In situ beam reduction of Pu(IV) and Bk(IV) as a route to trivalent transuranic coordination complexes with hydroxypyridinone chelators

Carter, Korey P.; Wacker, Jennifer N.; Smith, Kurt F.; Deblonde, Gauthier J. -P.; Moreau, Liane M.; Rees, Julian A.; Booth, Corwin H.; Abergel, Rebecca J.

doi:10.1107/S1600577522000200

Title: In situ beam reduction of Pu(IV) and Bk(IV) as a route to trivalent transuranic coordination complexes with hydroxypyridinone chelators

Journal Article · 24 February 2022 · Journal of Synchrotron Radiation (Online)

DOI: https://doi.org/10.1107/S1600577522000200 · OSTI ID:1846473

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; Smith, Kurt F.;

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The solution-state interactions of plutonium and berkelium with the octadentate chelator 3,4,3-LI(1,2-HOPO) (343-HOPO) were investigated and characterized by X-ray absorption spectroscopy, which revealed in situ reductive decomposition of the tetravalent species of both actinide metals to yield Pu(III) and Bk(III) coordination complexes. X-ray absorption near-edge structure (XANES) measurements were the first indication of in situ synchrotron redox chemistry as the Pu threshold and white-line position energies for Pu-343-HOPO were in good agreement with known diagnostic Pu(III) species, whereas Bk-343-HOPO results were found to mirror the XANES behavior of Bk(III)-DTPA. Extended X-ray absorption fine structure results revealed An—O _HOPO bond distances of 2.498 (5) and 2.415 (2) Å for Pu and Bk, respectively, which match well with bond distances obtained for trivalent actinides and 343-HOPO via density functional theory calculations. Pu(III)- and Bk(III)-343-HOPO data also provide initial insight into actinide periodicity as they can be compared with previous results with Am(III)-, Cm(III)-, Cf(III)-, and Es(III)-343-HOPO, which indicate there is likely an increase in 5 f covalency and heterogeneity across the actinide series.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231; AC02-76SF00515

OSTI ID:: 1846473

Journal Information:: Journal of Synchrotron Radiation (Online), Journal Name: Journal of Synchrotron Radiation (Online) Journal Issue: 2 Vol. 29; ISSN 1600-5775; ISSN JSYRES

Publisher:: International Union of Crystallography (IUCr)Copyright Statement

Country of Publication:: Denmark

Language:: English

References (65)

Influence of the HEPES Buffer on Electrochemical Reaction of the Copper(II)-Salicylaldoxime Complex Cuculić, Vlado; Mlakar, Marina; Branica, Marko Electroanalysis, Vol. 10, Issue 12 https://doi.org/10.1002/(SICI)1521-4109(199809)10:12<852::AID-ELAN852>3.0.CO;2-O	journal	September 1998
Solving the Hydration Structure of the Heaviest Actinide Aqua Ion Known: The Californium(III) Case Galbis, Elsa; Hernández-Cobos, Jorge; den Auwer, Christophe Angewandte Chemie International Edition, Vol. 49, Issue 22 https://doi.org/10.1002/anie.200906129	journal	April 2010
Spectroscopic and Computational Characterization of Diethylenetriaminepentaacetic Acid/Transplutonium Chelates: Evidencing Heterogeneity in the Heavy Actinide(III) Series Deblonde, Gauthier J. -P.; Kelley, Morgan P.; Su, Jing Angewandte Chemie International Edition, Vol. 57, Issue 17 https://doi.org/10.1002/anie.201709183	journal	March 2018
Sequestered Plutonium: [PuIV{5LIO(Me-3,2-HOPO)}2]—The First Structurally Characterized Plutonium Hydroxypyridonate Complex Gorden, Anne E. V.; Shuh, David K.; Tiedemann, Bryan E. F. Chemistry - A European Journal, Vol. 13, Issue 2 https://doi.org/10.1002/chem.200790005	journal	January 2007
Spontaneous Chelation‐Driven Reduction of the Neptunyl Cation in Aqueous Solution Carter, Korey P.; Smith, Kurt F.; Tratnjek, Toni Chemistry – A European Journal, Vol. 26, Issue 11 https://doi.org/10.1002/chem.201905695	journal	February 2020
Combining the Best of Two Chelating Titans: A Hydroxypyridinone‐Decorated Macrocyclic Ligand for Efficient and Concomitant Complexation and Sensitized Luminescence of f‐Elements Arnedo‐Sanchez, Leticia; Smith, Kurt F.; Deblonde, Gauthier J. ‐P. ChemPlusChem, Vol. 86, Issue 3 https://doi.org/10.1002/cplu.202100083	journal	March 2021
The size of actinoid(III) ions – structural analysis vs. common misinterpretations Lundberg, Daniel; Persson, Ingmar Coordination Chemistry Reviews, Vol. 318 https://doi.org/10.1016/j.ccr.2016.04.003	journal	July 2016
Photoreduction of iron by a synchrotron X-ray beam in low iron content soda-lime silicate glasses Gonçalves Ferreira, P.; de Ligny, D.; Lazzari, O. Chemical Geology, Vol. 346 https://doi.org/10.1016/j.chemgeo.2012.10.029	journal	May 2013
A close look at dose: Toward L-edge XAS spectral uniformity, dose quantification and prediction of metal ion photoreduction van Schooneveld, M. M.; DeBeer, S. Journal of Electron Spectroscopy and Related Phenomena, Vol. 198 https://doi.org/10.1016/j.elspec.2014.12.001	journal	January 2015
Plutonium(III) complexation by humic substances studied by X-ray absorption fine structure spectroscopy Schmeide, Katja; Reich, Tobias; Sachs, Susanne Inorganica Chimica Acta, Vol. 359, Issue 1 https://doi.org/10.1016/j.ica.2005.10.037	journal	January 2006
Structural investigations of PuIII phosphate by X-ray diffraction, MAS-NMR and XANES spectroscopy Popa, Karin; Raison, Philippe E.; Martel, Laura Journal of Solid State Chemistry, Vol. 230 https://doi.org/10.1016/j.jssc.2015.07.002	journal	October 2015
Controlling the Reduction of Chelated Uranyl to Stable Tetravalent Uranium Coordination Complexes in Aqueous Solution Carter, Korey P.; Smith, Kurt F.; Tratnjek, Toni Inorganic Chemistry, Vol. 60, Issue 2 https://doi.org/10.1021/acs.inorgchem.0c03088	journal	December 2020
Complexation of Lanthanides and Heavy Actinides with Aqueous Sulfur-Donating Ligands Bessen, Nathan P.; Popov, Ivan A.; Heathman, Colt R. Inorganic Chemistry, Vol. 60, Issue 9 https://doi.org/10.1021/acs.inorgchem.1c00257	journal	April 2021
Hydroxypyridinonate Complex Stability of Group (IV) Metals and Tetravalent f-Block Elements: The Key to the Next Generation of Chelating Agents for Radiopharmaceuticals Sturzbecher-Hoehne, Manuel; Choi, Taylor A.; Abergel, Rebecca J. Inorganic Chemistry, Vol. 54, Issue 7 https://doi.org/10.1021/acs.inorgchem.5b00033	journal	March 2015
Engineered Recognition of Tetravalent Zirconium and Thorium by Chelator–Protein Systems: Toward Flexible Radiotherapy and Imaging Platforms Captain, Ilya; Deblonde, Gauthier J. -P.; Rupert, Peter B. Inorganic Chemistry, Vol. 55, Issue 22 https://doi.org/10.1021/acs.inorgchem.6b02041	journal	November 2016
Structural Characterization of Am(III)- and Pu(III)-DOTA Complexes Audras, Matthieu; Berthon, Laurence; Berthon, Claude Inorganic Chemistry, Vol. 56, Issue 20 https://doi.org/10.1021/acs.inorgchem.7b01666	journal	October 2017
Bond Covalency and Oxidation State of Actinide Ions Complexed with Therapeutic Chelating Agent 3,4,3-LI(1,2-HOPO) Kelley, Morgan P.; Deblonde, Gauthier J. -P.; Su, Jing Inorganic Chemistry, Vol. 57, Issue 9 https://doi.org/10.1021/acs.inorgchem.8b00345	journal	April 2018
Redox Processes of Manganese Oxide in Catalyzing Oxygen Evolution and Reduction: An in Situ Soft X-ray Absorption Spectroscopy Study Risch, Marcel; Stoerzinger, Kelsey A.; Han, Binghong The Journal of Physical Chemistry C, Vol. 121, Issue 33 https://doi.org/10.1021/acs.jpcc.7b05592	journal	August 2017
Synthesis and Characterization of the Actinium Aquo Ion Ferrier, Maryline G.; Stein, Benjamin W.; Batista, Enrique R. ACS Central Science, Vol. 3, Issue 3 https://doi.org/10.1021/acscentsci.6b00356	journal	February 2017
Rational Design of Sequestering Agents for Plutonium and Other Actinides Gorden, Anne E. V.; Xu, Jide; Raymond, Kenneth N. Chemical Reviews, Vol. 103, Issue 11 https://doi.org/10.1021/cr990114x	journal	November 2003
Oxidation State and Local Structure of Plutonium Reacted with Magnetite, Mackinawite, and Chukanovite Kirsch, Regina; Fellhauer, David; Altmaier, Marcus Environmental Science & Technology, Vol. 45, Issue 17 https://doi.org/10.1021/es200645a	journal	September 2011
Plutonium(IV) Sequestration: Structural and Thermodynamic Evaluation of the Extraordinarily Stable Cerium(IV) Hydroxypyridinonate Complexes¹ Xu, Jide; Radkov, Emil; Ziegler, Marco Inorganic Chemistry, Vol. 39, Issue 18, p. 4156-4164 https://doi.org/10.1021/ic000063i	journal	September 2000
Higher Order Speciation Effects on Plutonium L ₃ X-ray Absorption Near Edge Spectra Conradson, Steven D.; Abney, Kent D.; Begg, Bruce D. Inorganic Chemistry, Vol. 43, Issue 1 https://doi.org/10.1021/ic0346477	journal	January 2004
Complexation of Pu(IV) with the Natural Siderophore Desferrioxamine B and the Redox Properties of Pu(IV)(siderophore) Complexes Boukhalfa, Hakim; Reilly, Sean D.; Neu, Mary P. Inorganic Chemistry, Vol. 46, Issue 3 https://doi.org/10.1021/ic061544q	journal	February 2007
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 Deblonde, Gauthier J-P.; Sturzbecher-Hoehne, Manuel; Abergel, Rebecca J. Inorganic Chemistry, Vol. 52, Issue 15 https://doi.org/10.1021/ic4010246	journal	July 2013
Using the Antenna Effect as a Spectroscopic Tool: Photophysics and Solution Thermodynamics of the Model Luminescent Hydroxypyridonate Complex [Eu ^III (3,4,3-LI(1,2-HOPO))] ⁻ Abergel, Rebecca J.; D’Aléo, Anthony; Ng Pak Leung, Clara Inorganic Chemistry, Vol. 48, Issue 23 https://doi.org/10.1021/ic9013703	journal	December 2009
Investigation of Aquo and Chloro Complexes of UO ₂ ²⁺ , NpO ₂ ⁺ , Np ⁴⁺ , and Pu ³⁺ by X-ray Absorption Fine Structure Spectroscopy Allen, P. G.; Bucher, J. J.; Shuh, D. K. Inorganic Chemistry, Vol. 36, Issue 21 https://doi.org/10.1021/ic970502m	journal	October 1997
Coordination Chemistry of Trivalent Lanthanide and Actinide Ions in Dilute and Concentrated Chloride Solutions Allen, P. G.; Bucher, J. J.; Shuh, D. K. Inorganic Chemistry, Vol. 39, Issue 3 https://doi.org/10.1021/ic9905953	journal	February 2000
On the Origin of Covalent Bonding in Heavy Actinides Kelley, Morgan P.; Su, Jing; Urban, Matthew Journal of the American Chemical Society, Vol. 139, Issue 29 https://doi.org/10.1021/jacs.7b03251	journal	July 2017
Covalency in Americium(III) Hexachloride Cross, Justin N.; Su, Jing; Batista, Enrique R. Journal of the American Chemical Society, Vol. 139, Issue 25 https://doi.org/10.1021/jacs.7b03755	journal	June 2017
Energy-Degeneracy-Driven Covalency in Actinide Bonding Su, Jing; Batista, Enrique R.; Boland, Kevin S. Journal of the American Chemical Society, Vol. 140, Issue 51 https://doi.org/10.1021/jacs.8b09436	journal	December 2018
Advancing Chelation Chemistry for Actinium and Other +3 f-Elements, Am, Cm, and La Stein, Benjamin W.; Morgenstern, Amanda; Batista, Enrique R. Journal of the American Chemical Society, Vol. 141, Issue 49 https://doi.org/10.1021/jacs.9b10354	journal	November 2019
In Situ Ru K-Edge X-Ray Absorption Fine Structure Studies of Electroprecipitated Ruthenium Dioxide Films with Relevance to Supercapacitor Applications Mo, Yibo; Antonio, Mark R.; Scherson, Daniel A. The Journal of Physical Chemistry B, Vol. 104, Issue 42 https://doi.org/10.1021/jp002355a	journal	October 2000
Chelation and stabilization of berkelium in oxidation state +IV Deblonde, Gauthier J. -P.; Sturzbecher-Hoehne, Manuel; Rupert, Peter B. Nature Chemistry, Vol. 9, Issue 9 https://doi.org/10.1038/nchem.2759	journal	April 2017
Emergence of californium as the second transitional element in the actinide series Cary, Samantha K.; Vasiliu, Monica; Baumbach, Ryan E. Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms7827	journal	April 2015
Ultra-selective ligand-driven separation of strategic actinides Deblonde, Gauthier J. -P.; Ricano, Abel; Abergel, Rebecca J. Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-10240-x	journal	June 2019
Probing electronic structure in berkelium and californium via an electron microscopy nanosampling approach Müller, Alexander; Deblonde, Gauthier J. -P.; Ercius, Peter Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-21189-1	journal	February 2021
Developing the 134Ce and 134La pair as companion positron emission tomography diagnostic isotopes for 225Ac and 227Th radiotherapeutics Bailey, Tyler A.; Mocko, Veronika; Shield, Katherine M. Nature Chemistry, Vol. 13, Issue 3 https://doi.org/10.1038/s41557-020-00598-7	journal	December 2020
Structural and spectroscopic characterization of an einsteinium complex Carter, Korey P.; Shield, Katherine M.; Smith, Kurt F. Nature, Vol. 590, Issue 7844 https://doi.org/10.1038/s41586-020-03179-3	journal	February 2021
Open questions in transplutonium coordination chemistry Carter, Korey P.; Pallares, Roger M.; Abergel, Rebecca J. Communications Chemistry, Vol. 3, Issue 1 https://doi.org/10.1038/s42004-020-00338-5	journal	August 2020
Developing scandium and yttrium coordination chemistry to advance theranostic radiopharmaceuticals Carter, Korey P.; Deblonde, Gauthier J. -P.; Lohrey, Trevor D. Communications Chemistry, Vol. 3, Issue 1 https://doi.org/10.1038/s42004-020-0307-0	journal	May 2020
Multiscale structural characterizations of mixed U( iv )–An( iii ) oxalates (An( iii ) = Pu or Am) combining XAS and XRD measurements Arab-Chapelet, B.; Martin, P. M.; Costenoble, S. Dalton Transactions, Vol. 45, Issue 16 https://doi.org/10.1039/C5DT04312C	journal	January 2016
Structural and thermodynamic investigation of An ^IV LI(O)HOPO Aupiais, J.; Younes, A.; Moisy, P. New Journal of Chemistry, Vol. 41, Issue 19 https://doi.org/10.1039/C7NJ02123B	journal	January 2017
Toxic heavy metal – Pb, Cd, Sn – complexation by the octadentate hydroxypyridinonate ligand archetype 3,4,3-LI(1,2-HOPO) Deblonde, Gauthier J. -P.; Lohrey, Trevor D.; An, Dahlia D. New Journal of Chemistry, Vol. 42, Issue 10 https://doi.org/10.1039/C7NJ04559J	journal	January 2018
Reductive activation of neptunyl and plutonyl oxo species with a hydroxypyridinone chelating ligand Carter, Korey P.; Jian, Jiwen; Pyrch, Mikaela M. Chemical Communications, Vol. 54, Issue 76 https://doi.org/10.1039/C8CC05626A	journal	January 2018
Exploring the electronic structure and speciation of aqueous and colloidal Pu with high energy resolution XANES and computations Vitova, Tonya; Pidchenko, Ivan; Fellhauer, David Chemical Communications, Vol. 54, Issue 91 https://doi.org/10.1039/C8CC06889E	journal	January 2018
Thiocyanate complexes of the lanthanides, Am and Cm Wilson, Richard E.; Carter, Tyler J.; Autillo, Matthieu Chemical Communications, Vol. 56, Issue 17 https://doi.org/10.1039/C9CC07612C	journal	January 2020
Combinatorial design of multimeric chelating peptoids for selective metal coordination Ricano, Abel; Captain, Ilya; Carter, Korey P. Chemical Science, Vol. 10, Issue 28 https://doi.org/10.1039/C9SC01068H	journal	January 2019
Efficient discrimination of transplutonium actinides by in vivo models Pallares, Roger M.; An, Dahlia D.; Deblonde, Gauthier J. -P. Chemical Science, Vol. 12, Issue 14 https://doi.org/10.1039/D0SC06610A	journal	January 2021
Advancing understanding of actinide( iii ) (Ac, Am, Cm) aqueous complexation chemistry Jones, Zachary R.; Livshits, Maksim Y.; White, Frankie D. Chemical Science, Vol. 12, Issue 15 https://doi.org/10.1039/D1SC00233C	journal	January 2021
3,4,3-LI(1,2-HOPO): In vitro formation of highly stable lanthanide complexes translates into efficacious in vivo europium decorporation Sturzbecher-Hoehne, Manuel; Ng Pak Leung, Clara; D'Aléo, Anthony Dalton Transactions, Vol. 40, Issue 33 https://doi.org/10.1039/c1dt10840a	journal	January 2011
High resolution x‐ray absorption spectroscopy with absolute energy calibration for the determination of absorption edge energies Kraft, S.; Stümpel, J.; Becker, P. Review of Scientific Instruments, Vol. 67, Issue 3 https://doi.org/10.1063/1.1146657	journal	March 1996
Siderocalin-mediated recognition, sensitization, and cellular uptake of actinides Allred, Benjamin E.; Rupert, Peter B.; Gauny, Stacey S. Proceedings of the National Academy of Sciences, Vol. 112, Issue 33 https://doi.org/10.1073/pnas.1508902112	journal	August 2015
Confirmation of standard error analysis techniques applied to EXAFS using simulations Booth, Corwin H.; Hu, Yung-Jin Journal of Physics: Conference Series, Vol. 190 https://doi.org/10.1088/1742-6596/190/1/012028	journal	November 2009
Biomimetic Actinide Chelators: an Update on the Preclinical Development of the Orally Active Hydroxypyridonate Decorporation Agents 3,4,3-Li(1,2-Hopo) and 5-Lio(Me-3,2-Hopo) Abergel, Rebecca J.; Durbin, Patricia W.; Kullgren, Birgitta Health Physics, Vol. 99, Issue 3 https://doi.org/10.1097/HP.0b013e3181c21273	journal	January 2010
X-ray-absorption fine-structure standards: A comparison of experiment and theory Li, G. G.; Bridges, F.; Booth, C. H. Physical Review B, Vol. 52, Issue 9 https://doi.org/10.1103/PhysRevB.52.6332	journal	September 1995
Relativistic XANES calculations of Pu hydrates Ankudinov, A. L.; Conradson, S. D.; Mustre de Leon, J. Physical Review B, Vol. 57, Issue 13 https://doi.org/10.1103/PhysRevB.57.7518	journal	April 1998
Real-space multiple-scattering calculation and interpretation of x-ray-absorption near-edge structure Ankudinov, A. L.; Ravel, B.; Rehr, J. J. Physical Review B, Vol. 58, Issue 12 https://doi.org/10.1103/PhysRevB.58.7565	journal	September 1998
Real-Space X-ray Absorption Package (RSXAP) Booth, Corwin H.; Bridges, Frank International Tables for Crystallography https://doi.org/10.1107/S1574870720003444	book	August 2021
Characterization of berkelium(III) dipicolinate and borate compounds in solution and the solid state Silver, M. A.; Cary, S. K.; Johnson, J. A. Science, Vol. 353, Issue 6302 https://doi.org/10.1126/science.aaf3762	journal	August 2016
Berkelium redox speciation Antonio, M. R.; Williams, C. W.; Soderholm, L. Radiochimica Acta, Vol. 90, Issue 12 https://doi.org/10.1524/ract.2002.90.12_2002.851	journal	January 2002
Plutonium(III,IV,VI) speciation in Gorleben groundwater using XAFS Dardenne, Kathy; Seibert, Alice; Denecke, Melissa A. Radiochimica Acta, Vol. 97, Issue 2 https://doi.org/10.1524/ract.2009.1581	journal	January 2009
X-ray absorption spectroscopic study of trivalent and tetravalent actinides in solution at varying pH values Brendebach, Boris; Banik, N. L.; Marquardt, Christian M. Radiochimica Acta, Vol. 97, Issue 12 https://doi.org/10.1524/ract.2009.1674	journal	January 2009
The redox behaviour of plutonium in humic rich groundwater Marquardt, Christian M.; Seibert, A.; Artinger, Robert Radiochimica Acta, Vol. 92, Issue 9-11 https://doi.org/10.1524/ract.92.9.617.55007	journal	January 2004
Actinide chelation: biodistribution and in vivo complex stability of the targeted metal ions Kullgren, Birgitta; Jarvis, Erin E.; An, Dahlia D. Toxicology Mechanisms and Methods, Vol. 23, Issue 1 https://doi.org/10.3109/15376516.2012.728641	journal	October 2012

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Title: In situ beam reduction of Pu(IV) and Bk(IV) as a route to trivalent transuranic coordination complexes with hydroxypyridinone chelators

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