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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.:
Oak Ridge National Laboratory, Oak Ridge Leadership Computing Facility (OLCF); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR) (SC-21)
OSTI Identifier:
1436161
Grant/Contract Number:  
AC02-05CH11231; AC05-00OR22725
Resource Type:
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. 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., and Abergel, Rebecca J. Mon . "Chelation and stabilization of berkelium in oxidation state +IV". United States. doi: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},
journal = {Nature Chemistry},
number = 9,
volume = 9,
place = {United States},
year = {2017},
month = {4}
}

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Cited by: 1 work
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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

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    Works referencing / citing this record:

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