Chelation and stabilization of berkelium in oxidation state +IV
Abstract
Berkelium (Bk) has been predicted to be the only transplutonium element able to exhibit both +III and +IV oxidation states in solution, but evidence of a stable oxidized Bk chelate has so far remained elusive. Here, in this work, we describe the stabilization of the heaviest 4+ ion of the periodic table, under mild aqueous conditions, using a siderophore derivative. The resulting Bk(IV) complex exhibits luminescence via sensitization through an intramolecular antenna effect. This neutral Bk(IV) coordination compound is not sequestered by the protein siderocalin - a mammalian metal transporter - in contrast to the negatively charged species obtained with neighbouring trivalent actinides americium, curium and californium (Cf). The corresponding Cf(III)-ligand-protein ternary adduct was characterized by X-ray diffraction analysis. Finally, combined with theoretical predictions, these data add significant insight to the field of transplutonium chemistry, and may lead to innovative Bk separation and purification processes.
- Authors:
-
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
- Fred Hutchinson Cancer Research Center, Seattle, WA (United States). Division of Basic Science
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Berkeley Center for Structural Biology
- Academy of Sciences of the Czech Republic, Prague (Czech Republic). J. Heyrovsky Institute of Physical Chemistry
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Computational Research Division
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR)
- OSTI Identifier:
- 1436161
- Grant/Contract Number:
- AC02-05CH11231; AC05-00OR22725
- Resource Type:
- Journal Article: Accepted Manuscript
- Journal Name:
- Nature Chemistry
- Additional Journal Information:
- Journal Volume: 9; Journal Issue: 9; Journal ID: ISSN 1755-4330
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
Citation Formats
Deblonde, Gauthier J. -P., Sturzbecher-Hoehne, Manuel, Rupert, Peter B., An, Dahlia D., Illy, Marie-Claire, Ralston, Corie Y., Brabec, Jiri, de Jong, Wibe A., Strong, Roland K., and Abergel, Rebecca J. Chelation and stabilization of berkelium in oxidation state +IV. United States: N. p., 2017.
Web. doi:10.1038/nchem.2759.
Deblonde, Gauthier J. -P., Sturzbecher-Hoehne, Manuel, Rupert, Peter B., An, Dahlia D., Illy, Marie-Claire, Ralston, Corie Y., Brabec, Jiri, de Jong, Wibe A., Strong, Roland K., & Abergel, Rebecca J. Chelation and stabilization of berkelium in oxidation state +IV. United States. https://doi.org/10.1038/nchem.2759
Deblonde, Gauthier J. -P., Sturzbecher-Hoehne, Manuel, Rupert, Peter B., An, Dahlia D., Illy, Marie-Claire, Ralston, Corie Y., Brabec, Jiri, de Jong, Wibe A., Strong, Roland K., and Abergel, Rebecca J. 2017.
"Chelation and stabilization of berkelium in oxidation state +IV". United States. https://doi.org/10.1038/nchem.2759. https://www.osti.gov/servlets/purl/1436161.
@article{osti_1436161,
title = {Chelation and stabilization of berkelium in oxidation state +IV},
author = {Deblonde, Gauthier J. -P. and Sturzbecher-Hoehne, Manuel and Rupert, Peter B. and An, Dahlia D. and Illy, Marie-Claire and Ralston, Corie Y. and Brabec, Jiri and de Jong, Wibe A. and Strong, Roland K. and Abergel, Rebecca J.},
abstractNote = {Berkelium (Bk) has been predicted to be the only transplutonium element able to exhibit both +III and +IV oxidation states in solution, but evidence of a stable oxidized Bk chelate has so far remained elusive. Here, in this work, we describe the stabilization of the heaviest 4+ ion of the periodic table, under mild aqueous conditions, using a siderophore derivative. The resulting Bk(IV) complex exhibits luminescence via sensitization through an intramolecular antenna effect. This neutral Bk(IV) coordination compound is not sequestered by the protein siderocalin - a mammalian metal transporter - in contrast to the negatively charged species obtained with neighbouring trivalent actinides americium, curium and californium (Cf). The corresponding Cf(III)-ligand-protein ternary adduct was characterized by X-ray diffraction analysis. Finally, combined with theoretical predictions, these data add significant insight to the field of transplutonium chemistry, and may lead to innovative Bk separation and purification processes.},
doi = {10.1038/nchem.2759},
url = {https://www.osti.gov/biblio/1436161},
journal = {Nature Chemistry},
issn = {1755-4330},
number = 9,
volume = 9,
place = {United States},
year = {Mon Apr 10 00:00:00 EDT 2017},
month = {Mon Apr 10 00:00:00 EDT 2017}
}
Web of Science
Figures / Tables:
Works referenced in this record:
Dose-Dependent Efficacy and Safety Toxicology of Hydroxypyridinonate Actinide Decorporation Agents in Rodents: Towards a Safe and Effective Human Dosing Regimen
journal, February 2013
- Bunin, Deborah I.; Chang, Polly Y.; Doppalapudi, Rupa S.
- Radiation Research, Vol. 179, Issue 2
Solution Thermodynamic Stability of Complexes Formed with the Octadentate Hydroxypyridinonate Ligand 3,4,3-LI(1,2-HOPO): A Critical Feature for Efficient Chelation of Lanthanide(IV) and Actinide(IV) Ions
journal, July 2013
- Deblonde, Gauthier J-P.; Sturzbecher-Hoehne, Manuel; Abergel, Rebecca J.
- Inorganic Chemistry, Vol. 52, Issue 15
Density-functional exchange-energy approximation with correct asymptotic behavior
journal, September 1988
- Becke, A. D.
- Physical Review A, Vol. 38, Issue 6
Solution thermodynamic evaluation of hydroxypyridinonate chelators 3,4,3-LI(1,2-HOPO) and 5-LIO(Me-3,2-HOPO) for UO 2 (VI) and Th(IV) decorporation
journal, June 2013
- Sturzbecher-Hoehne, M.; Deblonde, G. J. -P.; Abergel, R. J.
- Radiochimica Acta, Vol. 101, Issue 6
Highly Luminescent and Stable Hydroxypyridinonate Complexes: A Step Towards New Curium Decontamination Strategies
journal, July 2014
- Sturzbecher-Hoehne, Manuel; Kullgren, Birgitta; Jarvis, Erin E.
- Chemistry - A European Journal, Vol. 20, Issue 32
Relativistic double-zeta, triple-zeta, and quadruple-zeta basis sets for the actinides Ac–Lr
journal, October 2006
- Dyall, Kenneth G.
- Theoretical Chemistry Accounts, Vol. 117, Issue 4
The separation of berkelium(III) from cerium(III)
journal, February 1972
- Chudinov, E. G.; Pirozhkov, S. V.
- Journal of Radioanalytical Chemistry, Vol. 10, Issue 1
Liquid-liquid extraction method for the separation of cerium(IV) from berkelium(IV) and other elements
journal, October 1969
- Moore, Fletcher Langley.
- Analytical Chemistry, Vol. 41, Issue 12
Energy‐adjusted pseudopotentials for the actinides. Parameter sets and test calculations for thorium and thorium monoxide
journal, May 1994
- Küchle, W.; Dolg, M.; Stoll, H.
- The Journal of Chemical Physics, Vol. 100, Issue 10
Rapid Chemical Separation for Bk
journal, January 2002
- Maruyama, T.; Kaji, D.; Kaneko, T.
- Journal of Nuclear and Radiochemical Sciences, Vol. 3, Issue 1
Possible stabilization of the tetravalent oxidation state of berkelium and californium in acetonitrile with triphenylarsine oxide
journal, December 1987
- Payne, Gerard F.; Peterson, Joseph R.
- Inorganica Chimica Acta, Vol. 139, Issue 1-2
Intramolecular sensitization of americium luminescence in solution: shining light on short-lived forbidden 5f transitions
journal, January 2016
- Sturzbecher-Hoehne, M.; Yang, P.; D'Aléo, A.
- Dalton Transactions, Vol. 45, Issue 24
Latest achievements in the analytical chemistry of actinides
journal, January 1991
- Myasoedov, B. F.; Lebedev, I. A.
- Journal of Radioanalytical and Nuclear Chemistry Articles, Vol. 147, Issue 1
Element 97
journal, March 1950
- Thompson, S. G.; Ghiorso, A.; Seaborg, G. T.
- Physical Review, Vol. 77, Issue 6
Analysis of the crystal‐field spectra of the actinide tetrafluorides. II. AmF 4 , CmF 4 , Cm 4+ :CeF 4 , and Bk 4+ :CeF 4
journal, November 1994
- Liu, G. K.; Carnall, W. T.; Jursich, G.
- The Journal of Chemical Physics, Vol. 101, Issue 10
Characterization of berkelium(III) dipicolinate and borate compounds in solution and the solid state
journal, August 2016
- Silver, M. A.; Cary, S. K.; Johnson, J. A.
- Science, Vol. 353, Issue 6302
Berkelium redox speciation
journal, January 2002
- Antonio, M. R.; Williams, C. W.; Soderholm, L.
- Radiochimica Acta, Vol. 90, Issue 12
Absorption spectra of Bk(III) and Bk(IV) in several media
journal, February 1972
- Baybarz, R. D.; Stokely, J. R.; Peterson, J. R.
- Journal of Inorganic and Nuclear Chemistry, Vol. 34, Issue 2
The Neutrophil Lipocalin NGAL Is a Bacteriostatic Agent that Interferes with Siderophore-Mediated Iron Acquisition
journal, November 2002
- Goetz, David H.; Holmes, Margaret A.; Borregaard, Niels
- Molecular Cell, Vol. 10, Issue 5
NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations
journal, September 2010
- Valiev, M.; Bylaska, E. J.; Govind, N.
- Computer Physics Communications, Vol. 181, Issue 9, p. 1477-1489
Preliminary Data on 253Es and 249Bk Metabolism in Rats
journal, January 1972
- Hungate, F. P.; Ballou, J. E.; Mahlum, D. D.
- Health Physics, Vol. 22, Issue 6
The stability of tetravalent berkelium in acid solution and the absorption spectra of Bk(IV) and Bk(III)
journal, March 1973
- Gutmacher, R. G.; Bodé, D. D.; Lougheed, R. W.
- Journal of Inorganic and Nuclear Chemistry, Vol. 35, Issue 3
Laser induced fluorescence of 249Bk4+ in CeF4
journal, December 1987
- Jursich, G. M.; Beitz, J. V.; Carnall, W. T.
- Inorganica Chimica Acta, Vol. 139, Issue 1-2
Higher Oxidation States of Americium: Preparation, Characterization and Use for Separations
journal, September 2011
- Runde, Wolfgang H.; Mincher, Bruce J.
- Chemical Reviews, Vol. 111, Issue 9
Electron-transfer and f-d absorption bands of some lanthanide and actinide complexes and the standard (II-III) oxidation potential for each member of the lanthanide and actinide series
journal, June 1973
- Nugent, L. J.; Baybarz, R. D.; Burnett, J. L.
- The Journal of Physical Chemistry, Vol. 77, Issue 12
Siderocalin-mediated recognition, sensitization, and cellular uptake of actinides
journal, August 2015
- Allred, Benjamin E.; Rupert, Peter B.; Gauny, Stacey S.
- Proceedings of the National Academy of Sciences, Vol. 112, Issue 33
Optimization of Gaussian-type basis sets for local spin density functional calculations. Part I. Boron through neon, optimization technique and validation
journal, February 1992
- Godbout, Nathalie; Salahub, Dennis R.; Andzelm, Jan
- Canadian Journal of Chemistry, Vol. 70, Issue 2
Analytical Methods for the Bioavailability Evaluation of Hydroxypyridinonate Actinide Decorporation Agents in Pre-Clinical Pharmacokinetic Studies
journal, January 2013
- Y. Chang, Polly
- Journal of Chromatography & Separation Techniques, Vol. 04, Issue 07
Microscopic Distribution of Californium-249 and Berkelium-249 in the Soft Tissues of Beagles
journal, January 1972
- Taylor, G. N.; Jee, W. S. S.; Mays, C. W.
- Health Physics, Vol. 22, Issue 6
Perspective methods for Berkelium – 249 preparation and application
journal, November 2002
- Kosyakov, Valentin N.
- Journal of Nuclear Science and Technology, Vol. 39, Issue sup3
Intramolecular energy transfer and sensitized luminescence in actinide(III) β-diketone chelates
journal, May 1969
- Nugent, Leonard J.; Burnett, J. L.; Baybarz, R. D.
- The Journal of Physical Chemistry, Vol. 73, Issue 5
Extraction of tetravalent berkelium by high molecular weight amines in the presence of heteropolyanions
journal, March 1986
- Milyukova, M. S.; Malikov, D. A.; Kuzovkina, E. V.
- Journal of Radioanalytical and Nuclear Chemistry Letters, Vol. 104, Issue 2
Voltammetric Investigation of the Berkelium(IV/III) Couple in Concentrated Aqueous Carbonate Solutions
journal, January 1990
- Morris, D. E.; Hobart, D. E.; Palmer, P. D.
- Radiochimica Acta, Vol. 49, Issue 3
Chemical Properties of Berkelium
journal, June 1950
- Thompson, S. G.; Cunningham, B. B.; Seaborg, G. T.
- Journal of the American Chemical Society, Vol. 72, Issue 6
Biodistribution of the Multidentate Hydroxypyridinonate Ligand [ 14 C]-3,4,3-LI(1,2-HOPO), a Potent Actinide Decorporation Agent : BIODISTRIBUTION OF 3,4,3-LI(1,2-HOPO)
journal, April 2015
- Choi, Taylor A.; Endsley, Aaron N.; Bunin, Deborah I.
- Drug Development Research, Vol. 76, Issue 3
Present Status of Cerium(IV)-Cerium(III) Potentials
journal, December 1957
- Wadsworth, Earl.; Duke, F. R.; Goetz, C. A.
- Analytical Chemistry, Vol. 29, Issue 12
In Vitro Metabolism and Stability of the Actinide Chelating Agent 3,4,3-LI(1,2-HOPO)
journal, May 2015
- Choi, Taylor A.; Furimsky, Anna M.; Swezey, Robert
- Journal of Pharmaceutical Sciences, Vol. 104, Issue 5
New method for rapid separation of berkelium(IV) from cerium(IV) by anion exchange
journal, December 1967
- Moore, Fletcher Langley.
- Analytical Chemistry, Vol. 39, Issue 14
Isolation of berkelium by solvent extraction of the tetravalent species
journal, January 1957
- Peppard, D. F.; Moline, S. W.; Mason, G. W.
- Journal of Inorganic and Nuclear Chemistry, Vol. 4, Issue 5-6
Hydroxypyridinonate Complex Stability of Group (IV) Metals and Tetravalent f-Block Elements: The Key to the Next Generation of Chelating Agents for Radiopharmaceuticals
journal, March 2015
- Sturzbecher-Hoehne, Manuel; Choi, Taylor A.; Abergel, Rebecca J.
- Inorganic Chemistry, Vol. 54, Issue 7
The formal potential of the Bk(IV)-Bk(III) couple in several media
journal, January 1972
- Stokely, J. R.; Baybarz, R. D.; Peterson, J. R.
- Journal of Inorganic and Nuclear Chemistry, Vol. 34, Issue 1
Electronic energy level and intensity correlations in the spectra of the trivalent actinide aquo ions. III. Bk 3 +
journal, March 1984
- Carnall, W. T.; Beitz, J. V.; Crosswhite, H.
- The Journal of Chemical Physics, Vol. 80, Issue 6
Procedures for a fast separation of berkelium from complex mixtures of reaction products
journal, March 1983
- Liu, Yuan-Fang; Luo, Cheng; Moody, K. J.
- Journal of Radioanalytical Chemistry, Vol. 76, Issue 1
The absorption spectra of Bk3+ and Bk4+ in solution
journal, September 1967
- Gutmacher, R. G.; Hulet, E. K.; Lougheed, R.
- Journal of Inorganic and Nuclear Chemistry, Vol. 29, Issue 9
Dissociation constants of the transplutonium element chelates of diethylenetriaminepenta-acetic acid (DTPA) and the application of DTPA chelates to solvent extraction separations of transplutonium elements from the lanthanide elements
journal, August 1965
- Baybarz, R. D.
- Journal of Inorganic and Nuclear Chemistry, Vol. 27, Issue 8
Efficient Algorithms for Estimating the Absorption Spectrum within Linear Response TDDFT
journal, October 2015
- Brabec, Jiri; Lin, Lin; Shao, Meiyue
- Journal of Chemical Theory and Computation, Vol. 11, Issue 11
The size of actinoid(III) ions – structural analysis vs. common misinterpretations
journal, July 2016
- Lundberg, Daniel; Persson, Ingmar
- Coordination Chemistry Reviews, Vol. 318
Nephelauxetic Effect and Hypersensitivity in the Optical Spectra of Actinides
journal, December 1997
- Barbanel’, A.
- ract, Vol. 78, Issue s1
Works referencing / citing this record:
Combinatorial design of multimeric chelating peptoids for selective metal coordination
journal, January 2019
- Ricano, Abel; Captain, Ilya; Carter, Korey P.
- Chemical Science, Vol. 10, Issue 28
Spectroscopic and Computational Characterization of Diethylenetriaminepentaacetic Acid/Transplutonium Chelates: Evidencing Heterogeneity in the Heavy Actinide(III) Series
journal, March 2018
- Deblonde, Gauthier J. -P.; Kelley, Morgan P.; Su, Jing
- Angewandte Chemie International Edition, Vol. 57, Issue 17
Combinatorial design of multimeric chelating peptoids for selective metal coordination
journal, January 2019
- Ricano, Abel; Captain, Ilya; Carter, Korey P.
- Chemical Science, Vol. 10, Issue 28
Tuning the molecular antenna effect using donor and acceptor substituents on the optical properties of the [(C 5 F 5 ) 2 ThMCp 2 ] 2+ and [(C 5 F 5 ) 2 ThMCpL 2 ] + complexes, where M = Fe, Ru and Os and L = CO and C 5 H 5 N
journal, January 2018
- Cantero-López, Plinio; Páez-Hernández, Dayán; Arratia-Pérez, Ramiro
- New Journal of Chemistry, Vol. 42, Issue 13
The Chemistry of Lanthanides in Biology: Recent Discoveries, Emerging Principles, and Technological Applications
journal, August 2019
- Cotruvo, Joseph A.
- ACS Central Science, Vol. 5, Issue 9
Contemporary Chemistry of Berkelium and Californium
journal, June 2019
- White, Frankie D.; Dan, David; Albrecht‐Schmitt, Thomas E.
- Chemistry – A European Journal, Vol. 25, Issue 44
Inducing selectivity and chirality in group IV metal coordination with high-denticity hydroxypyridinones
journal, January 2019
- Deblonde, Gauthier J. -P.; Lohrey, Trevor D.; Abergel, Rebecca J.
- Dalton Transactions, Vol. 48, Issue 23
Ultra-selective ligand-driven separation of strategic actinides
journal, June 2019
- Deblonde, Gauthier J. -P.; Ricano, Abel; Abergel, Rebecca J.
- Nature Communications, Vol. 10, Issue 1
Reductive activation of neptunyl and plutonyl oxo species with a hydroxypyridinone chelating ligand
journal, January 2018
- Carter, Korey P.; Jian, Jiwen; Pyrch, Mikaela M.
- Chemical Communications, Vol. 54, Issue 76
Toxic heavy metal – Pb, Cd, Sn – complexation by the octadentate hydroxypyridinonate ligand archetype 3,4,3-LI(1,2-HOPO)
journal, January 2018
- Deblonde, Gauthier J. -P.; Lohrey, Trevor D.; An, Dahlia D.
- New Journal of Chemistry, Vol. 42, Issue 10
Transuranic Computational Chemistry
journal, November 2017
- Kaltsoyannis, Nikolas
- Chemistry - A European Journal, Vol. 24, Issue 12
Spectroscopic and Computational Characterization of Diethylenetriaminepentaacetic Acid/Transplutonium Chelates: Evidencing Heterogeneity in the Heavy Actinide(III) Series
journal, March 2018
- Deblonde, Gauthier J. -P.; Kelley, Morgan P.; Su, Jing
- Angewandte Chemie, Vol. 130, Issue 17
Ultra-selective ligand-driven separation of strategic actinides
journal, June 2019
- Deblonde, Gauthier J. -P.; Ricano, Abel; Abergel, Rebecca J.
- Nature Communications, Vol. 10, Issue 1
Investigating subtle 4f vs. 5f coordination differences using kinetically inert Eu( iii ), Tb( iii ), and Cm( iii ) complexes of a coumarin-appended 1,4,7,10-tetraazacyclododecane-1,4,7-triacetate (DO3A) ligand
journal, January 2018
- Junker, Anne Kathrine R.; Deblonde, Gauthier J. -P.; Abergel, Rebecca J.
- Dalton Transactions, Vol. 47, Issue 21
Figures / Tables found in this record: