skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: 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:
 [1];  [1];  [2];  [1];  [1];  [3];  [4];  [5];  [2];  [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
  2. Fred Hutchinson Cancer Research Center, Seattle, WA (United States). Division of Basic Science
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Berkeley Center for Structural Biology
  4. Academy of Sciences of the Czech Republic, Prague (Czech Republic). J. Heyrovsky Institute of Physical Chemistry
  5. 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}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 60 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1. Figure 1.: (A) Molecular structure of 3,4,3-LI(1,2-HOPO); the hydrogen atoms highlighted in red are labile. (B) Computed DFT structure of [BkIV3,4,3-LI(1,2-HOPO)]. (C) Experimental absorbance spectra of 3,4,3-LI(1,2-HOPO) complexes with Pu4+ (blue), Am3+ (magenta) and Bk (yellow) in aqueous solution. (D) Computed absorbance spectra for the Pu4+ (Supplementary Table S8), Bk4+,more » Bk3+ (green) and Am3+ (Supplementary Table S9) complexes. (E) Steady-state emission spectrum of [249BkIV3,4,3-LI(1,2-HOPO)] upon excitation at 320 nm in 0.1 M CHES buffer, pH 8.4, 25°C. (F) Jablonski diagrams for the ligand 3,4,3-LI(1,2-HOPO) and Cm3+, Bk3+, Bk4+ and Cf3+. Respective Bk4+ and An3+ energy levels correspond to those reported for Bk(IV)-doped CeF4(s)31 and for AnCl3 or An(III)-doped LaCl3(s).32« less

Save / Share:

Works referenced in this record:

Highly Luminescent and Stable Hydroxypyridinonate Complexes: A Step Towards New Curium Decontamination Strategies
journal, July 2014


Relativistic double-zeta, triple-zeta, and quadruple-zeta basis sets for the actinides Ac–Lr
journal, October 2006


The separation of berkelium(III) from cerium(III)
journal, February 1972


Energy‐adjusted pseudopotentials for the actinides. Parameter sets and test calculations for thorium and thorium monoxide
journal, May 1994


Rapid Chemical Separation for Bk
journal, January 2002


Intramolecular sensitization of americium luminescence in solution: shining light on short-lived forbidden 5f transitions
journal, January 2016


Latest achievements in the analytical chemistry of actinides
journal, January 1991


Element 97
journal, March 1950


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


Characterization of berkelium(III) dipicolinate and borate compounds in solution and the solid state
journal, August 2016


Berkelium redox speciation
journal, January 2002


Absorption spectra of Bk(III) and Bk(IV) in several media
journal, February 1972


The Neutrophil Lipocalin NGAL Is a Bacteriostatic Agent that Interferes with Siderophore-Mediated Iron Acquisition
journal, November 2002


NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations
journal, September 2010


Preliminary Data on 253Es and 249Bk Metabolism in Rats
journal, January 1972


The stability of tetravalent berkelium in acid solution and the absorption spectra of Bk(IV) and Bk(III)
journal, March 1973


Laser induced fluorescence of 249Bk4+ in CeF4
journal, December 1987


Higher Oxidation States of Americium: Preparation, Characterization and Use for Separations
journal, September 2011


Siderocalin-mediated recognition, sensitization, and cellular uptake of actinides
journal, August 2015


Optimization of Gaussian-type basis sets for local spin density functional calculations. Part I. Boron through neon, optimization technique and validation
journal, February 1992


Microscopic Distribution of Californium-249 and Berkelium-249 in the Soft Tissues of Beagles
journal, January 1972


Perspective methods for Berkelium – 249 preparation and application
journal, November 2002


Intramolecular energy transfer and sensitized luminescence in actinide(III) β-diketone chelates
journal, May 1969


Extraction of tetravalent berkelium by high molecular weight amines in the presence of heteropolyanions
journal, March 1986


Voltammetric Investigation of the Berkelium(IV/III) Couple in Concentrated Aqueous Carbonate Solutions
journal, January 1990


Chemical Properties of Berkelium
journal, June 1950


Present Status of Cerium(IV)-Cerium(III) Potentials
journal, December 1957


In Vitro Metabolism and Stability of the Actinide Chelating Agent 3,4,3-LI(1,2-HOPO)
journal, May 2015


New method for rapid separation of berkelium(IV) from cerium(IV) by anion exchange
journal, December 1967


Isolation of berkelium by solvent extraction of the tetravalent species
journal, January 1957


The formal potential of the Bk(IV)-Bk(III) couple in several media
journal, January 1972


Electronic energy level and intensity correlations in the spectra of the trivalent actinide aquo ions. III. Bk 3 +
journal, March 1984


The Protein Data Bank
journal, January 2000


Procedures for a fast separation of berkelium from complex mixtures of reaction products
journal, March 1983


The absorption spectra of Bk3+ and Bk4+ in solution
journal, September 1967


Efficient Algorithms for Estimating the Absorption Spectrum within Linear Response TDDFT
journal, October 2015


The size of actinoid(III) ions – structural analysis vs. common misinterpretations
journal, July 2016


Works referencing / citing this record:

Combinatorial design of multimeric chelating peptoids for selective metal coordination
journal, January 2019


Combinatorial design of multimeric chelating peptoids for selective metal coordination
journal, January 2019


Contemporary Chemistry of Berkelium and Californium
journal, June 2019


Inducing selectivity and chirality in group IV metal coordination with high-denticity hydroxypyridinones
journal, January 2019


Ultra-selective ligand-driven separation of strategic actinides
journal, June 2019


Reductive activation of neptunyl and plutonyl oxo species with a hydroxypyridinone chelating ligand
journal, January 2018


Toxic heavy metal – Pb, Cd, Sn – complexation by the octadentate hydroxypyridinonate ligand archetype 3,4,3-LI(1,2-HOPO)
journal, January 2018


Transuranic Computational Chemistry
journal, November 2017


Ultra-selective ligand-driven separation of strategic actinides
journal, June 2019


Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.