of their molecular and electronic structures. These studies suggest that NpIII complexes could act as single-molecule magnets, and that the lower oxidation state of NpII is chemically accessible. In comparison with lanthanide analogues, significant d- and f-electron contributions to key NpIII orbitals are observed, which shows that fundamental neptunium organometallic chemistry can provide new insights into the behaviour of f-elements.

  2. Polymetallic lanthanide (III) complexes for the design of new luminescent materials

    International Nuclear Information System (INIS)

    Marchal, C.

    2008-09-01

    The incorporation of f elements in highly organized polymetallic complexes is of great interest in supramolecular chemistry and allows the combination of their nano-scopic size with the magnetic or optical properties of the metal ions. However due to the difficulty in controlling the coordination environment of these ions, the assembly of lanthanide-based polynuclear architectures has lagged behind that of other systems. These factors make the rational design for the construction of supramolecular lanthanide complexes quite challenging. In order to better understand the factors determining the assembly of lanthanide-based polymetallic arrays, we designed two different types of organic ligands, which favor, in one case, formation of infinite polymetallic complexes (coordination polymers), and in the case the assembly of discrete polymetallic architectures. Thus, we show that the use of flexible and multi-dentate picolinate-derivative ligands enables the formation of infinite and luminescent infinite frameworks which display very interesting luminescent properties. Geometry of the ligand has a great influence on the final network architecture. Particularly, implementation of four picolinate units within a tetrapodal ligand results in the controlled assembly of 1-D coordination polymers. Conversely to favor the controlled assembly of discrete polymetallic arrays we use dissymmetric ligands which displays low denticity. Complexation studies of a tridentate 8- hydroxyquinoline-derivative ligand as well as a tetradentate ligand possessing an oxazoline ring are presented. (author)

  3. Organometallic neptunium(III) complexes.

    Science.gov (United States)

    Dutkiewicz, Michał S; Farnaby, Joy H; Apostolidis, Christos; Colineau, Eric; Walter, Olaf; Magnani, Nicola; Gardiner, Michael G; Love, Jason B; Kaltsoyannis, Nikolas; Caciuffo, Roberto; Arnold, Polly L

    2016-08-01

    Studies of transuranic organometallic complexes provide a particularly valuable insight into covalent contributions to the metal-ligand bonding, in which the subtle differences between the transuranium actinide ions and their lighter lanthanide counterparts are of fundamental importance for the effective remediation of nuclear waste. Unlike the organometallic chemistry of uranium, which has focused strongly on U(III) and has seen some spectacular advances, that of the transuranics is significantly technically more challenging and has remained dormant. In the case of neptunium, it is limited mainly to Np(IV). Here we report the synthesis of three new Np(III) organometallic compounds and the characterization of their molecular and electronic structures. These studies suggest that Np(III) complexes could act as single-molecule magnets, and that the lower oxidation state of Np(II) is chemically accessible. In comparison with lanthanide analogues, significant d- and f-electron contributions to key Np(III) orbitals are observed, which shows that fundamental neptunium organometallic chemistry can provide new insights into the behaviour of f-elements.

  4. Siderocalin-mediated recognition, sensitization, and cellular uptake of actinides.

    Science.gov (United States)

    Allred, Benjamin E; Rupert, Peter B; Gauny, Stacey S; An, Dahlia D; Ralston, Corie Y; Sturzbecher-Hoehne, Manuel; Strong, Roland K; Abergel, Rebecca J

    2015-08-18

    Synthetic radionuclides, such as the transuranic actinides plutonium, americium, and curium, present severe health threats as contaminants, and understanding the scope of the biochemical interactions involved in actinide transport is instrumental in managing human contamination. Here we show that siderocalin, a mammalian siderophore-binding protein from the lipocalin family, specifically binds lanthanide and actinide complexes through molecular recognition of the ligands chelating the metal ions. Using crystallography, we structurally characterized the resulting siderocalin-transuranic actinide complexes, providing unprecedented insights into the biological coordination of heavy radioelements. In controlled in vitro assays, we found that intracellular plutonium uptake can occur through siderocalin-mediated endocytosis. We also demonstrated that siderocalin can act as a synergistic antenna to sensitize the luminescence of trivalent lanthanide and actinide ions in ternary protein-ligand complexes, dramatically increasing the brightness and efficiency of intramolecular energy transfer processes that give rise to metal luminescence. Our results identify siderocalin as a potential player in the biological trafficking of f elements, but through a secondary ligand-based metal sequestration mechanism. Beyond elucidating contamination pathways, this work is a starting point for the design of two-stage biomimetic platforms for photoluminescence, separation, and transport applications.

  5. Extremity dosimetry in nuclear medicine services using thermoluminescent detectors

    International Nuclear Information System (INIS)

    Mebhah, D.; Djeffal, S.; Badreddine, A.; Medjahed, M.

    1993-01-01

    The Radiation Protection and Safety Centre in Algiers provides two types of dosemeters, one for monitoring doses to the whole body and skin and the other one for monitoring doses to the extremities of the body. In nuclear medicine services and radiopharmaceutical laboratories, hands and arms are often closer to a given radiation source than the main part of the body and therefore receive greater doses. In this context, extremity doses have been measured by a ring dosemeter and by a fingertip ultra-thin dosemeter. The ring dosemeter consists of a metallic ring with a circular indentation to hold a LiF chip which is covered with a 10 mg.cm -2 shrinkable black polyamide layer. The ultra-thin dosemeter contains a 5 mg.cm -2 LiF element for measuring doses at a depth of 7 mg.cm -2 . These extremity dosemeters have been characterised before their use in the field. They have also been tested using radioisotopes of various energies. The doses received by the monitored workers were correlated with the amount of the handled activity. The doses obtained using the fingertip and the ring dosemeters are presented and discussed from a radiological point of view. (author)

  6. The actinides-a beautiful ending of the Periodic Table

    International Nuclear Information System (INIS)

    Johansson, Boerje; Li, Sa

    2007-01-01

    The 5f elements, actinides, show many properties which have direct correspondence to the 4f transition metals, the lanthanides. The remarkable similarity between the solid state properties of compressed Ce and the actinide metals is pointed out in the present paper. The α-γ transition in Ce is considered as a Mott transition, namely, from delocalized to localized 4f states. An analogous behavior is also found for the actinide series, where the sudden volume increase from Pu to Am can be viewed upon as a Mott transition within the 5f shell as a function of the atomic number Z. On the itinerant side of the Mott transition, the earlier actinides (Pa-Pu) show low symmetry structures at ambient conditions; while across the border, the heavier elements (Am-Cf) present the dhcp structure, an atomic arrangement typical for the trivalent lanthanide elements with localized 4f magnetic moments. The reason for an isostructural Mott transition of the f electron in Ce, as opposed to the much more complicated cases in the actinides, is identified. The strange appearance of the δ-phase (fcc) in the phase diagram of Pu is another consequence of the border line behavior of the 5f electrons. The path leading from δ-Pu to α-Pu is identified

  7. The low-energy spectrum of (2, 0) theory on T5 x R

    International Nuclear Information System (INIS)

    Henningson, Maans

    2008-01-01

    We consider the ADE-series of (2, 0) supersymmetric quantum theories on T 5 x R, where the first factor is a flat spatial five-torus, and the second factor denotes time. The quantum states of such a theory Φ are characterized by a discrete quantum number f element of H 3 (T 5 , C), where the finite abelian group C is the center subgroup of the corresponding simply connected simply laced Lie group G. At energies that are low compared to the inverse size of the T 5 , the spectrum consists of a set of continua of states, each of which is characterized by the value of f and some number 5r of additional continuous parameters. By exploiting the interpretation of this theory as the ultraviolet completion of maximally supersymmetric Yang-Mills theory on T 4 x S 1 x R with gauge group G adj = G/C and coupling constant g given by the square root of the radius of the S 1 factor, one may compute the number N f r (Φ) of such continua. We perform these calculations in detail for the A- and D-series. While the Yang-Mills theory formalism is manifestly invariant under the SL 4 (Z) mapping class group of T 4 , the results are actually found to be invariant under the SL 5 (Z) mapping class group of T 5 , which provides a strong consistency check.

  8. Solid phase extraction of Am (III) by resins impregnated with multiply diglycolamide-functionalized ligands

    International Nuclear Information System (INIS)

    Gujar, R.B.; Ansari, S.A.; Mohapatra, P.K.; Verboom, W.

    2016-01-01

    Solvent extraction studies with multiply diglycolamide-functionalized extractants such as tripodal diglycolamide (T-DGA) or diglycolamide-functionalized calix(4)arene (C4DGA) ligands have shown excellent results as compared to those of normal DGA ligands such as TODGA. A very high selectivity for Am(III) has been reported with these ligands with respect to U(VI) and Pu(IV). High selectivities and large extraction efficiencies of these ligands towards trivalent f elements were ascribed to a co-operative complexation mechanism. Furthermore, the extraction efficiency of these ligands increased several folds in ionic liquid medium as compared to paraffinic solvents. It was of interest, therefore, to prepare extraction chromatographic resins by impregnation of solvent systems containing these ligands in an ionic liquid. In the present work, solid phase extraction studies were carried out using these two multiply diglycolamide-functionalized extractants, viz. T-DGA (resin I) and C4DGA (resin-II) containing the ionic liquid C 4 mim. NTf 2 impregnated on Chromosorb-W

  9. Geometry and electronic structure of an impurity-trapped exciton in the Cs2GeF6 crystal doped with U4+. The 5f17s1 manifold

    International Nuclear Information System (INIS)

    Ordejon, B.; Seijo, L.; Barandiaran, Z.

    2007-01-01

    Complete text of publication follows: Excitons trapped at impurity centres in highly ionic crystals were first described by McClure and Pedrini [Phys. Rev. B 32, 8465 (1985)] as excited states consisting of a bound electron-hole pair with the hole localized on the impurity and the electron on nearby lattice sites, and a very short impurity-ligand bond length. In this work we present a detailed microscopic characterization of an impurity - trapped exciton in Cs 2 GeF 6 doped with U 4+ . Its electronic structure has been studied by means of CASSCF/CASPT2/SOCI relativistic ab initio model potential (AIMP) embedded-cluster calculations on (UF 6 ) 2- and (UF 6 Cs 8 ) 6+ clusters embedded in Cs 2 GeF 6 . The local geometry of the impurity-trapped exciton, the potential energy curves, and the multi electronic wavefunctions, have been obtained as direct, non-empirical results of the methods. The calculated excited states appear to be significantly delocalized outside the UF 6 volume and their U-F bond length turns out to be very short, closer to that of a pentavalent uranium defect than to that of a tetravalent uranium defect. The wavefunctions of these excited states show a dominant U 5f 1 7s 1 configuration character. This result has never been anticipated by simpler models and reveals the unprecedented ability of diffuse orbitals of f-element impurities to act as electron traps in ionic crystals

  10. Stabilization of actinides and lanthanides in unusually high oxidation states

    International Nuclear Information System (INIS)

    Eller, P.G.; Penneman, R.A.

    1986-01-01

    Chemical environments can be chosen which stabilize actinides and lanthanides in unusually high or low oxidation states and in unusual coordination. In many cases, one can rationalize the observed species as resulting from strong charge/size influences provided by specific sites in host lattices (e.g., Tb(IV) in BaTbO 3 or Am(IV) in polytungstate anions). In other cases, the unusual species can be considered from an acid-base viewpoint (e.g., U(III) in AsF 5 /HF solution or Pu(VII) in Li 5 PuO 6 ). In still other cases, an interplay of steric and redox effects can lead to interesting comparisons (e.g., instability of double fluoride salts of Pu(V) and Pu(VI) relative to U, Np, and Am analogues). Generalized ways to rationalize compounds containing actinides and lanthanides in unusual valences (particularly high valences), including the above and numerous other examples, will form the focus of this paper. Recently developed methods for synthesizing high valent f-element fluorides using superoxidizers and superacids at low temperatures will also be described. 65 refs., 8 figs., 9 tabs

  11. Application of multi-step excitation schemes for detection of actinides and lanthanides in solutions by luminescence/chemiluminescence laser spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Izosimov, I. [Joint Institute for Nuclear Research, Joliot Curie 6, Dubna 141980 (Russian Federation)

    2016-07-01

    The use of laser radiation with tunable wavelength allows the selective excitation of actinide/lanthanide species with subsequent registration of luminescence/chemiluminescence for their detection. This work is devoted to applications of the time-resolved laser-induced luminescence spectroscopy and time-resolved laser-induced chemiluminescence spectroscopy for the detection of lanthanides and actinides. Results of the experiments on U, Eu, and Sm detection by TRLIF (Time Resolved Laser Induced Fluorescence) method in blood plasma and urine are presented. Data on luminol chemiluminescence in solutions containing Sm(III), U(IV), and Pu(IV) are analyzed. It is shown that appropriate selectivity of lanthanide/actinide detection can be reached when chemiluminescence is initiated by transitions within 4f- or 5f-electron shell of lanthanide/actinide ions corresponding to the visible spectral range. In this case chemiluminescence of chemiluminogen (luminol) arises when the ion of f element is excited by multi-quantum absorption of visible light. The multi-photon scheme of chemiluminescence excitation makes chemiluminescence not only a highly sensitive but also a highly selective tool for the detection of lanthanide/actinide species in solutions. (author)

  12. Citrate based ''TALSPEAK'' lanthanide-actinide separation process

    International Nuclear Information System (INIS)

    Del Cul, G.D.; Bond, W.D.; Toth, L.M.; Davis, G.D.; Dai, S.; Metcalf, D.H.

    1994-09-01

    The potential hazard posed to future generations by long-lived radionuclides such as the transuranic elements (TRU) is perceived as a major problem associated with the use of nuclear power. TRU wastes have to remain isolated from the environment for ''geological'' periods of time. The costs of building, maintaining, and operating a ''geological TRU repository'' can be very high. Therefore, there are significant economical advantages in segregating the relatively low volume of TRU wastes from other nuclear wastes. The chemical behavior of lanthanides and actinides, 4f and 5f elements respectively, is rather similar. As a consequence, the separation of these two groups is difficult. The ''TALSPEAK'' process (Trivalent Actinide Lanthanide Separations by Phosphorus-reagent Extraction from Aqueous Complexes) is one of the few means available to separate the trivalent actinides from the lanthanides. The method is based on the preferential complexation of the trivalent actinides by an aminopolyacetic acid. Cold experiments showed that by using citric acid the deleterious effects produced by impurities such as zirconium are greatly reduced

  13. A data base for thermodynamic modeling of +III actinide solubility in concentrated Na-Cl-SO4-CO3-PO4 electrolytes

    International Nuclear Information System (INIS)

    Novak, C.F.; Crafts, C.C.; Dhooge, N.J.

    1995-01-01

    The literature contains thermodynamic parameters for describing the chemical behavior of the following: Am(III) in dilute NaHCO 3 media; Nd(III) in dilute to concentrated Na 2 CO 3 and NaHCO 3 media; Pu(III) in dilute to concentrated NaCl media; Nd(III)/Am(III) in dilute to concentrated Na 2 SO 4 media; and Am(III) in NaH 2 PO 4 media. We have combined this information into a thermodynamic data base for the general +III actinide, An(III), using the analogy for chemical behavior of f-elements in the same oxidation state. This internally consistent data base is based on equilibrium thermodynamics and the specific ion interaction activity coefficient formalism of Pitzer. This data base forms the basis for the prediction of potential Am(III) and Pu(III) dissolved concentrations in the concentrated natural brines associated with the Waste Isolation Pilot Plant (WIPP) in Southeastern New Mexico, USA

  14. Generalized localization for the double trigonometric Fourier series and the Walsh-Fourier series of functions in L log +L log + log +L

    International Nuclear Information System (INIS)

    Bloshanskaya, S K; Bloshanskii, I L; Roslova, T Y

    1998-01-01

    For an arbitrary open set Ω subset of I 2 =[0,1) 2 and an arbitrary function f element of L log + L log + log + L(I 2 ) such that f=0 on Ω the double Fourier series of f with respect to the trigonometric system Ψ=E and the Walsh-Paley system Ψ=W is shown to converge to zero (over rectangles) almost everywhere on Ω. Thus, it is proved that generalized localization almost everywhere holds on arbitrary open subsets of the square I 2 for the double trigonometric Fourier series and the Walsh-Fourier series of functions in the class L log + L log + log + L (in the case of summation over rectangles). It is also established that such localization breaks down on arbitrary sets that are not dense in I 2 , in the classes Φ Ψ (L)(I 2 ) for the orthonormal system Ψ=E and an arbitrary function such that Φ E (u)=o(u log + log + u) as u→∞ or for Φ W (u)=u( log + log + u) 1-ε , 0<ε<1

  15. Decamethylytterbocene Complexes of Bipyridines and Diazabutadienes: Multiconfigurational Ground States and Open-Shell Singlet Formation

    Energy Technology Data Exchange (ETDEWEB)

    Booth, Corwin H.; Walter, Marc D.; Kazhdan, Daniel; Hu, Yung-Jin; Lukens, Wayne W.; Bauer, Eric D.; Maron, Laurent; Eisenstein, Odile; Andersen, Richard A.

    2009-04-22

    Partial ytterbium f-orbital occupancy (i.e., intermediate valence) and open-shell singlet formation are established for a variety of bipyridine and diazabutadiene adducts with decamethylytterbocene, (C5Me5)2Yb, abbreviated as Cp*2Yb. Data used to support this claim include ytterbium valence measurements using Yb LIII-edge X-ray absorption near-edge structure spectroscopy, magnetic susceptibility, and complete active space self-consistent field (CASSCF) multiconfigurational calculations, as well as structural measurements compared to density functional theory calculations. The CASSCF calculations indicate that the intermediate valence is the result of a multiconfigurational ground-state wave function that has both an open-shell singlet f13(?*)1, where pi* is the lowest unoccupied molecular orbital of the bipyridine or dpiazabutadiene ligands, and a closed-shell singlet f14 component. A number of other competing theories for the unusual magnetism in these materials are ruled out by the lack of temperature dependence of the measured intermediate valence. These results have implications for understanding chemical bonding not only in organolanthanide complexes but also for f-element chemistry in general, as well as understanding magnetic interactions in nanoparticles and devices.

  16. Final Project Report for ER15351 ''A Study of New Actinide Zintl Ions Materials''

    International Nuclear Information System (INIS)

    Peter K. Dorhout

    2007-01-01

    The structural chemistry of actinide main-group metal materials provides the fundamental basis for the understanding of structural coordination chemistry and the formation of materials with desired or predicted structural features. The main-group metal building blocks, comprising sulfur-group, phosphorus-group, or silicon-group elements, have shown versatility in oxidation state, coordination, and bonding preferences. These building blocks have allowed us to elucidate a series of structures that are unique to the actinide elements, although we can find structural relationships to transition metal and 4f-element materials. In the past year, we investigated controlled metathesis and self-propagating reactions between actinide metal halides and alkali metal salts of main-group metal chalcogenides such as K-P-S salts. Ternary plutonium thiophosphates have resulted from these reactions at low temperature in sealed ampules. we have also focused efforts to examine reactions of Th, U, and Pu halide salts with other alkali metal salts such as Na-Ge-S and Na-Si-Se and copper chloride to identify if self-propagating reactions may be used as a viable reaction to prepare new actinide materials and we prepared a series of U and Th copper chalcogenide materials. Magnetic measurements continued to be a focus of actinide materials prepared in our laboratory. We also contributed to the XANES work at Los Alamos by preparing materials for study and for comparison with environmental samples

  17. Catalytic effect in opening the coordination sphere of an organo-f-complex

    International Nuclear Information System (INIS)

    Andrea, T.; Wang, J.; Gourevich, I.; Eisen, M.S.

    2002-01-01

    Organo-f-complexes have been studied in the last decade showing unique stoichiometric and catalytic properties, which are deeply influenced by the nature of the x ancillary ligands. Opening of the metal center coordination sphere is obtained by replacing the pentamethylcyclopentadienyl ligation in Cp* 2 MR 2 (Cp* = C 5 Me 5 , M = f-element metal, R = a-bonded ligand) by the bridged ancillary ligation Anna-Me 2 SiCp 2MR 2 (Cp* = C 5 Me 4 ). For organolanthanides, this change allows an increase (10-100 fold) in rates for the olefin insertion into the M-R bond [1] and in organoactinides; this modification has been shown to cause an increase (103 fold) in their catalytic activity for the hydrogenation of 1-hexene [2]. Recently, we have shown that organoactinides of the type Cp* 2 MR 2 (Cp* = C 5 Me 5 ; M = Th, U; R = CH 3 ) are active catalysts for both the oligomerization and hydrosilylation of terminal alkynes [3J. Thus, a conceptual question arises regarding the use of an open organoactinide such as Me 2 SiCp* 2 U n Bu 2 as compared to Cp* 2 UR 2 . This opening in the coordination sphere at the metal center should be unique in such a way that it is reasonable expected the increase of the reactivity towards product formation in the hydrosilylation and metathesis catalytic processes of terminal alkynes. In this poster we report, and quantitatively compare, the effects of the ansa-organouranium complex (Me 2 SiCp'' 2 U n Bu) 2 O The synthesis of the complex was achieved as described in equations 1 and 2

  18. Complexes of groups 3,4, the lanthanides and the actinides containing neutral phophorus donor ligands

    International Nuclear Information System (INIS)

    Fryzuk, M.D.; Haddad, T.S.; Berg, D.J.

    1990-01-01

    Of relevance to this review are complexes of the early transition elements, in particular groups 3 and 4 and the lanthanides and actinides. In this review the authors have attempted to collect all the data up to the end of 1988 for complexed of groups 3 and 4, the lanthanides and the actinides that contain phosphorus donor ligands. The 1989s have seen a renaissance of the use of phosphine donors for the early d elements (groups 3 and 4) and the f elements. Neutral phosphorus donors are defined as primary (PH 2 R), secondary (PH 2 ) or tertiary phosphines (PR 3 ), including complexes of phosphine, PH 3 . Also reviewed are complexes of PF 3 and phosphites, P(OR) 3 . Specifically excluded are phosphido derivates, PR 2 . The ability of a neutral phosphorus donor to bind the metals of groups 3 and 4, the lanthanides and the actinides is now well established. While there are still no examples of lanthanum or actinium phosphine complexes, such derivatives should be accessible at least for lanthanum. series. However, there is no obvious chemical reason to suggest that such derivatives cannot be generated. The phosphine ligands that appear to generate the most stable phosphine-metal interaction are chelating phosphines such as dmpe, trmpe and trimpsi. In addition, the use of the chelate effect in conjunction with a hard ligand such as the amide in - N(SiMe 2 CH 2 PMe 2 ) 2 , or an alkoxide as found in - OC(BU t ) 2 CH 2 PMe 2 , also appears to be effective in anchoring the phosphine donor to the metal. The majority of low oxidation state derivatives of the group 4 elements are stabilized by phosphine donors in contrast with other parts of the transition series where one finds that classic π-acceptor-type ligands such as CO or RNC are utilized. 233 refs

  19. Advancing Understanding of the +4 Metal Extractant Thenoyltrifluoroacetonate (TTA-); Synthesis and Structure of MIVTTA4 (MIV = Zr, Hf, Ce, Th, U, Np, Pu) and MIII(TTA)4- (MIII = Ce, Nd, Sm, Yb).

    Science.gov (United States)

    Cary, Samantha K; Livshits, Maksim; Cross, Justin N; Ferrier, Maryline G; Mocko, Veronika; Stein, Benjamin W; Kozimor, Stosh A; Scott, Brian L; Rack, Jeffrey J

    2018-04-02

    Thenoyltrifluoroacetone (HTTA)-based extractions represent popular methods for separating microscopic amounts of transuranic actinides (i.e., Np and Pu) from macroscopic actinide matrixes (e.g. bulk uranium). It is well-established that this procedure enables +4 actinides to be selectively removed from +3, + 5, and +6 f-elements. However, even highly skilled and well-trained researchers find this process complicated and (at times) unpredictable. It is difficult to improve the HTTA extraction-or find alternatives-because little is understood about why this separation works. Even the identities of the extracted species are unknown. In addressing this knowledge gap, we report here advances in fundamental understanding of the HTTA-based extraction. This effort included comparatively evaluating HTTA complexation with +4 and +3 metals (M IV = Zr, Hf, Ce, Th, U, Np, and Pu vs M III = Ce, Nd, Sm, and Yb). We observed +4 metals formed neutral complexes of the general formula M IV (TTA) 4 . Meanwhile, +3 metals formed anionic M III (TTA) 4 - species. Characterization of these M(TTA) 4 x- ( x = 0, 1) compounds by UV-vis-NIR, IR, 1 H and 19 F NMR, single-crystal X-ray diffraction, and X-ray absorption spectroscopy (both near-edge and extended fine structure) was critical for determining that Np IV (TTA) 4 and Pu IV (TTA) 4 were the primary species extracted by HTTA. Furthermore, this information lays the foundation to begin developing and understanding of why the HTTA extraction works so well. The data suggest that the solubility differences between M IV (TTA) 4 and M III (TTA) 4 - are likely a major contributor to the selectivity of HTTA extractions for +4 cations over +3 metals. Moreover, these results will enable future studies focused on explaining HTTA extractions preference for +4 cations, which increases from Np IV to Pu IV , Hf IV , and Zr IV .

  20. Optical properties of LiYF4:U3+. Infrared laser use

    International Nuclear Information System (INIS)

    Louis, M.

    1995-01-01

    In this study are proposed a complete interpretation of the optical spectra of trivalent uranium in LiYF 4 (LYF). Single crystals of uranium doped LYF were grown by Czochralski method with different concentration (0.05%-0.20%). The obtained crystals have pale green color, characteristic of tetravalent uranium. The absorption spectra show that effectively only U 4+ is present in this crystal. In order to reduce the oxidation state of the U 4+ , the pale green crystal containing 0.07% of U 4+ was exposed to gamma irradiation. The sample becomes orange brown and the absorption spectrum is characteristic of U 3+ . The irradiation technology is an efficient method to convert 100% of U 4+ in U 3+ . From the analysis of the polarized optical absorption and emission spectra the spectroscopic parameters have been determined. The Judd-Ofelt theory was applied in order to simulate the intensity of the 5 f 3 →5 f 3 transitions between Stark levels of U 3+ in LYF. Because of the large crystal field splitting of the J multiplet in the actinides a set of phenomenological intensity parameters is introduced to describe the transition probabilities between crystal field sublevels. A continuous laser emission of an actinide ion at ambient temperature has been revealed. In the last part of this thesis the fundamental aspect of the energy transfer process that takes place in laser crystal LYF codoped with an 4 f element Nd 3+ and an 5 f one U 3+ has been investigated. (author). 111 refs., 69 figs., 19 tabs

  1. 2010 INORGANIC CHEMISTRY GORDON RESEARCH CONFERENCE JUNE 20 - 25, 2010

    Energy Technology Data Exchange (ETDEWEB)

    JOHN LOCKEMEYER

    2010-06-25

    The Inorganic Chemistry GRC is one of the longest-standing of the GRCs, originating in 1951. Over the years, this conference has played a role in spawning many other GRCs in specialized fields, due to the involvement of elements from most of the periodic table. These include coordination, organometallic, main group, f-element, and solid state chemistries; materials science, catalysis, computational chemistry, nanotechnology, bioinorganic, environmental, and biomedical sciences just to name a few. The 2010 Inorganic Chemistry GRC will continue this tradition, where scientists at all levels from academic, industrial, and national laboratories meet to define the important problems in the field and to highlight emerging opportunities through exchange of ideas and discussion of unpublished results. Invited speakers will present on a wide variety of topics, giving attendees a look at areas both inside and outside of their specialized areas of interest. In addition to invited speakers, the poster sessions at GRCs are a key feature of the conference. All conferees at the Inorganic Chemistry GRC are invited to present a poster on their work, and here the informal setting promotes the free exchange of ideas and fosters new relationships. As in previous years, we will offer poster presenters the opportunity to compete for one of several program spots in which they can give an oral presentation based on the subject matter of their poster. This is a great way to get your work noticed by the scientists attending the meeting, especially for those early in their career path such as junior faculty members, postdoctoral fellows, and those at comparable ranks. Anyone interested in participating in the poster competition should bring an electronic slide presentation and a small hard copy of their poster to submit to the committee.

  2. Selectivity in Ligand Binding to Uranyl Compounds: A Synthetic, Structural, Thermodynamic and Computational Study

    Energy Technology Data Exchange (ETDEWEB)

    Arnold, John [Univ. of California, Berkeley, CA (United States)

    2017-12-06

    The uranyl cation (UO22+) is the most abundant form of uranium on the planet. It is estimated that 4.5 billion tons of uranium in this form exist in sea water. The ability to bind and extract the uranyl cation from aqueous solution while separating it from other elements would provide a limitless source of nuclear fuel. A large body of research concerns the selective recognition and extraction of uranyl. A stable molecule, the cation has a linear O=U=O geometry. The short U-O bonds (1.78 Å) arise from the combination of uranium 5f/6d and oxygen 2p orbitals. Due to the oxygen moieties being multiply bonded, these sites were not thought to be basic enough for Lewis acidic coordination to be a viable approach to sequestration. We believe that the goal of developing a practical system for uranium separation from seawater will not be attained without new insights into our existing fundamental knowledge of actinide chemistry. We posit that detailed studies of the kinetic and thermodynamic factors that influence interactions between f-elements and ligands with a range of donor atoms is essential to any major advance in this important area. The goal of this research is thus to broaden the coordination chemistry of the uranyl ion by studying new ligand systems via synthetic, structural, thermodynamic and computational methods. We anticipate that this fundamental science will find use beyond actinide separation technologies in areas such as nuclear waste remediation and nuclear materials.

  3. Trace and toxic elements in foodstuffs in Japan

    International Nuclear Information System (INIS)

    Muramatsu, Y.; Sumiya, M.; Yanagisawa, K.; Ohmomo, Y.

    1994-01-01

    Concentrations of trace elements in several foodstuffs collected in Japan were analyzed by neutron activation analysis (NAA), inductively-coupled plasma atomic emission spectrometry (ICP-AES) and anodic striping voltametry (ASV). The elements analyzed were as follows: Zn, Se, As, Hg, Cs, Cr, Co, Fe, Rb, Br and K by NAA; Mn, Ba, Sr, Mg, Ca, P, K, Zn, Cu and Fe by ICP-AES; and Pb, Cd, Cu and Zn by ASV. Because of the high consumption of rice in Japan, the focus of analysis was on this foodstuff. Concentrations of K, Mg, Mn, P and Zn in different polished rice samples were similar, whereas those of Br, Co, Cs, Rb and Se varied. Levels of toxic elements in polished rice were generally lower than those in other foodstuffs. The highest concentrations of As, Hg, Se and Zn were found in marine products, i.e.. Hijiki-algae (As: 59 mg/kg, dry), tuna (Hg: 1.1 mg/kg, dry), bonito (Se: 4.5 mg/kg, dry) and oysters (Zn: 350 mg/kg, dry). Dietary intakes of As, Ca, Cd, Cu, Fe, Hg, K, Mg, Mn, P, Pb, Se and Zn by Japanese were estimated by using these analytical results and published food consumption data in Japan. We have also identified the major sources of the elements in dietary intakes as follows: (a) about 90% of the As was derived from marine products (fish and seaweed); (b) about 70% of the Hg was derived from fish; (c) about 40-60% of the Cd and the Mn and 20-40% of the Zn, Cu and Mg was derived from rice; (d) selenium was mostly derived from fish, meat and eggs; (e) more than 20% of the Ca was derived from milk and milk products; (f) elements such as Fe, K, P and Pb was derived from different sorts of foodstuffs. (author). 7 refs, 1 fig., 7 tabs

  4. Activation of SO2 with [(η(5) -C5 Me5 )2 Ln(THF)2 ] (Ln=Eu, Yb) leading to dithionite and sulfinate complexes.

    Science.gov (United States)

    Klementyeva, Svetlana V; Gamer, Michael T; Schmidt, Anna-Corina; Meyer, Karsten; Konchenko, Sergey N; Roesky, Peter W

    2014-10-13

    The reaction of decamethylytterbocene [(η(5) -C5 Me5 )2 Yb(THF)2 ] with SO2 at low temperature gave two new compounds, namely, the Yb(III) dithionite/sulfinate complex [{(η(5) -C5 Me5 )2 Yb(μ3 ,1κ(2) O(1,3) ,2κ(3) O(2,2',4) -S2 O4 )}2 {(η(5) -C5 Me5 )Yb(μ,1κO,2κO'-C5 Me5 SO2 )}2 ] (1) and the Yb(III) dithionite complex [{(η(5) -C5 Me5 )2 Yb}2 (μ,1κ(2) O(1,3) ,2κ(2) O(2,4) -S2 O4 )] (2). After extraction of 1, the mixture was heated to give the dinuclear tetrasulfinate complex [{(η(5) -C5 Me5 )Yb}2 (μ,κO,κO'-C5 Me5 SO2 )4 ] (3 a). In contrast, from the reaction of [(η(5) -C5 Me5 )2 Eu(THF)2 ] with SO2 only the tetrasulfinate complex [{(η(5) -C5 Me5 )Eu}2 (μ,κO,κO'-C5 Me5 SO2 )4 ] (3 b) was isolated. Two major reaction pathways were observed: 1) reductive coupling of two SO2 molecules to form the dithionite anion S2 O4 (2-) ; and 2) nucleophilic attack of one metallocene C5 Me5 ligand on the sulfur atom of SO2 . The compounds presented are the first dithionite and sulfinate complexes of the f-elements. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Thorium and uranium redox-active ligand complexes; reversible intramolecular electron transfer in U(dpp-BIAN)2/ U(dpp-BIAN)2(THE)

    Energy Technology Data Exchange (ETDEWEB)

    Schelter, Eric John [Los Alamos National Laboratory; Wu, Ruilian [Los Alamos National Laboratory; Scott, Brian L [Los Alamos National Laboratory; Thompson, Joe D [Los Alamos National Laboratory; Batista, Enrique R [Los Alamos National Laboratory; Morris, David E [Los Alamos National Laboratory; Kiplinger, Jaqueline L [Los Alamos National Laboratory

    2008-01-01

    Actinide complexes of the redox-active ligand dpp-BIAN{sup 2-} (dpp-BIAN = bis(2,6-diisopropylphenyl)acenaphthylene), An(dpp-BIAN){sub 2}(THF){sub n} (An = Th, n = 1; An = U, n = 0, 1) have been prepared. Solid-state magnetic and single-crystal X-ray data for U(dpp-BIAN){sub 2}(THF){sub n} show when n = 0, the complex exists in an f{sup 2}-{pi}*{sup 4} configuration; whereas an intramolecular electron transfer occurs for n = 1, resulting in an f{sup 3}-{pi}*{sup 3} ground configuration. The magnetic data also indicate that interconversion between the two forms of the complex is possible, limited only by the ability of THF vapor to penetrate the solid on cooling of the sample. Spectroscopic data indicate the complex exists solely in the f{sup 2}-{pi}*{sup 4} form in solution, evidenced by the appearance of only small changes in the electronic absorption spectra of the U(dpp-BIAN){sub 2} complex on titration with THF and by measurement of the solution magnetic moment m d{sub 8}-tetrahydrofuran using Evans method. Electrochemistry of the complexes is reported, with small differences observed in wave potentials between metals and in the presence of THF. These data represent the first example of a well-defined, reversible intramolecular electron transfer in an f-element complex and the second example of oxidation state change through dative interaction with a metal ion.

  6. CMPO-calix[4]arenes with spacer containing intramolecular hydrogen bonding: Effect of local rigidification on solvent extraction toward f-block elements

    International Nuclear Information System (INIS)

    Chu, Hongzhu; He, Lutao; Jiang, Qian; Fang, Yuyu; Jia, Yiming; Yuan, Xiangyang; Zou, Shuliang; Li, Xianghui; Feng, Wen; Yang, Yuanyou; Liu, Ning; Luo, Shunzhong; Yang, Yanqiu; Yang, Liang; Yuan, Lihua

    2014-01-01

    Highlights: • Three CMPO-calix[4]arenes with spacer containing intramolecular hydrogen bonds were designed and synthesized. • The influence of local rigidification caused by intramolecular hydrogen bonds upon extraction of f-elements was investigated. • Selective extraction is realized via tuning local chelating surroundings by aid of intramolecular hydrogen bonds. -- Abstract: To understand intramolecular hydrogen bonding in effecting liquid–liquid extraction behavior of CMPO-calixarenes, three CMPO-modified calix[4]arenes (CMPO-CA) 5a–5c with hydrogen-bonded spacer were designed and synthesized. The impact of spacer rotation that is hindered by introduction of intramolecular hydrogen bonding upon extraction of La 3+ , Eu 3+ , Yb 3+ , Th 4+ , and UO 2 2+ has been examined. The results show that 5b and 5c containing only one hydrogen bond with a less hindered rotation spacer extract La 3+ more efficiently than 5a containing two hydrogen bonds with a more hindered rotation spacer, demonstrating the importance of local rigidification of spacer in the design of extractants in influencing the coordination environment. The large difference in extractability between La 3+ and Yb 3+ (or Eu 3+ ) by 5b (or 5c), and the small difference by 5a, suggests intramolecular hydrogen bonding do exert pronounced influence upon selective extraction of light and heavy lanthanides. Log–log plot analysis indicates a 1:1, 2:1 and 1:1 stoichiometry (ligand/metal) for the extracted complex formed between 5b and La 3+ , Th 4+ , UO 2 2+ , respectively. Additionally, their corresponding acyclic analogs 7a–7c exhibit negligible extraction toward these metal ions. These results reveal the possibility of selective extraction via tuning local chelating surroundings of CMPO-CA by aid of intramolecular hydrogen bonding

  7. High resolution X-ray emission spectroscopy: An advanced tool for actinide research

    Science.gov (United States)

    Vitova, T.; Brendebach, B.; Dardenne, K.; Denecke, M. A.; Lebid, A.; Löble, M.; Rothe, J.; Batuk, O. N.; Hormes, J.; Liu, D.; Breher, F.; Geckeis, H.

    2010-03-01

    High resolution X-ray emission spectroscopy (HRXES) is becoming increasingly important for our understanding of electronic and coordination structures. The combination of such information with development of quantum theoretical tools will advance our capability for predicting reactivity and physical behavior especially of 5f elements. HRXES can be used to remove lifetime broadening by registering the partial fluorescence yield emitted by the sample (i.e., recording a windowed signal from the energy dispersed fluorescence emission while varying incident photon energy), thereby yielding highly resolved X-ray absorption fine structure (XAFS) spectra. Such spectra often display resonant features not observed in conventional XAFS. The spectrometer set-up can also be used for a wide range of other experiments, for example, resonant inelastic X-ray scattering (RIXS), where bulk electron configuration information in solids, liquids and gases is obtained. Valence-selective XAFS studies, where the local structure of a selected element's valence state present in a mixture of valence states can be obtained, as well as site-selective XAFS studies, where the coordination structure of a metal bound to selected elements can be differentiated from that of all the other ligating atoms. A HRXES spectrometer has been constructed and is presently being commissioned for use at the INE-Beamline for actinide research at the synchrotron source ANKA at FZK. We present the spectrometer's compact, modular design, optimized for attaining a wide range of energies, and first test measurement results. Examples from HRXES studies of lanthanides, actinides counter parts, are also shown.

  8. Thermodynamic Features of Benzene-1,2-Diphosphonic Acid Complexes with Several Metal Ions

    Energy Technology Data Exchange (ETDEWEB)

    Syouhei Nishihama; Ryan P. Witty; Leigh R Martin; Kenneth L. Nash

    2013-08-01

    Among his many contributions to the advancement of f-element chemistry and separation science, Professor Gregory R. Choppin’s research group completed numerous investigations featuring the application of distribution techniques to the determination of metal complexation equilibrium quotients. Most of these studies focused on the chemistry of lanthanide and actinide complexes. In keeping with that tradition, this report discusses the complex formation equilibrium constants for complexes of trivalent europium (Eu3+) with benzene-1,2-diphosphonic acid (H4BzDP) determined using solvent extraction distribution experiments in 0.2 M (Na,H)ClO4 media in the temperature range of 5 – 45 degrees C. Protonation constants for HnBzDP4-n and stoichiometry and stability of BzDP4- complexes with Zn2+, Ni2+, and Cu2+ have also been determined using potentiometric titration (at I = 0.1 M) and 31P NMR spectroscopy. Heats of protonation of HnBzDPn-4 species have been determined by titration calorimetry. From the temperature dependence of the complex Eu3+-HnBzDPn-4 equilibrium constant, a composite enthalpy (?H = -15.1 (+/-1.0) kJ mol-1) of complexation has been computed. Comparing these thermodynamic parameters with literature reports on other diphosphonic acids and structurally similar carboxylic acids indicates that exothermic heats of complexation are unique to the Eu-BzDP system. Comparisons with thermodynamic data from the literature indicate that the fixed geometry imposed by the benzene ring enhances complex stability.

  9. Phase compatibilities of YBa2Cu3O(9-delta) type structure in quintenary systems Y-Ba-Cu-O-X (impurity)

    Science.gov (United States)

    Karen, P.; Fjellvag, H.; Kjekshus, A.

    1990-01-01

    Electrical transport properties of the oxidic high T(sub c) superconductors are significantly affected by the presence of minor amounts of various elements adventing as impurities, e.g., from the chemical environment during manufacturing. YBa2Cu3O(9-delta) is prone to an extinction of the superconductivity on (partial) substitution of all four elemental components. E.g., Pr (for Y), La (for Ba), Zn (for Cu) or peroxygroup (for O) substituents will alter some of the superconductivity preconditions, like mixed valence state in Cu3O7/O(9-delta) network or structural distortion of the network. Although various pseudoternary chemical equilibrium phase diagrams of the Y(O)-Ba(O)-Cu(O) system now are available, no consensus is generally shown, however, this is partly due to lack of compatible definitions of the equilibrium conditions. Less information is available about the phase compatibilities in the appropriate quaternary phase diagram (including oxygen) and virtually no information exists about any pentenary phase diagrams (including one impurity). Unfortunately, complexity of such systems, stemming both from number of quaternary or pentenary compounds and from visualizing the five-component phase system, limits this presentation to more or less close surroundings of the YBa2Cu3O(9-delta) type phase in appropriate pseudoquaternary or pseudopseudoternary diagrams, involving Y-Ba-Cu and O, O-CO2, alkaline metals, Mg and alkaline earths, and Sc and most of the 3-d and 4-f elements. The systems were investigated by means of x ray diffraction, neutron diffraction and chemical analytical methods on samples prepared by sol-gel technique from citrates. The superconductivity was characterized by measuring the diamagnetic susceptibility by SQUID.

  10. Actinides and lanthanides under pressure: the pseudopotential approach

    International Nuclear Information System (INIS)

    Richard, N.

    2002-01-01

    In the Density Functional Theory Framework, the pseudopotential formalism offers a broader scope of study than other theoretical methods such as global relaxation of the parameters of the cell or ab initio molecular dynamics simulations. This method has been widely used to study light elements or transition metals but never to study f elements. We have generated two non local norm conserving Trouillier-Martins pseudopotentials (one in LDA and one in GGA) for the cerium. To check the validity of the pseudopotentials, we have calculated the equilibrium volume and the incompressibility modulus and compared our results to previous all-electron calculations. If the GGA and non linear core corrections are used, the equation of state is in a good agreement with the experimental equation of state. A static study of the previously proposed high pressure phases give a transitions fcc-a''(I)-bct. Using the pseudopotentials we have generated, an ab initio molecular dynamics simulation at constant pressure, in the region between 5 and 12 GPa where the stable phase of cerium is not well defined, lead us to predict that a centred monoclinic structure, as the a''(I) phase previously observed in some experiments, is the most stable phase. We have also generated pseudopotentials for the light actinides (Th, Pa, U and Np). We have study their phase transitions under pressure at zero temperature. We compared our results with all electron results. The structure parameters have always been relaxed in this study. And for the first time in pseudopotential calculation, the spin-orbit coupling has been taken into account. The curves describing the variation of the volume or the incompressibility modulus depending on the elements and the phase transitions are always in agreement with the one found in the all electron calculations. (author)

  11. Actinides and lanthanides under pressure: the pseudopotential approach; Actinides et terres rares sous pression: approche pseudopotentiel

    Energy Technology Data Exchange (ETDEWEB)

    Richard, N

    2002-07-01

    In the Density Functional Theory Framework, the pseudopotential formalism offers a broader scope of study than other theoretical methods such as global relaxation of the parameters of the cell or ab initio molecular dynamics simulations. This method has been widely used to study light elements or transition metals but never to study f elements. We have generated two non local norm conserving Trouillier-Martins pseudopotentials (one in LDA and one in GGA) for the cerium. To check the validity of the pseudopotentials, we have calculated the equilibrium volume and the incompressibility modulus and compared our results to previous all-electron calculations. If the GGA and non linear core corrections are used, the equation of state is in a good agreement with the experimental equation of state. A static study of the previously proposed high pressure phases give a transitions fcc-a''(I)-bct. Using the pseudopotentials we have generated, an ab initio molecular dynamics simulation at constant pressure, in the region between 5 and 12 GPa where the stable phase of cerium is not well defined, lead us to predict that a centred monoclinic structure, as the a''(I) phase previously observed in some experiments, is the most stable phase. We have also generated pseudopotentials for the light actinides (Th, Pa, U and Np). We have study their phase transitions under pressure at zero temperature. We compared our results with all electron results. The structure parameters have always been relaxed in this study. And for the first time in pseudopotential calculation, the spin-orbit coupling has been taken into account. The curves describing the variation of the volume or the incompressibility modulus depending on the elements and the phase transitions are always in agreement with the one found in the all electron calculations. (author)

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-01-01

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

  13. Uranyl complexes formed with a para-t-butylcalix[4]arene bearing phosphinoyl pendant arms on the lower rim. Solid and solution studies

    Energy Technology Data Exchange (ETDEWEB)

    Ramirez, F. de M. [Instituto Nacional de Investigaciones Nucleares, La Marquesa, Ocoyoacac (Mexico). Dept. de Quimica; Varbanov, S. [Bulgarian Academy of Sciences, Sofia (Bulgaria). Inst. of Organic Chemistry with Center of Phytochemistry; Buenzli, J.C.G. [Ecole Polytechnique Federale de Lausanne (EPFL) (Switzerland). Inst. of Chemical Sciences and Engineering; Rivas-Silva, J.F.; Ocana-Bribiesca, M.A. [Instituto de Fisica de la BUAP, Puebla (Mexico); Cortes-Jacome, M.A.; Toledo-Antonio, J.A. [Instituto Mexicano del Petroleo/Programa de Ingenieria Molecular (Mexico)

    2012-07-01

    The current interest in functionalized calixarenes with phosphorylated pendant arms resides in their coordination ability towards f elements and capability towards actinide/rare earth separation. Uranyl cation forms 1:1 and 1:2 (M:L) complexes with a tetra-phosphinoylated p-tert-butylcalix[4]arene, B{sub 4}bL{sup 4}: UO{sub 2}(NO{sub 3}){sub 2}(B{sub 4}bL{sup 4}){sub n} . xH{sub 2}O (n = 1, x = 2, 1; n = 2, x = 6, 2). Spectroscopic data point to the inner coordination sphere of 1 containing one monodentate nitrate anion, one water molecule and the four phosphinoylated arms bound to UO{sub 2}{sup 2+} while in 2, uranyl is only coordinated to calixarene ligands. In both cases the U(VI) ion is 8-coordinate. Uranyl complexes display enhanced metal-centred luminescence due to energy transfer from the calixarene ligands; the luminescence decays are bi-exponential with associated lifetimes in the ranges 220 {mu}s < {tau}{sub s} < 250 {mu}s and 630 {mu}s < {tau}{sub L} < 640 {mu}s, pointing to the presence of two species with differently coordinated calixarene, as substantiated by a XPS study of U(4f{sub 5/2,7/2}), O(1s) and P(2p) levels on solid state samples. The extraction study of UO{sub 2}{sup 2+} cation and trivalent rare-earth (Y, La, Eu) ions from acidic nitrate media by B{sub 4}bL{sup 4} in chloroform shows the uranyl cation being much more extracted than rare earths. (orig.)

  14. Present Status of Nitrogen Fixation by Reactor Radiation; Etat Actuel des Recherches sur l'oxydation directe de l'azote sous irradiation dans des reacteurs; Sovremennoe sostoyani opytov po okisleniyu azota izlucheniem iz reaktorov; Estado actual de las investigaciones sobre fijacion del nitrogeno por irradiacion en reactores

    Energy Technology Data Exchange (ETDEWEB)

    Harteck, P; Dondes, S [Rensselaer Polytechnic Institute, Troy, NY (United States)

    1960-07-15

    fision liberada en las fibras de vidrio y de la resistencia termica del circuito. Otro circuito, que habra de funcionar a 50 - 75 atmosferas y 600{sup o}C se encuentra en curso de construccion. Estos circuitos permitiran evaluar las caracteristicas de un sistema continuo, incluido el comportamient o de los productos de fision liberados en la corriente gaseosa. Los autores distinguen tres fases en la cinetica compleja de la oxidacion del nitrogeno: reacciones iniciales en el sistema;, reacciones subsiguientes a la fijacion de cierta cantidad de nitrogeno y, por ultimo, cinetica del equilibrio alcanzado en presencia de radiaciones. Se estudian las condiciones necesarias para la formacion de N{sub 2}0{sub 5}, N{sub 2}0{sub 4} y O{sub 3}, asi como los efectos que ejercen sobre el proceso en conjunto. (author) [Russian] Pri issledovaniyakh okisleniya azota izlucheniem iz reaktorov, kotorye proizvodilis ' v Rensselerovskom institute i v Brukkhejvenskoj natsional'noj laboratorii v techenie ryada let, byla ispol'zovana, v kachestve neposredstvennogo ioniziruyushchego izlucheniya, ehnergiya otdachi oskolkov deleniya putem rasseyaniya urana-235 v steklyannom volokne diametrom priblizitel'no v 5 mikronov. Bylo opredeleno vliyanie temperatury, davleniya i sootnosheniya mezhdu kolichestvom azota i kolichestvom kisloroda na velichinu radiatsionno-khimicheskogo vykhoda G na okislenie azota i rezul'taty byli soobshcheny v tekhnicheskoj literature. Nizhe daetsya kratkaya svodka ehtoj raboty. Upomyanutaya vyshe rabota proizvodilas' nad staticheskimi sistemami ; nedavno proizvedennaya rabota okhvatyvala kak staticheskie, tak i tsiklicheskie sistemy. V staticheskikh sistemakh glavnoe vnimanie obrashchalos' na vliyanie intensivnosti izlucheniya, v osobennosti v sostoyanii kineticheskogo ravnovesiya izlucheniya. Bylo ustanovleno, chto obrazovanie N0{sub 2}. i N{sub 2}0 V smesyakh azota i kisloroda v proportsiyakh 4:1 i 2: 1 proiskhodit do polnogo istoshcheniya yusloroda. TSiklicheskaya

  15. Plasma Containment and Stability in a Megajoule Theta-Pinch Experiment; Confinement et Stabilite du Plasma dans un Dispositif a Striction Azimutale de un Megajoule; Uderzhanie i ustojchivost' plazmy pri provedenii ehksperimenta s' megadzhoulevym teta-pinchem; Confinamiento y Estabilidad del Plasma en un Experimento de Estriccion Azimutal de 1 MJ

    Energy Technology Data Exchange (ETDEWEB)

    Bodin, H. A.B.; Green, T. S.; Newton, A. A.; Niblett, G. B.F.; Reynolds, J. A. [United Kingdom Atomic Energy Authority, Culham Laboratory, Abingdon, Berks. (United Kingdom)

    1966-04-15

    tecnicas: las principales son la interferometrta optica para evaluar el numero total de particulas capturadas, un analisis de la emision en la zona continua del espectro visible para obtener la densidad de lineas en funcion de la posicion axial, y el empleo de microsondas piezoelectricas de presion para medir el tamaflo de la abertura de perdidas. Los resultados muestran que el plasma sufre difusion del campo magnetico en las fases iniciales y enfriamiento de los electrones por irradiacion debida a impurezas o por conduccion termica a lo largo de las lineas de fuerza. Como consecuencia, el valor {beta} del plasma desciende a 0,5 aproximadamente, a la densidad magnetica maxima, con lo que se agrandan las aberturas magneticas de los extremos de la bobina, originando asi el escape axial del plasma. Los principales problemas aun pendientes de solucion se refieren al perfeccionamiento de un dispositivo de precalentamiento que permita obtener un plasma de temperatura mas elevada con un valor {beta} proximo a la unidad, y a la reduccion de la velocidad de perdida de energia delos electrones. (author) [Russian] Pri provedenii poslednih jeksperimentov po polucheniju vysokotemperaturnoj plazmy na tetatrone byla ispol'zovana bystraja megadzhoulevaja batareja kondensatorov. Odnozahodnaja katushka, dlinoj 200 sm i diametrom 10 sm, sozdaet pole intensivnost'ju 76 kg s poluperiodom 12 mksek. Dejterievyj gaz ispol'zuetsja pri nachal'nyh davlenijah v diapazone 10-50 militor. i predvaritel'no ioniziruetsja aksial'nym tokom. Posledujushhee smeshhenie plazmy k stenkam kvarcevoj razrjadnoj trubki ustranjaetsja v rezul'tate umen'shenija izgiba uderzhivajushhih magnitnyh silovyh linij s ispol'zovaniem linii parallel'nogo polosnogo propuskanija mezhdu katushkoj i kollektorom. Budet obsuzhden vopros o proishozhdenii krugovogo dvizhenija plazmy s maloj amplitudoj vokrug central'noj osi ravnovesija, tak nazyvaemogo javlenija ''kachanija''. Obshhie osobennosti razrjada analizirovalis' putem

  16. Continuous Calcination of High-Level Radioactive Wastes by Means of a Rotary-Ball Kiln; Calcination Continue de Dechets de Haute Activite dans un Four Rotatif a Billes; 041d 0415 041f 0420 0415 0420 042b 0412 041d 041e 0415 041a 0410 041b 042c 0426 0418 041d 0418 0420 041e 0412 0410 041d 0418 0415 0412 042b 0421 041e 041a 041e 0410 041a 0422 0418 0412 041d 042b 0425 041e 0422 0425 041e 0414 041e 0412 0412 041e 0412 0420 0410 0429 0410 042e 0429 0415 0419 0421 042f 0428 0410 0420 041e 0412 041e 0419 041f 0415 0427 0418 ; Calcinacion Continua de Desechos de Elevada Radiactividad en un Horno de Bolas Rotatorio

    Energy Technology Data Exchange (ETDEWEB)

    Regan, W. H.; Hatch, L. P.; Domish, R. F. [Brookhaven National Laboratory, Upton, Long Island, NY (United States)

    1963-02-15

    svodit do minimuma kontrolirovanie radioaktivnoj pyli. Poskol'ku nekondensi- rupciesja gazy v sistemu ne dobavljajutsja, otlichnoe ustranenie pyli dostigaetsja neposredstvennoj kondensaciej vyhodjashhih gazov, posle chego nebol'shaja chast' nekondensirupcihsja veshhestv propuskaetsja cherez skrubber i absoljutnyj fil'tr. V Brukhejvene postroen promyshlennyj kal'cinator, kotoryj v nastojashhee vremja ispol'zuetsja dlja ispytanija oborudovanija i razrabatyvaemyh metodov pererabotki. Vrashhajushhajasja pech' imeet diametr 2o sm, dlina nagrevaemoj chasti ee svyshe 2 m. Ona prednaznachena dlja kal'cinirovanija svyshe 22 l othodov v chas. V doklade privodjatsja osnovnye osobennosti Brukhejvenskoj obzhigatel'noj pechi, prichem osoboe vnimanie udeljaetsja germetizacii vrashhajushhihsja uzlov. Obsuzhdajutsja takzhe rezul'taty jekspluatacii opytnoj ustanovki, rabotajushhej na model'nom neradioaktivnom rastvore nitrata aljuminija. (author)

  17. Radiation Polymerization of Acetylene Hydrocarbons. Special Features; Particularites de la polymerisation radiochimique des hydrocarbures acetyleniques; Radiatsionnaya polimerizatsiya atsetilenovykh proizvodnykh; Particularidades de la radiopolimerizacion de los hidrocarburos acetilenicos

    Energy Technology Data Exchange (ETDEWEB)

    Barkalov, I. M.; Gol' danskij, V. I.; Go, Min' -Gao

    1963-11-15

    termo- i fotookislitel'noj destruktsii polimerov. Udobnym sposobom polucheniya podobnykh polimerov yavlyaetsya radiatsionnaya polimerizatsiya atsetilenovykh proizvodnykh. Tol'ko ehtot sposob obespechivaet poluchenie polimerov, svobodnykh ot zagryazneniya initsiatorami pri nizkikh temperaturakh. Kinetika radiatsionnoj polimerizatsii fenilatsetilena i drugikh atsetilenovykh proizvodnykh imeet ryad osobennostej, kharakternykh dlya ionnoj polimerizatsii, no sovershenno neobychnykh dlya radikal'noj (skorost' polimerizatsii proportsional'na pervoj stepeni skorosti initsiirovaniya; ehnergiya aktivatsii ochen' mala; ket ingibirovaniya kislorodom). Tem ne menee ehta polimerizatsiya yavlyaetsya, vidimo, radikal'noj. K takomu vyvodu my prishli na osnove issledovaniya initsiirovaniya polimerizatsii atsetilenovykh uglevodorodov tipichno radikal'nymi initsiatorami - perekis'yu benzoila i dinitrilom azoizomaslyanoj kisloty. V ehtoj svyazi izuchalis' osobennosti kinetiki i mekhanizma raspada perekisi v prisutstvii atsetilenovykh uglevodorodov (naprimer, fenilatsetilena, dejtero-fenilatsetilena i metilfenilatsetilena). Izuchalis' takzhe kinetika radiatsionnoj sopolimerizatsii fenilatsetilena s razlichnymi vinilovymi monomerami i sostav sopolimerov pri razlichnykh iskhodnykh smesyakh. EHti dannye, a takzhe rezul'taty izucheniya kinetiki ingibirovannoj polimerizatsii fenilatsetilena (ingibitor - benzokhinon) ukazyvayut na maluyu reaktsionnuyu spooobnost' fenilatsetilenovogo radikala. Sil'nye otkloneniya ot pravila additivnosti pri radiatsionnoj polimerizatsii v razlichnykh rastvoritelyakh svidetel'stvuyut o nalichii sil'nogo perenosa ehnergii k atsetilenovym uglevodorodam i ikh polimeram. (author)

  18. Radiation Synthesis of Stannous Dibromodibutyl; Synthese radiochimique de l'etain dibromopibutyle; Radiatsionno-khimicheskij sintez dibromdibutilolova; Sintesis radioquimica del dffiromodibutilestano

    Energy Technology Data Exchange (ETDEWEB)

    Abramova, L. V.; Vereshchinskij, I. V.; Kocheshkov, K. A.; Miretskij, V. Yu.; Pozdneev, V. V.; Ryabukhin, Yu. S.; Sheverdina, N. I.

    1963-11-15

    nerzhaveyushchej stali ob''emom 2-1) byl snabzhen meshalkoj. Ustanovka montirovalas' na istochnike {gamma}-izlucheniya Co{sup 60}. Opyty provodilis' pri temperature 80 {+-} 5{sup o}C i atmosfernom davlenii. Moshchnost' dozy sostavlyala {approx}50 rad/sek (po ferrosul'fatnomu dozimetru). Primenyalos' metallicheskoe poroshkoobraznoe olovo i bromistyj butil raznoj stepeni ochistki. Komponenty reaktsii bralis' v razlichnykh sootnosheniyakh. Ustanovlennoe chto v dannykh usloviyakh protekaet napravlennaya radiatsionnokhimicheskaya reaktsiya, v rezul'tate kotoroj v osnovnom obrazuetsya dibromdibutilolovo s vysokim kolichestvennym vykhodom. Pokazano, chto protsess protekaet s induktsionnym periodom, dlitel'nost' kotorogo zavisit ot chistoty iskhodnogo bromistogo butila. EHtot zhe faktor zametno vliyaet ne skorost' obrazovaniya tselevogo produkta. Najdeno, chto olovo, ne voshedshee v reaktsiyu, mozhet povtorno ispol'zovat'sya dlya polucheniya dibromdibutilolova. Pri ehtom polnost'yu ustranyaetsya induktsionnyj period. Otmechennye osobennosti sozdayut predposylki dlya provedeniya nepreryvnogo protsessa. Predlozhen mekhanizm reaktsij dlya ob{sup y}asneniya zakonomernostej protsessa, protekayushchego so znachitel'nym radiatsionno-khimicheskim vykhodom. (author)

  19. Standardization of Radionuclides in the Electrotechnical Laboratory, Tokyo; Etalonnage des radionuclides au Laboratoire d'electrotechniqu e de Tokyo; Standartizatsiya radioizotopov v ehlektrotekhnichesko j laboratorii v Tokio; Normalizacion de radionuclidos en el Laboratorio de Electrotecnica de Tokio

    Energy Technology Data Exchange (ETDEWEB)

    Naito, Masashi; Inouye, Yajiro; Yura, Osamu [Electrotechnical Laboratory, Tokyo (Japan)

    1960-06-15

    metodo se midio la actividad de los nuclidos Sr{sup 90}-Y{sup 90}, So{sup 60} y Cs{sup 187}. La preci- sion de las mediciones fue del orden de +{+-} 2%. 2) Recuento {alpha} 2 {pi}. - Se midio la radiactividad de muestras de RaD + RaE + RaF, U{sup 238} y Po{sup 210} utilizando el mismo aparato que en el metodo de recuento |3 4 l. La precision de las mediciones fue de {+-} 2, {+-} 1 y {+-} 1%, respectivamente. 3) Recuento por coincidencias. - Para aplicar este metodo, se emplearon aparatos de recuento {beta}-{gamma}-y {gamma}-{gamma}. Como detector de rayos {gamma} se utilizo un contador de centeleo [cristal de Nal (TI) de 1 pulgada de diametro y 1 pulgada de largo] y como detector de rayos{beta} un contador Geiger-Mueller. Recientemente, para estudiar las diferencias existentes entre el metodo de recuento {beta} 4{pi}y el de coincidencias, en lugar de utilizar un contador Geiger- Mueller, los autores recurrieron a un modelo especial de contador proporcional {beta} 4 {pi}, que puede ser tambien empleado independientemente , es decir, sin los circuitos de coincidencia. Los resultados obtenidos con el metodo de coinci dencias {beta}-{gamma} difieren ligeramente (3-4%) de los alcanzados con el metodo {beta} 4 {pi} La discrepancia puede deberse a la autoabsorcion. En cambio, los resultados del metodo de coincidencias {gamma}-{gamma} para el So{sup 60} concuerdan con los obtenidos al aplicar el metodo de coincidencias {beta}-{gamma}. (author) [Russian] Posle 1953 goda v ehlektrotekhnichesko j laboratorii s pomoshch'yu vychislitel'nog o metoda 4 {pi} {beta}-scheta i metoda sovpadenij bylo proizvedeno absolyutnoe izmerenie nekotorykh izotopov. Podrobnosti metoda vychislenij v nashej laboratorii budut opisany v sleduyushchem poryadke: 1) Metod 4 ({pi}) ({beta})-scheta. Byl skonstruirova n zvonkovyj gazovyj pro- portsional'nyj schetchik 4 ({pi}) ({beta})-izluchenij. Byli issledovany ego vychislitel'nye kharakteristiki , v osobennosti nadezhnost' takikh primenyaemykh gazov. Pri

  20. The Technology and Applications of Large Fission Product Beta Sources; Technologie et applications des grandes sources beta de fission; Tekhnologiya i primenenie krupnykh istochnikov beta-izluchenij, ispuskaemykh produktami deleniya; Tecnologia y utilizacion de los productos de fision como fuentes de irradiacion beta de elevada intensidad

    Energy Technology Data Exchange (ETDEWEB)

    Silverman, Joseph [Radiation Applications Incorporated (United States)

    1960-07-15

    ) [Russian] Beta-izluchatel i ne vkhodili ran'she v raschet v kachestve krupnykh istochnikov izlucheniya, tak kak v proshlom predstavlyayushchie interes protsessy oblucheniya osnovyvalis' na ispol'zovanii chastits, obladayushchikh sposobnost'yu glubokogo proniknoveniya; poehtomu glavnoe vnimanie sosredotochivalos' na ispol'zovanii gamma-izluchenij i iskusstvenno uskorennykh ehlektronov. Okolo chetyrekh let tomu nazad stalo ochevidnym, chto otkryvaetsya shirokaya oblast' vozmozhnykh primenenij, svyazannykh s poverkhnostnym oblucheniem, kak naprimer, izmenenie poverkhnosti obrazovavshegos ya sloya plastmassy putem sopolimerizatsionnogo narashchivaniya i poverkhnostnoj pasterizatsii pishchevykh produktov. Dlya ehtikh primenenij proniknovenie v glubinu yavlyaetsya neehkonomnym, a vozmozhno i vrednym. Est'eshche dve drugie oblasti, v kotorykh proizvedennye mekhanicheskim putem ehlektrony ne ochen' podkhodyat: khimicheskij sintez v nakhodyashchikhsya pod davleniem sosudakh s primeneniem oblucheniya i nekotorye vidy tsepnykh reaktsij so svobodnymi radikalami, dlya kotorykh proizvoditel'nost ' na kilovatt umen'shaetsya proportsional'no kvadratnomu kornyu moshchnosti dozy. Istochniki beta-izluchenij s shirokim polem pokazali ochevidnye potentsial'ny e preimushchestva dlya vsekh ehtikh operatsij i poskol'ku oni poluchayutsya v bol'shikh kolichestvakh za schet protsessov deleniya, to predstavlyalos ' tselesoobrazny m sdelat' tshchatel'nuyu pereotsenku vozmozhnostej ikh primeneniya. Vvidu ehtogo pod pokrovitel'stvom Komissii po atomnoj ehnergii SSHA bylo proizvedeno issledovanie primenenij i tekhnologii istochnikov beta-izluchenij, ispuskaemykh produktami deleniya. EHto issledovanie privelo k sleduyushchim rezul'tatam: 1. Otkryvayutsya perspektivny e vozmozhnosti primeneniya v kommercheskom masshtabe istochnikov beta-izluchenij, ispuskaemykh produktami deleniya, v oblasti oblucheniya produktov, v osobennosti dlya izmeneniya putem sopolimerizatsionnogo narashchivaniya obrazovavshikhsya

  1. Ranges of Iodine and Bromine Isotopes Produced in the Interaction of High-Energy Protons with Uranium; Isotopes de l'Iode et du Brome Produits par l'Interaction de Protons de Haute Energie avec l'Uranium; 041f 0420 041e 0411 0415 0413 0418 0418 0417 041e 0422 041e 041f 041e 0412 0419 041e 0414 0410 0418 0411 0420 041e 041c 0410 , 041f 041e 041b 0423 0427 0415 041d 041d 042b 0425 041f 0420 0418 0412 0417 0410 0418 041c 041e 0414 0415 0419 0421 0422 0412 0418 0418 041f 0420 041e - 0422 041e 041d 041e 0412 0411 041e 041b 042c 0428 041e 0419 042d 041d 0415 0420 0413 0418 0418 0421 0423 0420 0410 041d 041e 041c ; Alcance de los Isotopos del Yodo y del Bromo Producidos en la Interaccion de Protones de Alta Energia con el Uranio

    Energy Technology Data Exchange (ETDEWEB)

    Brandt, R. [CERN, Geneva (Switzerland); Max Planck Institut fuer Kernphysik, Heidelberg, Federal Republic of Germany (Germany)

    1965-07-15

    'noe uvelichenie funkcii vozbuzhdenija svyshe 1 Bjev. Izotopy broma po sushhestvu imejut tu zhe samuju zavisimost' probegov, Krivaja vyhoda izotopov broma iz urana imeet te zhe samye osnovnye osobennosti, chto i sootvetstvujushhaja krivaja dlja joda. Sil'noe uvelichenie proizvodstva izotopov s nedostatkom nejtronov snova nabljudaetsja pri bol'shih jenergijah bombardirujushhih chastic. Obsuzhdenie kasaetsja glavnym obrazom jetih izotopov s nedostatkom nejtronov. Oni poluchajutsja po sushhestvu tol'ko pri jenergii svyshe 1 Bjev, i ih probeg pri bolee vysokoj jenergii bombardirujushhih chastic sostavljaet tol'ko priblizitel'no polovinu probega obychnyh produktov delenija, chto govorit o tom, chto oni poluchajutsja ne v rezul'tate, delenija, a drugim putem. Jeti vyvody obsuzhdajutsja v svete modelej ''rasshheplenija'' i ''fragmentacii'', prichem daetsja novoe opredelenie jetim terminam. (author)

  2. Critical Survey of the Analysis of Microscopic Distribution of some Bone-Seeking Radionuclides and Assessment of Absorbed Dose; Analyse de la Distribution Microscopique de Radionucleides Osteophiles et Determination de la Dose Absorbee; Kriticheskij obzor dannykh analiza mikroskopicheskogo raspredeleniya otkladyvayushchikhsya v kostyakh radioizotopov i opredelenie pogloshchennoj dozy; Estudio Critico de la Distribucion Microscopica de Algunos Radionuclidos Osteofilos y Evaluacion de la Dosis Absorbida

    Energy Technology Data Exchange (ETDEWEB)

    Jee, W. S.S.

    1964-10-15

    raspredelenija'dozy, vkljuchajushhee opisanie neodnorodnogo raspredelenija radiacii, protivorechashhego prinjatoj teorii odnorodnogo raspredelenija, poluchennogo na osnovanii dannyh zaderzhki izotopov vo vsem organizme. Bez nekotorogo znanija mikroskopicheskogo raspredelenija dozy vo vremeni i prostranstve slishkom legko sdelat' nevernye vyvody i propustit' vazhnye zakljuchenija pri popytke poluchit' sravnitel'nye dannye o toksichnosti radioizotopov. Ob{sup e}m opublikovannoj literatury po izmereniju mikroskopicheskogo raspredelenija doz radiacii ochen' ogranichen, chto svjazano so slozhnost'ju problemy. Sushhestvujushhie metody vkljuchajut avto-radiografiju i ochen' trudoemki. Oni vkljuchajut takzhe podschet raspadov i mikrodensimetriju. Polnoe raspredelenie dozy dlja dannoj kosti vo vremeni i prostranstve javljaetsja ogromnoj zadachej. Mikroskopicheskoe raspredelenie v skelete otkladyvajushhihsja v kostjah izotopov (radij-226, stroncij-90, plutonij-239 i radioaktivnyj torij-228) sluzhit prekrasnoj illjustraciej slozhnosti problemy. Pervonachal'naja doza obluchenija i doza, izmenjajushhajasja so vremenem, opisany dlja radija i plutonija, v osobennosti podcherkivaetsja neodnorodnost' raspredelenija dozy v kostjah i razlichnyh uchastkah vnutri kosti. Naprimer, maksimal'nye poverhnostnye trabekuljarnye otlozhenija plutonija v pozvonkah v 1,5 raza vyshe, chem maksimal'nye koncentracii v trabekulah metafiza bedra. Kojefficient otnoshenija doz poverhnostnyh otlozhenij plutonija v razlichnyh uchastka distal'nogo otdela bedra raven: trabekuly metafiza - 3; jendostil'- 2,6; trabekuly jepifiza - 1,5; gaversovy kanaly - 1,2 i peristil' - t. Maksimal'nye lokalizovannye poverhnostnye otlozhenija v trabekulah pozvonkov v 35 - 66 raz vyshe rasschitannoj srednej moshhnosti dozy v rezul'tate zaderzhki izotopov v organizme. Obsuzhdajutsja izmenenija s techeniem vremeni nachal'noj neodnorodnoj lokalizacii radija i plutonija v otnoshenii haraktera kletochnogo vosproizvodstva kosti i poteri

  3. High-Volume Non-Destructive Test Applications at the Hanford Atomic Products Operation; Applications Industrielles des Essais Non Destructifs a l'Etablissement Nucleaire de Hanford; Provedenie bol'shogo chisla nedestruktivnykh ispytanii v ''khenford atomik prodakts opereishen''; Ensayos No Destructivos en Gran Escala Aplicados en Hanford

    Energy Technology Data Exchange (ETDEWEB)

    Worlton, D. C. [Pacific Northwest Laboratory, Battelle Memorial Institute, Richland, WA (United States)

    1965-10-15

    . Razrabotany novye jekonomicheskie sposoby poluchenija standartov po defektam, poskol'ku imejutsja chrezvychajno vazhnye metody, obespechivajushhie edinoobrazie dejstvujushhih harakteristik samih preobrazovatelej. Razrabotan pribor po avtomaticheskomu obsledovaniju trub, i vkratce izlagajutsja rezul'taty ego obychnogo ispol'zovanija po ispytaniju trub, obshhej dlinoj pochti 30 tys. futov. I, nakonec, rassmatrivaetsja metod tokov Fuko, razrabotannyj special'no dlja obsledovanija ustanovlennyh trub teploobmennika. Jetot metod neset v sebe novye osobennosti, on registriruet ukazanija o defektah na shkale oscillografa, razmery i konfiguracija kotorogo vskryvajut velichinu defekta, ego raspolozhenie v stenke truby i glubinu. Na diagramm registrirujutsja kolebanija shhupa i neopasnye petli trub i izgiby vmeste s harakternym obrazcom, chetko otlichajushhimsja ot nastojashhih defektov. Vkratce izlagajutsja rezul'taty primenenija jetih ispytanij dlja trub obshhej dlinoj 750 tys futov, ustanovlennyh v trudnyh polevyh uslovijah. (author)

  4. Reactor Physics Development for Advanced Gas-Cooled Reactors; Recherches en Physique des Reacteurs, pour des Reacteurs Perfectionnes Refroidis par un Gaz; Razrabotka metodov v oblasti reaktornoj fiziki dlya usovershenstvovannogo reaktora s gazovym okhlazhdeniem; Progresos de la Fisica de los Reactores de Tipo Avanzado Refrigerados por Gas

    Energy Technology Data Exchange (ETDEWEB)

    Moore, J. [United Kingdom Atomic Energy Authority (United Kingdom)

    1964-04-15

    reshetki dlja reaktora AGR i proverki teoreticheskih metodov, razrabotannyh dlja geterogennyh aktivnyh zon reaktorov, ispol'zovalis' kriticheskaja ustanovka APEX i reaktor nulevoj moshhnosti HERO s obychnymi raspolozhenijami reshetok , i kombinacijami izmenjajushhih rabotu reaktora jelementov, naprimer regulirujushhih sterzhnej. Teoreticheskie metody, razrabotannye i primenjavshiesja do nastojashhego vremeni, izvestny kak ''getrekontrol'' i FTD2. Jeksperimenty imeli cel'ju podrobno proverit' osobennosti jetih metodov, i dlja opredelenija soglasovannogo mezhdu soboj rjada konstant reshetki, sootvetstvujushhih rezul'tatam jeksperimentov, byli proanalizirovany rezul'taty izmerenij, vypolnennyh na rjade ''reaktornyh'' aktivnyh zon razlichnogo razmera v ustanovkah APEX i HERO. Jeti chisto jempiricheskie konstanty byli zatem ispol'zovany v metodah getrekontrol' i FTD2 dlja uspeshnogo planirovanija vvoda v jekspluataciju i vybora vida nagruzki dlja Uindskejlskogo AGR. Daetsja ssylka na jeksperimental'nye metody, kotorye byli provereny ilj special'no razrabotany dlja reshenija vstretivshihsja problem. Osobyj interes predstavljajut metody, ispol'zovavshiesja dlja izmerenija jeffektov reaktivnosti v reaktorah APEX, HERO i AGR i dlja opredelenija dannyh tonkoj struktury i raspredelenija jenergij v slozhnyh toplivnyh sborkah. Osushhestvljaemye v nastojashhee vremja teoreticheskie raboty skoncentrirovany, glavnym obrazom, na razrabotke al'ternativnogo metoda v otnoshenii ''getrekontrolja'' i FTD2 dlja rascheta aktivnyh zon reaktora posle znachitel'nogo vygoranija topliva. Na jetom zhe budut skoncentrirovany raboty i v budushhem. Zadachej programmy jeksperimentov na ustanovke HERO javljaetsja ispytanie jetih metodov na slozhnyh aktivnyh zonah, vkljuchaja aktivnye zony s toplivom, proizvodjashhim plutonij. Dopolnitel'nye dannye o vlijanii plutonija bydut polucheny blagodarja jekspluatacii reaktora AGR i fizicheskim izmerenijam obluchennogo topliva. (author)

  5. Some Uses of Radioisotopes and Radiations in Entomology; Quelques emplois des radioelements et des rayonnements en entomologie; Nekotorye vidy primeneniya radioehlementov i oblucheniya v ehntomologii; Algunas aplicaciones de los radioelementos y de las radiaciones en entomologia

    Energy Technology Data Exchange (ETDEWEB)

    Courtois, G. [Centre d' Etudes Nucleaires de Saclay (France); Lecomte, J. [Institut National de la Recherche Agronomique, Station de Recherches sur l' Abeille et les Insectes Sociaux, Bures-Sur-Yvette (France)

    1963-09-15

    dosificar el potasio en las hormigas y en las abejas. Los autores han ensayado la marcacion de acrididos con {sup 192}Ir y describen en la memoria los resultados obtenidos. Se ha hecho tambien un estudio de la distribucion de ciertos radioisotopos ( {sup 32}P y {sup 35}S) en el cuerpo de la abeja por medio del metodo autorradiografico. (author) [Russian] Stat'ya soderkhit obzor metodov primeneniya radioehlementov v ehntomologii, razrabotannykh v nashikh dvukh tsentrakh v techenie poslednikh let. Pervye raboty otnosilis' k pchelam i v osobennosti k dal'nosti poletov pchel-sborshchits iz pchelosem'i. Issledovanie provodilos' s pomoshch'yu mecheniya izotopom Au{sup 198}. Prodolzheniem rabot po opredeleniyu dozy, poluchennoj osob'yu v protsesse mecheniya, yavilos' opredelenie radiorezistentnosti pchely i letal'noj dozy, lezhashchej v predelakh 90 000 p. Au{sup 198} byl takzhe ispol'zovan dlya issledovaniya obmena pishchej vnutri ul'ya. Vmeste s tem,dlya izucheniya obmena pishchej vnutri ul'ev mezhdu rabochimi osobyami (muzhskimi osobyami, rabochimi pchelami, matkami) ili mezhdu razlichnymi royami primenyalsya R{sup 92}. Nedavno analogichnye issledovaniya trofilaksii byli provedeny na osakh. Au{sup 188} byl takzhe osnovnym radioehlementom v rabote s muravejnikami. Naibolee interesnym rezul'tatom pervogo issledovaniya yavilos' otkrytie obmena pishchej mezhdu muravejnikami, otstoyashchimi drug ot druga na rasstoyanii svyshe 50 m, i raznymi vidami murav'ev (Formica rufa i Formica polyctena). V protsesse vtorogo issledovaniya, s pomoshch'yu mecheniya puti dvizheniya murav'ev, a ne samogo muravejnika, bylo vyyavleno raspredelenie obyazannostej vnutri muravejnika. Mechenye murav'i sledovali po odnomu i tomu zhe marshrutu i redko obmenivalis' s drugimi osobyami toj zhe kolonii. V protsesse ehtogo opyta uzhe do mecheniya byla ustanovlena anormal'naya radioaktivnost' murav'ev, obuslovlennaya prezhde vsego nalichiem (Sr + Nb){sup 95}. EHto otkrytie govorit o tendentsii k nakopleniyu v

  6. Research with a Natural-Uranium Light-Water Subcritical Assembly; Recherches au Moyen d'un Ensemble Sous-Critique a Uranium Naturel et a Eau Ordinaire; Issledovaniya na podkriticheskoj sborke,rabotayushchej na prirodnom urane i obychnoj vode; Investigaciones con un Conjunto Subcritico de Uranio Natural y Agua Ligera

    Energy Technology Data Exchange (ETDEWEB)

    Koskinen, H. [Institute of Technical Physics, Otaniemi (Finland)

    1964-02-15

    novym. Chast' ego nosit predvaritel'nyj harakter, poskol'ku jeksperimenty i obrabotka dannyh eshhe ne zakoncheny. Rabota na sborke koncentriruetsja na dvuh osnovnyh zadachah, a imenno: 1. Jeksperimental'noe izuchenie prigodnosti metodov rascheta, ispol'zuemyh,v chastnosti, v sluchajah osoboj geometrii (neravnomernoe raspredelenie topliva, konfiguracii podkriticheskoj sborki, granicy osoboj formy i t.d.). Teoreticheskoe issledovanie zdes' zachastuju privodit k nekotorym trudnostjam, svjazannym s konvergenciej. Pojetomu neobhodimo sravnenie s raspredelenijami izmerennyh potokov. 2. Izuchenie osobyh svojstv reshetok, zagruzhennyh prirodnym uranom i obychnoj vodoj, i v osobennosti prigodnosti neskol'kih gruppovyh modelej zamedlenija dlja odnorodnyh i neodnorodnyh struktur aktivnoj zony . Schitaetsja, chto sborka s odnim tol'ko istochnikom spontannogo delenija osobenno pri- go'dna dlja provedenija issledovanij takogo tipa, esli my prenebregaem plohoj statistikoj. Ob{sup j}asnjaetsja jeto dvumja prichinami: 1. Spektr pervichnogo istochnika mozhno schitat' identichnym so spektrom vyzvannogo delenija, pojetomu otsutstvujut perehodnye izmenenija jenergii, podobnye tem, kotorye nabljudajutsja v sluchae ispol'zovanija istochnika bystryh nejtronov. 2. Prostranstvennaja moshhnost' pervichnogo istochnika proporcional'na poperechnomu secheniju delenija topliva, kogda reshetka takzhe raschityvaetsja kak funkcija prostranstvennyh koordinat. Takaja harakternaja cherta takzhe pridaet prostotu forme uravnenij potoka i vo mnogih sluchajah shodstvo s kriticheskimi sistemami. V rezul'tate provedenija tshhatel'nogo analiza raspredelenija potokov v takoj sisteme mozhno poluchit' informaciju otnositel'no prigodnosti special'nyh modelej zamedlenija. Vozmozhno takzhe poluchit' raz{sup j}asnenie takih voprosov, kak delenie pod dejstviem bystryh nejtronov vzaimodejstvija i verojatnost' rezonansnoj utechki, zavisimoj ot prostranstva. Po mneniju avtora, podkriticheskaja sborka s zhidkim zamedlitelem

  7. Spectroscopic and thermodynamic study of the complexation of Cm(III) and Eu(III) with hydrophilic bis-triazinyl pyridines

    International Nuclear Information System (INIS)

    Ruff, Christian

    2013-01-01

    In the present work the complexation of Cm(III) and Eu(III) with a hydrophilic 2,6-bis-(1,2,4-triazinyl)-pyridine (aq-BTP) is studied. Aq-BTP complexes actinides(III) selectively over lanthanides(III) in nitric acid solution. The object of this work is the identification and the spectroscopic and thermodynamic characterization of the Cm(III) and Eu(III) complex species present in solution. The results should contribute to a better fundamental understanding of the driving force behind BTPs selectivity towards trivalent actinides on a molecular level. Time-resolved laser fluorescence spectroscopy (TRLFS), luminescence and UV/Vis spectroscopy are applied. Information on the structure of M(III)-aq-BTP complex species is obtained from density functional theory. Three different M(III) complex species containing one, two or three aq-BTP ligands are identified in H 2 O at pH 3.0. Relative fluorescence intensity factors are determined for each of the [M(aq-BTP) n ] complexes (M = Cm(III)/Eu(III), n = 1 - 3). These factors are required to quantify the complexes. The stability constant logβ 3 of the [Cm(aq-BTP) 3 ] complex (which is the one relevant to extraction processes) is two orders of magnitude higher than that of the corresponding Eu(III) complex. This difference is in agreement with the separation factor (SF Am(III)/Eu(III) = 150) determined experimentally by liquid-liquid extraction. The difference in the stability constants originates from the different reaction enthalpies for the formation of the [M(aq-BTP) 3 ] complexes. These results represent the thermodynamic driving force for the aq-BTPs selectivity towards trivalent actinides over lanthanides. Comparing the stability constants of the [M(aq-BTP) n ] species (M = Cm(III)/Eu(III), n = 1 - 3) shows an increasing selectivity with increasing number of coordinated aq-BTP ligands. Hence, high selectivity is achieved if the f-element ions are fully coordinated by nine N-donor atoms (three aq-BTP ligands). A less

  8. KURRI progress report 2011. April 2011 - March 2012

    International Nuclear Information System (INIS)

    2012-01-01

    , application studies on effective use of F-elements, science and engineering of unstable nuclei and their uses on condensed matter physics, abnormal aggregation of proteins by post-translation modifications and study of repair mechanism, and development of neutron imaging application. Collaboration research was on slow neutron physics and neutron scattering, nuclear physics and nuclear data, reactor physics and reactor engineering, material science and radiation effects, geochemistry and environmental science, life science and medical science, neutron capture therapy, TRU and nuclear chemistry, and accelerator physics. (T. Tanaka)

  9. Uranyl and/or rare-earth mellitates in extended organic-inorganic networks: A unique case of hetero-metallic cation-cation interaction with U-VI=O-Ln(III) bonding (Ln = Ce, Nd)

    International Nuclear Information System (INIS)

    Volkringer, Christophe; Henry, Natacha; Grandjean, Stephane; Loiseau, Thierry

    2012-01-01

    A series of uranyl and lanthanide (trivalent Ce, Nd) mellitates (mel) has been hydrothermally synthesized in aqueous solvent. Mixtures of these 4f and 5f elements also revealed the formation of a rare case of lanthanide-uranyl coordination polymers. Their structures, determined by XRD single-crystal analysis, exhibit three distinct architectures. The pure lanthanide mellitate Ln 2 (H 2 O) 6 (mel) possesses a 3D framework built up from the connection of isolated LnO 6 (H 2 O) 3 polyhedra (tri-capped trigonal prism) through the mellitate ligand. The structure of the uranyl mellitate (UO 2 ) 3 (H 2 O) 6 - (mel).11.5H 2 O is lamellar and consists of 8-fold coordinated uranium atoms linked to each other through the organic ligand giving rise to the formation of a 2D 3 6 net. The third structural type, (UO 2 ) 2 Ln(OH)(H 2 O) 3 (mel).2.5H 2 O, involves direct oxygen bondings between the lanthanide and uranyl centers, with the isolation of a hetero-metallic dinuclear motif. The 9-fold coordinated Ln cation, LnO 5 (OH)(H 2 O) 3 , is linked to the 7-fold coordinated uranyl (UO 2 )O-4(OH) (pentagonal bipyramid) via one μ 2 -hydroxo group and one μ 2 -oxo group. The latter is shared between the uranyl bonding (U=O = 1.777(4)1.779(6) angstrom) and a long Ln-O bonding (Ce-O = 2.822(4) angstrom; Nd-O = 2.792(6) angstrom). This unusual linkage is a unique illustration of the so-called cation cation interaction associating 4f and 5f metals. The dinuclear motif is then further connected through the mellitate ligand, and this generates organic inorganic layers that are linked to each other via discrete uranyl (UO 2 )O 4 units (square bipyramid), which ensure the three-dimensional cohesion of the structure. The mixed U-Ln carboxylate is thermally decomposed from 260 to 280 degrees C and then transformed into the basic uranium oxide (U 3 O 8 ) together with U-Ln oxide with the fluorite structural type ('(Ln,U)O 2 '). At 1400 degrees C, only fluorite type '(Ln,U)O 2 ' is formed with

  10. Pulse radiolysis study on solvated electrons in ionic liquid with controlling water content

    International Nuclear Information System (INIS)

    Yang Jinfeng; Kondoh, T.; Yoshida, Y.; Nagaishi, R.

    2006-01-01

    Room-temperature ionic liquids, which are nonvolatile and nonflammable, have been proposed as 'green solvents' for new applications in chemical synthesis, separation chemistry, electrochemistry and other areas. In the separation chemistry, the hydrophobic ionic liquids have been practically expected to be alternative to traditional organic solvents for solvent extraction of 4f and 5f elements from the viewpoints of the immiscibility in water, especially in the spent nuclear fuel reprocessing. However, the chemical reaction or kinetics studies are important to apply the ionic liquids for various processes. To understand the effects of ionic liquids on chemical reactions, pulse radiolysis studies of ionic liquid have been carried out on nanosecond scale by using a 27 MeV electron beam and an analyzing light source of xenon lamp. In the experiment, a hydrophobic ionic liquid of diethylmethyl(2-methoxy)ammonium-bis(trifluoromethanesulfonyl)imide (DEMMA-TFSI) salt was used. The ionic liquid of DEMMA-TFSI was prepared by reacting equimolar amounts of diethylmethyl(2-methoxy)ammonium chloride (C 10 H 20 F 6 N 2 O 5 S 2 Cl, >98%, Nisshinbo) with lithium bis(trifluoromethanesulfonyl)imide (LiN(SO 2 CF 3 ) 2 , SynQuest Labs., Inc.) in aqueous solutions at room temperature. The ionic liquid was separated from the aqueous phase, purified by repeated extractions with water to LiCl and excess reagent, and finally dried at 110 degree C under vacuum. The transient absorptions of the ionic liquid were measured at wavelengths from 350 to 1400 nm, in which two photodiodes of silicon ( 1000 nm) were used. The spectrum of solvated electrons in the ionic liquid of DEMMA-TFSI was obtained with an absorption peak of 1060 nm and a wide bandwidth of about 600 nm (FWHM). The decay constant of the solvated electrons in the ionic liquid was 1.54 x 10 7 s -1 , which is independent on the wavelength. The absorption peak of the spectrum was blue-shifted from 1060 to 780 nm with increasing water

  11. Thermodynamic study on the complexation of Trivalent actinide and lanthanide cation by N-donor ligands in homogeneous conditions; Etude thermodynamique de la complexation des ions actinide (III) et lanthanide (III) par des ligands polyazotes en milieu homogene

    Energy Technology Data Exchange (ETDEWEB)

    Miguirditchian, M

    2004-07-01

    Polydentate N-donor ligands, alone or combined with a synergic acid, may selectively extract minor actinides(III) from lanthanide(III) ions, allowing to develop separation processes of long-live radioelements. The aim of the researches carried out during this thesis was to better understand the chemical mechanisms of the complexation of f-elements by Adptz, a tridentate N-donor ligand, in homogeneous conditions. A thermodynamic approach was retained in order to estimate, from an energetic point of view, the influence of the different contributions to the reaction, and to acquire a complete set of thermodynamic data on this reaction. First, the influence of the nature of the cation on the thermodynamics was considered. The stability constants of the 1/1 complexes were systematically determined by UV-visible spectrophotometry for every lanthanide ion (except promethium) and for yttrium in a mixed solvent methanol/water in volume proportions 75/25%. The thermodynamic parameters ({delta}H{sup 0} {delta}{sup S}) of complexation were estimated by the van't Hoff method and by micro-calorimetry. The trends of the variations across the lanthanide series are compared with similar studies. The same methods were applied to the study of three actinide(III) cations: plutonium, americium and curium. The comparison of these values with those obtained for the lanthanides highlights the increase of stability of these complexes by a factor of 20 in favor of the actinide cations. This gap is explained by a more exothermic reaction and is associated, in the data interpretation, to a higher covalency of the actinide(III)-nitrogen bond. Then, the influence of the change of solvent composition on the thermodynamic of complexation was studied. The thermodynamic parameters of the complexation of europium(III) by Adptz were determined for several fractions of methanol. The stability of the complex formed increases with the percentage of methanol in the mixed solvent, owing to an

  12. U(SMes*)n, (n=3, 4) and Ln(SMes*)3 (Ln = La, Ce, Pr, Nd): Lanthanide(III)/actinide(III) differentiation in agostic interactions and an unprecedented eta(3) Ligation mode of the aryl-thiolate ligand, from X-ray diffraction and DFT analysis

    International Nuclear Information System (INIS)

    Roger, Mathieu; Barros, Noemi; Arliguie, Therese; Thuery, Pierre; Maron, Laurent; Ephritikhine, Michel

    2006-01-01

    Reaction of U(NEt 2 ) 4 with HS-2,4,6- t Bu 3 C 6 H 2 (HSMes*) gave U(SMes*) 3 (NEt 2 )(py) (1), whereas similar treatment of U[N(SiMe 3 )SiMe 2 CH 2 ][N(SiMe 3 ) 2 ] 2 afforded U(SMes*)[N(SiMe 3 ) 2 ] 3 (2) and U(SMes*) 3 [N(SiMe 3 ) 2 ]. The first neutral homoleptic uranium(IV) thiolate to have been crystallographically characterized, U(SMes*) 4 (4), was isolated from the reaction of U(BH 4 ) 4 and KSMes*. The first homoleptic thiolate complex of uranium(III), U(SMes*) 3 (5), was synthesized by proton-lysis of U[N(SiMe 3 ) 2 ] 3 with HSMes* in cyclohexane. The crystal structure of 5 exhibits the novel η 3 ligation mode for the aryl-thiolate ligand. Comparison of the crystal structure of 5 with those of the isomorphous lanthanide congeners Ln(SMes*) 3 (Ln) La, Ce, Pr, and Nd) indicates that the U-S, U-C ipso , and U-C ortho bond lengths are shorter than the corresponding ones in the 4f-element analogues, when taking into account the variation in the ionic radii of the metals. The distance between the uranium and the carbon atoms involved in the U center dot center dot center dot H-C ε agostic interaction of each thiolate ligand is shorter, by ∼ 0.05 angstrom, than that expected from a purely ionic bonding model. The lanthanide( III)/actinide(III) differentiation was analyzed by density functional theory (DFT). The nature of the M-S bond is shown to be ionic strongly polarized at the sulfur for M) U and ion-covalent (i.e. strongly ionic with low orbital interaction), for M) Ln. The strength of the U center dot center dot center dot H-C ε agostic interaction is proposed to be controlled by the maximization of the interaction between U + and S - under steric constraints. The η 3 ligation mode of the aryl-thiolate ligand is also obtained from DFT. (authors)

  13. U(SMes*)n, (n = 3, 4) and Ln(SMes*)3 (Ln = La, Ce, Pr, Nd): lanthanide(III)/actinide(III) differentiation in agostic interactions and an unprecedented eta3 ligation mode of the arylthiolate ligand, from X-ray diffraction and DFT analysis.

    Science.gov (United States)

    Roger, Mathieu; Barros, Noémi; Arliguie, Thérèse; Thuéry, Pierre; Maron, Laurent; Ephritikhine, Michel

    2006-07-12

    Reaction of U(NEt(2))(4) with HS-2,4,6-(t)Bu(3)C(6)H(2) (HSMes) gave U(SMes)(3)(NEt(2))(py) (1), whereas similar treatment of U[N(SiMe(3))SiMe(2)CH(2)][N(SiMe(3))(2)](2) afforded U(SMes)[N(SiMe(3))(2)](3) (2) and U(SMes)(3)[N(SiMe(3))(2)]. The first neutral homoleptic uranium(IV) thiolate to have been crystallographically characterized, U(SMes)(4) (4), was isolated from the reaction of U(BH(4))(4) and KSMes. The first homoleptic thiolate complex of uranium(III), U(SMes)(3) (5), was synthesized by protonolysis of U[N(SiMe(3))(2)](3) with HSMes in cyclohexane. The crystal structure of 5 exhibits the novel eta(3) ligation mode for the arylthiolate ligand. Comparison of the crystal structure of 5 with those of the isomorphous lanthanide congeners Ln(SMes)(3) (Ln = La, Ce, Pr, and Nd) indicates that the U-S, U-C(ipso)(), and U-C(ortho)() bond lengths are shorter than the corresponding ones in the 4f-element analogues, when taking into account the variation in the ionic radii of the metals. The distance between the uranium and the carbon atoms involved in the U...H-C epsilon agostic interaction of each thiolate ligand is shorter, by approximately 0.05 A, than that expected from a purely ionic bonding model. The lanthanide(III)/actinide(III) differentiation was analyzed by density functional theory (DFT). The nature of the M-S bond is shown to be ionic strongly polarized at the sulfur for M = U and iono-covalent (i.e. strongly ionic with low orbital interaction), for M = Ln. The strength of the U...H-C epsilon agostic interaction is proposed to be controlled by the maximization of the interaction between U(+) and S(-) under steric constraints. The eta(3) ligation mode of the arylthiolate ligand is also obtained from DFT.

  14. Feasible and realiable ab initio atomistic modeling for nuclear waste management

    Energy Technology Data Exchange (ETDEWEB)

    Beridze, George

    2016-07-01

    The studies in this PhD dissertation focus on finding a computationally feasible ab initio methodology which would make the reliable first principle atomistic modeling of nuclear materials possible. Here we tested the performance of the different DFT functionals and the DFT-based methods that explicitly account for the electronic correlations, such as the DFT+U approach, for prediction of structural and thermochemical properties of lanthanide- and actinide-bearing materials. In the previous studies, the value of the Hubbard U parameter, required by the DFT+U method, was often guessed or empirically derived. We applied and extensively tested the recently developed ab initio methods such as the constrained local density approximation (cLDA) and the constrained random phase approximation (cRPA), to compute the Hubbard U parameter values from first principles, thus making the DFT+U method a real it ab initio parameter free approach. Our successful benchmarking studies of the parameter-free DFT+U method, for prediction of the structures and the reaction enthalpies of actinide- and lanthanide-bearing molecular compounds and solids indicate, that the linear response method (cLDA) provides a very good, and consistent with the cRPA prediction, estimate of the Hubbard U parameter. In particular, we found that the Hubbard U parameter value, which describes the strength of the on-site Coulomb repulsion between f-electrons, depends strongly on the oxidation state of the f-element, its local bonding environment and crystalline structure of the materials, which has never been considered in such detail before. We have shown, that the applied computational approach substantially, if not dramatically, reduces the error of the predicted reaction enthalpies making the accuracy of the prediction comparable with the uncertainty of the computational unfeasible, higher order methods of quantum chemistry, and experiments. The derived methodology resulted in various, already published

  15. Molecular and polymeric uranyl and thorium hybrid materials featuring methyl substituted pyrazole dicarboxylates and heterocyclic 1,3-diketones

    Science.gov (United States)

    Carter, Korey P.; Kerr, Andrew T.; Taydakov, Ilya V.; Cahill, Christopher L.

    2018-02-01

    A series of seven novel f-element bearing hybrid materials have been prepared from either methyl substituted 3,4 and 4,5-pyrazoledicarboxylic acids, or heterocyclic 1,3- diketonate ligands using hydrothermal conditions. Compounds 1, [UO2(C6H4N2O4)2(H2O)], and 3, [Th(C6H4N2O4)4(H2O)5]·H2O feature 1-Methyl-1H-pyrazole-3,4-dicarboxylate ligands (SVI-COOH 3,4), whereas 2, [UO2(C6H4N2O4)2(H2O)], and 4, [Th(C6H5N2O4)(OH)(H2O)6]2·2(C6H5N2O4)·3H2O feature 1-Methyl-1H-pyrazole-4,5-dicarboxylate moieties (SVI-COOH 4,5). Compounds 5, [UO2(C13H15N4O2)2(H2O)]·2H2O and 6, [UO2(C11H11N4O2)2(H2O)]·4.5H2O feature 1,3-bis(4-N1-methyl-pyrazolyl)propane-1,3-dione and 1,3-bis(4-N1,3-dimethyl-pyrazolyl)propane-1,3-dione respectively, whereas the heterometallic 7, [UO2(C11H11N4O2)2(CuCl2)(H2O)]·2H2O is formed by using 6 as a metalloligand starting material. Single crystal X-ray diffraction indicates that all coordination to either [UO2]2+ or Th(IV) metal centers is through O-donation as anticipated. Room temperature, solid-state luminescence studies indicate characteristic uranyl emissive behavior for 1 and 2, whereas those for 5 and 6 are weak and poorly resolved.

  16. Experimental studies and tests on An(III)/Ln(III) separation using the TODGA extractant

    Energy Technology Data Exchange (ETDEWEB)

    Heres, Xavier; Sorel, Christian; Miguirditchian, Manuel; Cames, Beatrice; Hill, Clement; Bisel, Isabelle; Espinoux, Denis; Viallesoubranne, Carole; Baron, Pascal; Lorrain, Brigitte [CEA/DEN/MAR/DRCP, Marcoule, BP17171, 30207 Bagnols/Ceze (France)

    2009-06-15

    Minor actinide recycling by separation and transmutation is worldwide considered as one of the most promising strategies to reduce the inventory of radioactive waste, thus contributing to make nuclear energy more sustainable. One of the different options investigated at the CEA Marcoule and within the ACSEPT project (a European collaborative project partly funded by the 7. EURATOM Framework Program) to separate trivalent minor actinide (Am(III)-Cf(III)) from the fission and activation products contained in PUREX raffinates is the TODGA process, which consists in: 1. Co-extracting trivalent 4f and 5f elements from highly acidic PUREX raffinates by a mixture of TODGA (tetraoctyl-diglycolamide) and TBP (tributyl-phosphate), dissolved in HTP (hydrogenated tetra-propene). 2. Selectively stripping the trivalent minor actinides by a hydrophilic poly-aminocarboxylic acid used as a complexing agent in a buffered aqueous solution, while the trivalent lanthanides are kept in the organic solvent thanks to a sodium nitrate salting-out effect. 3. Stripping the lanthanides in a diluted nitric acid solution. The major difficulty of this TODGA separation process is to tune the pH in a very narrow range of operating conditions in the second step, because of the high sensitivity of the performances of the flow-sheet vs pH. This difficulty was however overcome. This paper describes the development of the TODGA process from experimental studies to hot test implementation in shielded cells of the ATALANTE facility, including (i) the optimization of the extraction system (both the formulation of the organic solvent and those of the aqueous scrubbing and stripping solutions), (ii) the implementation of a cold test in small scale mixer-settlers in the G1 facility (MARCEL loop), using a surrogate feed composed of major fission products, (iii) the validation of some steps of the process, using a surrogate feed, spiked with Am-241 and Eu-152, and similar laboratory contactors (medium activity

  17. Water-soluble tetrapodal N, O ligands incorporating soft N-heterocycles for the selective complexation of Am(III) over Ln(III)

    Energy Technology Data Exchange (ETDEWEB)

    Heitzmann, M.; Gateau, Ch.; Delangle, P. [CEA Grenoble, Inac, Service de Chimie Inorganique et Biologique, UMR E 3 CEA UJF, FRE CNRS 3200, F-38054 Grenoble (France); Chareyre, L.; Miguirditchian, M.; Charbonnel, M.Ch. [CEA Marcoule, DEN, DRCP, SCPS, F-30207, Bagnols-sur-Ceze (France)

    2010-07-01

    A series of four water-soluble N, O-tetrapodal ligands derived from ethylenediamine, bearing hard acetate groups and soft N-heterocycles, either pyridine or pyrazine, was developed to study the impact of the softness of N-donors on the complexation properties with trivalent f ions. Two novel ligands of enhanced soft character, bearing three pyridines (L{sup 3py}) or three pyrazines (L{sup 3pz}), were synthesized and the related lanthanide complexes were studied in solution. The ligand containing three pyridyl-methyl moieties L{sup 3py} gives complexes with a coordination similar to EDTA, i.e. a hexa-dentate coordination mode as indicated by NMR and luminescence decays (q = 3) and stability constants in the range log {beta}{sub 110} = 6.99-9.3 (La-Lu). On the other hand, the softest molecule L{sup 3pz} forms much less stable complexes with log {beta}{sub 110} = 4.0-4.4 (La-Eu). The selective back-extraction of Am(III) from organic solutions containing 4f and 5f elements was tested with the four water-soluble complexing agents. The ligand L{sup 3pz} demonstrates poor stripping ability and selectivity. In contrast, the three ligands L{sup py}, L{sup pz} and L{sup 3py} give interesting back-extraction results with Eu/Am separation factors ranging from 36 to 46, which are significantly higher than with HEDTA. This exemplifies the role of the N-hetero-cycle softness in enhancing the separation between Am(III) and Eu(III). Interestingly, the pyrazine-based ligand, L{sup pz}, demonstrates the best stripping properties, with a distribution factor that approaches that of HEDTA in the same conditions (D{sub Am{approx}}0.3). This molecule is a good compromise between softness and hardness and forms complexes still stable at pH 3 due to its low basicity. (authors)

  18. Feasible and realiable ab initio atomistic modeling for nuclear waste management

    International Nuclear Information System (INIS)

    Beridze, George

    2016-01-01

    The studies in this PhD dissertation focus on finding a computationally feasible ab initio methodology which would make the reliable first principle atomistic modeling of nuclear materials possible. Here we tested the performance of the different DFT functionals and the DFT-based methods that explicitly account for the electronic correlations, such as the DFT+U approach, for prediction of structural and thermochemical properties of lanthanide- and actinide-bearing materials. In the previous studies, the value of the Hubbard U parameter, required by the DFT+U method, was often guessed or empirically derived. We applied and extensively tested the recently developed ab initio methods such as the constrained local density approximation (cLDA) and the constrained random phase approximation (cRPA), to compute the Hubbard U parameter values from first principles, thus making the DFT+U method a real it ab initio parameter free approach. Our successful benchmarking studies of the parameter-free DFT+U method, for prediction of the structures and the reaction enthalpies of actinide- and lanthanide-bearing molecular compounds and solids indicate, that the linear response method (cLDA) provides a very good, and consistent with the cRPA prediction, estimate of the Hubbard U parameter. In particular, we found that the Hubbard U parameter value, which describes the strength of the on-site Coulomb repulsion between f-electrons, depends strongly on the oxidation state of the f-element, its local bonding environment and crystalline structure of the materials, which has never been considered in such detail before. We have shown, that the applied computational approach substantially, if not dramatically, reduces the error of the predicted reaction enthalpies making the accuracy of the prediction comparable with the uncertainty of the computational unfeasible, higher order methods of quantum chemistry, and experiments. The derived methodology resulted in various, already published

  19. Uranium hetero-bimetallic complexes: synthesis, structure and magnetic properties

    International Nuclear Information System (INIS)

    Le Borgne, Th.

    2000-01-01

    The aim of this thesis is to synthesize molecular complexes with uranium and transition metal ions in close proximity, to determine the nature of the magnetic interaction between them. We decided to use Schiff bases as assembling ligands, which are unusual for uranium (IV). Although the simplest Schiff bases, such as H 2 Salen, lead to ligand exchange reactions, the bi-compartmental Schiff base H 4 L 6 (bis(3-hydroxy-salicylidene) - 2,2-dimethyl-propylene) allows the crystal structure determination of the complex [L 6 Cu(pyr)]U[L 6 Cu].2pyr, obtained by reaction of the metallo-ligand H 2 L 6 Cu with U(acac) 4 . In this manner, the complexes [L 6 Co(pyr)] 2 U and [L 6 Ni(pyr)] 2 U.pyr were also isolated, as well as the compounds in which the paramagnetic ions have been exchanged by the diamagnetic ions Zn II , Zr IV and Th IV ': [L 6 Zn(pyr)] 2 U, [L 6 Cu] 2 Zr and [L 6 Cu(pyr)]Th[L 6 Cu].2pyr. These complexes are the first which involve three metallic centres assembling by the means of a hexa-dentate Schiff base. The crystalline structures show, for all these complexes, the outstanding orthogonal arrangement of the two fragments L 6 M around the central atom which is in a dodecahedral environment of eight oxygen atoms of two Schiff bases. The syntheses of the isostructural complexes Cu2 II and Zn 2 U in which the uranium (IV) ion is close, in the first one, to the paramagnetic ion Cu II and, in the second one, to the diamagnetic ion Zn II , has allowed the use of the empiric method to determine the nature of the magnetic interaction between an f element and a transition metal. The comparison of the magnetic behaviour of two complexes Cu 2 U and Zn 2 U, expressed by the variation of χT vs T, reveals the ferromagnetic interaction in the heart of the triad Cu-U-Cu. The magnetic behaviour of the complexes Cu 2 Th et Cu 2 Zr which does not show any coupling between the two copper (II) ions and the weak antiferromagnetic interaction in the Ni 2 U compound, favour the

  20. Preparation and performance characterization of AlF{sub 3} as interface stabilizer coated Li{sub 1.24}Ni{sub 0.12}Co{sub 0.12}Mn{sub 0.56}O{sub 2} cathode for lithium-ion batteries

    Energy Technology Data Exchange (ETDEWEB)

    Ding, Jingjing; Lu, Zhongpei; Wu, Manman; Liu, Cong; Ji, Hongmei; Yang, Gang, E-mail: gyang@cslg.edu.cn

    2017-06-01

    Highlights: • AlF{sub 3} coated LNCM synthesized by self-propagating combustion method. • F element of AlF{sub 3} has weak interaction with LNCM to form stable coating layer. • AlF{sub 3} layer promotes the stability and lithium diffusion ability of LNCM. • LNCM@2(*)%AlF{sub 3} operated at 20 mA g{sup −1} delivers 223 mAh g{sup −1} at the 60th cycle. • LNCM@2%AlF{sub 3} operated at 55 °C delivers 219 mAh g{sup −1} at the 50th cycle. - Abstract: Li{sub 1.24}Ni{sub 0.12}Co{sub 0.12}Mn{sub 0.56}O{sub 2} (LNCM) with high specific capacity is a potential cathode for commercial lithium-ion batteries (LIBs). To improve the high-rate capacity and cyclic stability, LNCM sample is successfully coated by minor AlF{sub 3}. The crystal structure and electrochemical properties of the bare and coated samples are investigated by X-ray diffractometry (XRD), scanning and transmission electron microscopy (SEM, TEM), cyclic voltammetry (CV), galvanostatic intermittent titration technique (GITT), and charge/discharge measurements. The coating layer AlF{sub 3} efficiently plays a positive role in enhancing rate performance and cyclic stability of LNCM. At 0.5 A g{sup −1}, the specific discharge capacity of LNCM@2%AlF{sub 3} is 149 mAh g{sup −1} much higher than 35 mAh g{sup −1} in bare LNCM. At 20 mA g{sup −1}, the specific discharge capacity of LNCM@2%AlF{sub 3} is 223 mAh g{sup −1} at the 60th cycle in comparison with 203 mAh g{sup −1} in bare LNCM. Moreover, a proper AlF{sub 3} coating layer efficiently ensures the stability of LNCM cathode operated at higher temperature. LNCM@2%AlF{sub 3} operated at 55 °C remains 219 mAh g{sup −1} at the 50th cycle, much higher than bare LNCM only remains 99 mAh g{sup −1} at the 40th cycle.

  1. Thermal Neutron Spectral and Spatial Distributions in Light-Water-Moderated Uranium Lattices; Distributions Spectrale et Spatiale des Neutrons Thermiques dans des Reseaux a Uranium et a Eau Leger; Spektral'noe i prostranstvennoe raspredelenie teplovykh nejtronov v uranovykh reshetkakh s vodnym zamedlitelem; Distribuciones Espectral y Espacial de los Neutrones Termicos en los Reticulados de Uranio Moderados por Agua Ligera

    Energy Technology Data Exchange (ETDEWEB)

    Hardy, J.; Volpe, J. J.; Klein, D.; Schmidt, E.; Gelbard, E. [Bettis Atomic Power Laboratory, Pittsburgh, PA (United States)

    1964-02-15

    razlichnymi priblizhenijami k teorii perenosa i integral'nomu jadru rassejanija terlovyh nejtronov. Pervaja serija opytov zakljuchaetsja v izmerenii blok-jeffektov teplovyh nejtronov v raz- nyh jachejkah reshetki sborki TRH, reaktora s vodnym zamedlitelem na slegka obogashhennom urane s cilindricheskimi toplivnymi jelementami, raspolozhennymi po geksagonal'noj sisteme. Sravnivalis' dannye ob ispol'zovanii teplovyh nejtronov s dannymi, poluchennymi v Monte Karlo. Primenjalis' funkcii Radkovskogo i Nelkina. Funkcija vlijanija Radkovskogo daet priblizhenie pervogo porjadka, shiroko ispol'zuemoe pri proektirovanii reaktorov. Funk- cija vlijanija Nelkina predstavljaet soboj bolee novoe i bolee podrobnoe opisanie integral'- nogo jadra rassejanija. Poskol'ku raschetnye znachenija pogloshhenija teplovyh nejtronov zavisjat ot vybora in- tegral'nogo jadra rassejanija, v osobennosti esli jeto ne maksvellovskij spektr potokov nej- tronov, drugaja serija opytov po izmereniju aktivacii na sborke TRH prednaznachalas' dlja bolee neposredstvennogo opredelenija integral'nogo jadra rassejanija. Opyty provodilis' v uslovijah, pri kotoryh iskazhenie spektra v osnovnom vyzyvalos' ravnomernym otravleniem. Izmerenija provodilis' v zapolnennoj vodoj trubke diametrom 10sm v reshetke TRX. Stenka trubki byla napolnena poroshkom B{sup 10}, jeffektivno razryvaja svjaz' mezhdu vnutrennej poverh- nost'ju trubki i reshetkoj reaktora pri jenergii nizhe 10 kjev. Otnositel'nye znachenija aktivacii teplovymi nejtronami i radial'nye konfiguracii chuvstvitel'nyh v otnoshenii spektrov detektorov izmerjalis' v dvuh sluchajah s polucheniem sootvetstvenno pochti maksvellovskogo spektra (dlja chistoj vody) i spektra, sil'no iskazhen- nogo v rezul'tate otravlenija kadmiem. Dlja jetogo opyta raschety s kazhdoj funkciej provodilis' v gruppe jenergii 12 s pribli- zheniem P{sub 3} . V rezul'tate rascheta sobstvennyh znachenij prostranstvennyh form, jeksponen- cial'no raspadajushhihsja v letargii, kotorye podderzhivajutsja v

  2. The Economical Application of Non-Destructive Testing to Reactor Components, Especially Jacket Tubing; Avantages Economiques du Controle Non Destructif des Pieces de Reacteurs, Notamment des Tubes de Gainage; Ehkonomicheskoe primenenie nedestruktivnykh ispytanij dlya reaktornykh komponentov, v chastnosti obolochechnykh trub; Aplicacion en Condiciones Economicas de Ensayos No Destructivos a las Piezas de los Reactores, en Especial a los Tubos de Revestimiento

    Energy Technology Data Exchange (ETDEWEB)

    Renken, C. J. [Metallurgy Division Argonne National Laboratory Argonne, IL (United States)

    1965-10-15

    ', predostavljaemuju pro- vedeniem ispytanij bez razrushenija obolochki dlja sohranenija kachestva produkta na razlich- nyh stadijah processa izgotovlenija, a takzhe ispol'zovanie rezul'tatov ispytanie dlja togo, chtoby opredelit' te momenty, kotorye verojatnee v sego vyzovut defekty v komponente v processe izgotovlenija. Chashhe v sego poluchaetsja tak, chto ispytanie bez razrushenija obolochki v nachal'nyh stadijah izgotovlenija komponenta ne mozhet byt' zameshheno jekonomicheski vy- godno inache,esli voobshhe jeto vozmozhno, kak tol'ko putem obsledovanija komponenta v vide goto - vogo produkta ili polufabrikata. Privodjatsja primery dlja illjustracii jetoj tochki zrenija, oso -benno v otnoshenii sistemy trub dlja primenenija obolochki teplovydeljajushhego jelementa i primenenij v teploobmennikah. Primenenie razlichnyh ispytanij bez razrushenija obolochki obrazca podrobnym obrazom opisyvaetsja v programme razrabotok po izgotovleniju trub. Daetsja sravnenie rashodov na izgotovlenie i obsledovanie nekotoryh sistem trub, ispol'- zovavshihsja Argonnskoj nacional'noj laboratoriej dlja pokrytija jetih trubobolochkoj. Hotja obsledovanie komponenta v okonchatel'nom vide mozhet 'yt' svedeno do minimuma posredstvom takih procedur, odnako nel'zja vse jeti sluchai ustranit' celikom. Podrobnym obrazom obsuzhdaetsja jekonomicheskoe provedenie ispytanij plastinok i trub, v osobennosti poslednih. Obsuzhdenie vedetsja glavnym obrazom o komponentah iz nerzhavejushhej stali, cirkalloja i nekotoryh ogneupornyh metallicheskih splavah. Na raz- lichnyh primerah pokazyvaetsja, chto hotja ispol'zovanie radiografii i smachivajushhih rea- gentov mozhet okazat'sja ves'ma poleznym, a mozhet byt' dazhe i neobhodimym delom pri provedenii ispytanij, odnako objazatel'no, kak pravilo, sleduet provodit' tshhatel'noe o b - sledovanie tonkostennyh trub s pomoshh'ju libo ul'trazvuka, libo jelektromagnitnogo metoda kak s tochki zrenija tehnicheskih, tak i jekonomicheskih aspektov. Ob{sup j}asnjaetsja optimal'naja oblast

  3. Radioisotopes and Radiation in Animal and Plant Insect Pest Control; Emploi des radioisotopes et des rayonnements dans la lutte contre les insectes nuisibles aux plantes et aux animaux; Ispol'zovanie radioizotopov i radiashchi v bor'be s nasekomymi-vreditelyami rastenij i zhivotnykh; Utilizacion de los radioisotopos y de las radiaciones en la lucha contra los insectos nocivos para las plantas y los animales

    Energy Technology Data Exchange (ETDEWEB)

    Andreev, S. V.; Martens, B. K.; Samojlova, V. A.; Molchanova, Z. I. [Vsesoyuznyj Institut Zashchity Rastenij, Leningrad, SSSR (Russian Federation)

    1963-09-15

    . Krome togo, metod daet vozmozhnost' issledovat' slozhnejshij kompleks voprosov parazitizma i khishchnichestva (voprosy izucheniya pishchevykh tsiklov promekhutochnogo pitaniya i khemataksisa). Primenenie metoda samomarkirovki polevykh gryzunov s pomoshch'yu radioaktivnykh primanok pozvolilo ustanovit' razmery pishchevykh arealov. Ispol'zovanie pestitsidov, sintezirovannykh o radioaktivnymi izotopami, v sochetanii s metodom radiokhromatografii, flyuorometrii i drugimi pozvolilo issledovat' slozhnejshie biokhimicheskie protsessy, protekayushchie v rasteniyakh i nasekomykh pod vliyaniem toksikantov. Na primere fosfornoorganicheskikh soedinenij tipa tiofosa i metafosa byla ustanovlena skorost' gidroliza ehtikh insektitsidov v zavisimosti ot fazy razvitiya rasteniya i ego fiziologicheskogo sostoyaniya, a takkhe uslovij vneshnej sredy. Opredelena dlitel'nost' sokhraneniya ostatochnykh kolichestv toksikantov na sel'skokhozyajstvennoj produktsii v zavisimosti ot srokov khimicheskikh obrabotok. S pomoshch'yu radioaktivnykh izotopov vyyavleny osobennosti metaboliticheskikh protsessov, ustojchivykh i neustojchivykh k gerbitsidam rastenij. Vnesenie v pestitsidy izotopov s korotkim periodom poluraspada v indikatornykh kolichestvakh daet vozmozhnost' proizvodit' otsenku kachestva obrabotki semennogo materiala i posevov sel'skokhozyajstvennykh rastenij pestitsidami pri ispol'zovanii razlichnykh sistem opryskivatelej, a takzhe opredelyat' optimal'nye normy ikh raskhoda. Putem vozdejstviya ioniziruyushchikh izluchenij na ehntomopatogennye mikroorganizmy (Beauverla basslana Unill.) dokazana vozmozhnost' povysit' ikh virulentnost' v tselyakh uluchsheniya mikrobiologicheskogo metoda bor'by s vrednymi nasekomymi. Sterilizutatsee i letal'noe dejstvie ionizirudtsikh izluchenij mozhet byt' ispol'zovano kak aktivnoe sredstvo bor'by s vrednymi nasekomymi. Primeneniem gamma radiatsii ustanovleny sterilizukhkhtsie dozy dlya ryada nasekomykh-vreditelej zapasov (Calandra granarla L., Acanthoscelides

  4. Advanced Extraction Methods for Actinide/Lanthanide Separations

    International Nuclear Information System (INIS)

    Scott, M.J.

    2005-01-01

    high level liquid wastes and a general actinide clean-up procedure. The selectivity of the standard extractant for tetravalent actinides, (N,N-diisobutylcarbamoylmethyl) octylphenylphosphineoxide (CMPO), was markedly improved by the attachment of three CMPO-like functions onto a triphenoxymethane platform, and a ligand that is both highly selective and effective for An(IV) ions was isolated. A 10 fold excess of ligand will remove virtually all of the 4+ actinides from the acidic layer without extracting appreciable quantities of An(III) and Ln(III) unlike simple CMPO ligands. Inspired by the success of the DIAMEX industrial process for extractions, three new tripodal chelates bearing three diglycolamide and thiodiglycolamide units precisely arranged on a triphenoxymethane platform have been synthesized for an highly efficient extraction of trivalent f-element cations from nitric acid media. A single equivalent of ligand will remove 80% of the Ln(III) ion from the acidic layer since the ligand is perfectly suited to accommodate the tricapped trigonal prismatic geometry preferred by the metal center. The ligand is perhaps the most efficient binder available for the heavier lanthanides and due to this unique attribute, the extraction event can be easily followed by 1H NMR spectroscopy confirming the formation of a TPP complex. The most lipophilic di-n-butyl tris-diglycolamide was found to be a significantly weaker extractant in comparison to the di-isopropyl analogs. The tris-thiodiglycolamide derivative proved to be an ineffective chelate for f-elements and demonstrated the importance of the etheric oxygens in the metal binding. The results presented herein clearly demonstrate a cooperative action of these three ligating groups within a single molecule, confirmed by composition and structure of the extracted complexes, and since actinides prefer to have high coordination numbers, the ligands should be particularly adept at binding with three arms. The use of such an

  5. Advanced Extraction Methods for Actinide/Lanthanide Separations

    Energy Technology Data Exchange (ETDEWEB)

    Scott, M.J.

    2005-12-01

    high level liquid wastes and a general actinide clean-up procedure. The selectivity of the standard extractant for tetravalent actinides, (N,N-diisobutylcarbamoylmethyl) octylphenylphosphineoxide (CMPO), was markedly improved by the attachment of three CMPO-like functions onto a triphenoxymethane platform, and a ligand that is both highly selective and effective for An(IV) ions was isolated. A 10 fold excess of ligand will remove virtually all of the 4+ actinides from the acidic layer without extracting appreciable quantities of An(III) and Ln(III) unlike simple CMPO ligands. Inspired by the success of the DIAMEX industrial process for extractions, three new tripodal chelates bearing three diglycolamide and thiodiglycolamide units precisely arranged on a triphenoxymethane platform have been synthesized for an highly efficient extraction of trivalent f-element cations from nitric acid media. A single equivalent of ligand will remove 80% of the Ln(III) ion from the acidic layer since the ligand is perfectly suited to accommodate the tricapped trigonal prismatic geometry preferred by the metal center. The ligand is perhaps the most efficient binder available for the heavier lanthanides and due to this unique attribute, the extraction event can be easily followed by 1H NMR spectroscopy confirming the formation of a TPP complex. The most lipophilic di-n-butyl tris-diglycolamide was found to be a significantly weaker extractant in comparison to the di-isopropyl analogs. The tris-thiodiglycolamide derivative proved to be an ineffective chelate for f-elements and demonstrated the importance of the etheric oxygens in the metal binding. The results presented herein clearly demonstrate a cooperative action of these three ligating groups within a single molecule, confirmed by composition and structure of the extracted complexes, and since actinides prefer to have high coordination numbers, the ligands should be particularly adept at binding with three arms. The use of such an

  6. Institute of Energy and Climate Research IEK-6. Nuclear waste management report 2013/2014. Material science for nuclear waste management

    International Nuclear Information System (INIS)

    Neumeier, S.; Klinkenberg, M.; Bosbach, D.

    2016-01-01

    secondary phases for the long-term safety assessment is one of the major research topics in the institute. The fundamental understanding of a long-standing open issue regarding the thermodynamics of radium-barium-sulfate solid solutions and its applicability in long-term safety assessments for nuclear waste disposal could be resolved. This was achieved by a novel approach combining atomistic simulations, radiochemical batch-type laboratory experiments and modern analytical techniques supported by thermodynamic modelling allowing a reliable description of Ra solubility control by a (Ba,Ra)SO_4 solid solution. This research is supported by the Swedish waste management agency SKB. (2) A major step forward was achieved regarding the prediction of actinide- and lanthanide-bearing materials properties by atomistic simulations. Performance tests of the DFT+U method for calculations of f-element-bearing systems (the Hubbard U parameter derived from first principle methods) showed that this method, in contrast to standard DFT, results in exceptionally good predictions of the formation and reaction enthalpies as well as the structures of lanthanide- and actinide-bearing materials. (3) The actinide solid state chemistry group has been very active in recent years to unravel the crystal structure of actinide containing oxo-salts. From the 1101 new crystal structure entries in the ICSD crystal structure database between 2005 and 2012, Prof. Evgeny Alekseev has contributed to 98 entries (almost 10%).

  7. Institute of Energy and Climate Research IEK-6. Nuclear waste management report 2013/2014. Material science for nuclear waste management

    Energy Technology Data Exchange (ETDEWEB)

    Neumeier, S.; Klinkenberg, M.; Bosbach, D. (eds.)

    2016-07-01

    secondary phases for the long-term safety assessment is one of the major research topics in the institute. The fundamental understanding of a long-standing open issue regarding the thermodynamics of radium-barium-sulfate solid solutions and its applicability in long-term safety assessments for nuclear waste disposal could be resolved. This was achieved by a novel approach combining atomistic simulations, radiochemical batch-type laboratory experiments and modern analytical techniques supported by thermodynamic modelling allowing a reliable description of Ra solubility control by a (Ba,Ra)SO{sub 4} solid solution. This research is supported by the Swedish waste management agency SKB. (2) A major step forward was achieved regarding the prediction of actinide- and lanthanide-bearing materials properties by atomistic simulations. Performance tests of the DFT+U method for calculations of f-element-bearing systems (the Hubbard U parameter derived from first principle methods) showed that this method, in contrast to standard DFT, results in exceptionally good predictions of the formation and reaction enthalpies as well as the structures of lanthanide- and actinide-bearing materials. (3) The actinide solid state chemistry group has been very active in recent years to unravel the crystal structure of actinide containing oxo-salts. From the 1101 new crystal structure entries in the ICSD crystal structure database between 2005 and 2012, Prof. Evgeny Alekseev has contributed to 98 entries (almost 10%).

  8. Uranium hetero-bimetallic complexes: synthesis, structure and magnetic properties; Complexes heterobimetalliques de l'uranium: synthese, structure et proprietes magnetiques

    Energy Technology Data Exchange (ETDEWEB)

    Le Borgne, Th

    2000-10-04

    The aim of this thesis is to synthesize molecular complexes with uranium and transition metal ions in close proximity, to determine the nature of the magnetic interaction between them. We decided to use Schiff bases as assembling ligands, which are unusual for uranium (IV). Although the simplest Schiff bases, such as H{sub 2}Salen, lead to ligand exchange reactions, the bi-compartmental Schiff base H{sub 4}L{sup 6} (bis(3-hydroxy-salicylidene) - 2,2-dimethyl-propylene) allows the crystal structure determination of the complex [L{sup 6}Cu(pyr)]U[L{sup 6}Cu].2pyr, obtained by reaction of the metallo-ligand H{sub 2}L{sup 6}Cu with U(acac){sub 4}. In this manner, the complexes [L{sup 6}Co(pyr)]{sub 2}U and [L{sup 6}Ni(pyr)]{sub 2}U.pyr were also isolated, as well as the compounds in which the paramagnetic ions have been exchanged by the diamagnetic ions Zn{sup II}, Zr{sup IV} and Th{sup IV}': [L{sup 6}Zn(pyr)]{sub 2}U, [L{sup 6}Cu]{sub 2}Zr and [L{sup 6}Cu(pyr)]Th[L{sup 6}Cu].2pyr. These complexes are the first which involve three metallic centres assembling by the means of a hexa-dentate Schiff base. The crystalline structures show, for all these complexes, the outstanding orthogonal arrangement of the two fragments L{sup 6}M around the central atom which is in a dodecahedral environment of eight oxygen atoms of two Schiff bases. The syntheses of the isostructural complexes Cu2{sup II} and Zn{sub 2}U in which the uranium (IV) ion is close, in the first one, to the paramagnetic ion Cu{sup II} and, in the second one, to the diamagnetic ion Zn{sup II}, has allowed the use of the empiric method to determine the nature of the magnetic interaction between an f element and a transition metal. The comparison of the magnetic behaviour of two complexes Cu{sub 2}U and Zn{sub 2}U, expressed by the variation of {chi}T vs T, reveals the ferromagnetic interaction in the heart of the triad Cu-U-Cu. The magnetic behaviour of the complexes Cu{sub 2}Th et Cu{sub 2}Zr which does not

  9. Reactions of Hot Hydrogen Atoms with Ethylene. The Role of Excited Ethyl Radicals as Intermediate Products; Reactions des Atomes Chauds d'Hydrogene avec l'Ethylene. Le Role des Radicaux Ethyle Excites Comme Produits Intermediaires; Reaktsiya goryachikh atomov vodoroda s ehtilenom. Rol' vozbuzhdennykh ehtil'nykh radikalov kak promezhutochnykh produktov; Reacciones de Atomos Calientes de Hidrogeno con Etileno Papel de los Radicales Etilicos Excitados como Productos Intermedios

    Energy Technology Data Exchange (ETDEWEB)

    Dzantiev, B. G.; Shvedchikov, A. P. [Institut Himicheskoj Fiziki AN SSSR, SSSR (Russian Federation)

    1965-04-15

    temperatura sobre el rendimiento de C{sub 2}H{sub 6} y C{sub 4}H{sub 10} por radiolisis del C{sub 2}H{sub 4} y fotolisis de mezclas de C{sub 2}H{sub 4} -HI, los autores establecen una hipotesis sobre la formacion de radicales etilicos excitados (C{sub 2}H*{sub 5}). Estos ultimos se obtienen como resultado de la combinacion de atomos de hidrogeno calientes generados por radiolisis o por fotolisis, con el etileno: J* + C{sub 2}H{sub 4} = C{sub 2}H*{sub 5}. Demuestran que el radical C2Hf interviene facilmente en la reaccion C{sub 2}H*{sub 5} + RH = C{sub 2}H{sub 6} + R, que explica el 'exceso' de etano formado durante la radiolisis del etileno. (author) [Russian] Izvestno, chto v rezul'tate jadernyh reakcij Li{sup 6}(n, {alpha})T i He{sup 3}(n, p) T obrazujutsja gorjachie atomy radioaktivnogo vodoroda. Vysokaja himicheskaja aktivnost' takih atomov vo mnogom opredeljaet osobennosti himicheskih posledstvij jadernyh prevrashhenij. Odnako gorjachie atomy vodoroda mogut igrat' sushhestvennuju rol' ne tol'ko v jadernoj himii, no i v drugih oblastjah himii vysokih jenergij: pri radiolize, fotolize i t.d. V nastojashhej rabote sdelana popytka sopostavit' povedenie gorjachih atomov vodoroda, poluchaemyh razlichnym putem: pri reakcii i{sup 6}(n, {alpha})T (E{sub otd} = 2,7 Mjev), radioliticheski (E Tilde-Operator neskol'koojev), fotoliticheski (E Tilde-Operator 1 - 1,5 jev; gorjachij vodorod poluchaetsja iz HJ pri fotolize s {lambda}2537A). V kachestve mishenej dlja poluchenija atomov tritija ispol'zovalis' kristally i plenki Li{sub 2}Co{sub 3}, Li{sup 6}F, Li{sup 6}OH, Li{sup 6}BO{sub 2} * 8H{sub 2}. Oblucheniju podvergali gazoobraznyj jetilen (R = 5-10 atm.) i ego smesi s ammiakom, geliem i ingibitorami. Obluchenie provodilos' na rjoaktore tipa IRT-1000 pri potoke teplovyh nejtronov 10{sup 11} - 10{sup 12} n/cm{sup 2}sek. Mechennye po tritiju soedinenija i produkty radiacionno-himicheskih reakcij opredeljali gazohromatograficheski s pomoshh'ju dvuh posledovatel'no soedinennyh

  10. Geochemistry and mineralogy

    Energy Technology Data Exchange (ETDEWEB)

    Plecas, I.; Dimovic, S.; Orta, M.M.; Alba, M.D.; Alvero, R.; Becerro, A.I.; Castro, M.A.; Chain, P.; Escudero, A.; Naranjo, M.; Pavon, E.; Trillo, J.M.; Vejsada, J.; Vokal, A.; Zadvernyuk, H.P.; Fedorenko, Y.G.; Zlobenko, B.P.; Koromyslichenko, T.I.; Battaglia, S.; Cervelli, M.; Millot, R.; Girard, J.P.; Missana, T.; Garcia-Gutierrez, M.; Alonso, U.; Muurinen, A.; Carlsson, T.; Chain, P.; Alba, M.D.; Becerro, A.I.; Castro, M.A.; Escudero, A.; Gonzalez-Carrascosa, T.; Hurtado, S.; Pavon, E.; Villa, M.; Bourg, I.C.; Sposito, G.; Bourg, A.C.M.; Marques Fernandes, M.; Rabung, Th.; Dahn, R.; Baeyens, B.; Bradbury, M.H.; Breynaert, E.; Maes, A.; Bruggeman, C.; Maes, I.A.; Vancluysen, J.; Credoz, A.; Bildstein, O.; Jullien, M.; Raynal, J.; Petronin, J.C.; Trotignon, L.; Pokrovsky, O.; Jacquier, P.; Beaucaire, C.; Vuillaume, A.L.; Wittebroodt, Ch.; Ly, J.; Page, J.; Savoye, S.; Pitsch, H.; Jacques, D.; Wang, L.; Galunin, E.; Chain, P.; Alba, M.D.; Vidal, M.; Grandia, F.; Domenech, C.; Arcos, D.; Duro, L.; Bruno, J.; Andre, L.; Pauwels, H.; Azaroual, M.; Albrecht, A.; Romero, M.A.; Aerts, S.; Boven, P.; Van Geet, M.; Boever, P. de; Alonso, U.; Albarran, N.; Missana, T.; Garcia-Gutierrez, M.; Truche, L.; Berger, G.; Guillaume, D.; Jacquot, E.; Tournassat, Ch.; Lerouge, C.; Brendle, J.; Greneche, J.M.; Touzelet, St.; Blanc, Ph.; Gaucher, E.C.; Thoenen, T.; Klinkenberg, M.; Kaufhold, S.; Dohrmann, R.; Siegesmund, S.; Liu, D.J.; Bruggeman, C.; Maes, N.; Weber, T.; Trotignon, L.; Pozo, C.; Bildstein, O.; Combarieu, G. de; Frugier, P.; Menut, D

    2007-07-01

    (Ca, Mg) in the Callovo-Oxfordian formation: implications for pore water composition modeling; a Monte Carlo sensitivity analysis of modelled Opalinus clay pore waters from the Mont Terri rock laboratory; the microstructural investigation of Opalinus clay proposal of a carbonate distribution model; the influence of natural organic matter on the sorption behaviour of Eu on illite (as model component for Boom clay); the fate of boron and dynamics of reactive transport processes in the near field of a HLW disposal; the sulfate-reducing bacteria (Desulfovibrio desulfuricans) activity monitored by magnetic measurements in Bure clay-stones (France) and Mont Terri clay-stones (Switzerland); the influence of EDTA and isosaccharinate organic ligands on the uptake and migration of europium in the Callovo-Oxfordian argillite; the experimental determination of thermodynamic properties of a chlorite; the structural incorporation of trivalent f elements into the tri-octahedral clay mineral hectorite; heavy metals migration in argillaceous rocks: on the use of laser-induced breakdown spectroscopy microprobe (Libs microprobe) as a microanalysis tool; the isotopic anomalies observed at the vicinity of fractures in pore water of Tournemire shales: experimental artefacts or local paleo-circulations?; the effect of temperature on the retention capacity of compacted bentonite: an experimental and numerical investigation; the retention of Cs in Boom Clay: comparison of data from batch sorption tests and diffusion experiments on clay cores; the sorption and engineering characteristics of some clay/shale deposits from nigeria as landfill liner; the influence of organic matter composition on iodine sorption: from fresh to thermally matured peat; the observation of microstructure of compacted Bentonite by X-ray micro CT method optimized with computer simulation; the hydration and hydrolysis of Sm{sup 3+} and Eu{sup 3+} in clay interlayer: neutron diffraction study; a molecular simulations of