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Title: Influence of a Pre-organized N-Donor Group on the Coordination of Trivalent Actinides and Lanthanides by an Aminopolycarboxylate Complexant

Abstract

Thermodynamic influence of a pre-organized N-donor group on the coordination of trivalent actinides and lanthanides by aminopolycarboxylate aqueous complexant was investigated. The synthesized complexant N-2-methylpicolinate-ethylenediamine-N,N',N'-triacetic acid, EDTA-Mpic, resembles ethylenediamine-N,N,N',N'-tetraacetic acid, EDTA, with single acetate pendant arm replaced by 6-carboxypyridin-2-yl-methyl group. The rigidified N-donor picolinate functionality shows profound impact on the ligand protonation, and trivalent f-element complexation equilibria as demonstrated using potentiometric, spectroscopic, liquid-liquid metal partitioning studies and molecular dynamics calculations. While the coordination pocket of EDTA-Mpic is somewhat hardened by the N-methylpicolinate the substantial amplification of its total acidity offers the advantage of sustaining metal complexation in aqueous mixtures of unprecedented acidity for this class of reagents. As a result the EDTA-Mpic complexant may be considered the best option for efficient f-element recovery and An3+/Ln3+ differentiation in acidic media.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [1]
  1. Idaho National Lab. (INL), Idaho Falls, ID (United States). Aqueous Separations and Radiochemistry
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Idaho National Lab. (INL), Idaho Falls, ID (United States)
Sponsoring Org.:
USDOE Office of Nuclear Energy (NE)
OSTI Identifier:
1564104
Alternate Identifier(s):
OSTI ID: 1596093; OSTI ID: 1635428
Report Number(s):
INL/JOU-18-51606-Rev001
Journal ID: ISSN 0947-6539; TRN: US2000855
Grant/Contract Number:  
AC05-00OR22725; DE-AC07-05ID14517
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Volume: 25; Journal Issue: 10; Journal ID: ISSN 0947-6539
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS; 37 - INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 38 - RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; trivalent f-elements; lanthanides; actinides; aminopolycarboxylates; metal coordination; thermodynamics; molecular dynamics

Citation Formats

Heathman, Colt R., Grimes, Travis S., Jansone-Popova, Santa, Roy, Santanu, Bryantsev, Vyacheslav S., and Zalupski, Peter R. Influence of a Pre-organized N-Donor Group on the Coordination of Trivalent Actinides and Lanthanides by an Aminopolycarboxylate Complexant. United States: N. p., 2019. Web. doi:10.1002/chem.201804723.
Heathman, Colt R., Grimes, Travis S., Jansone-Popova, Santa, Roy, Santanu, Bryantsev, Vyacheslav S., & Zalupski, Peter R. Influence of a Pre-organized N-Donor Group on the Coordination of Trivalent Actinides and Lanthanides by an Aminopolycarboxylate Complexant. United States. doi:10.1002/chem.201804723.
Heathman, Colt R., Grimes, Travis S., Jansone-Popova, Santa, Roy, Santanu, Bryantsev, Vyacheslav S., and Zalupski, Peter R. Mon . "Influence of a Pre-organized N-Donor Group on the Coordination of Trivalent Actinides and Lanthanides by an Aminopolycarboxylate Complexant". United States. doi:10.1002/chem.201804723. https://www.osti.gov/servlets/purl/1564104.
@article{osti_1564104,
title = {Influence of a Pre-organized N-Donor Group on the Coordination of Trivalent Actinides and Lanthanides by an Aminopolycarboxylate Complexant},
author = {Heathman, Colt R. and Grimes, Travis S. and Jansone-Popova, Santa and Roy, Santanu and Bryantsev, Vyacheslav S. and Zalupski, Peter R.},
abstractNote = {Thermodynamic influence of a pre-organized N-donor group on the coordination of trivalent actinides and lanthanides by aminopolycarboxylate aqueous complexant was investigated. The synthesized complexant N-2-methylpicolinate-ethylenediamine-N,N',N'-triacetic acid, EDTA-Mpic, resembles ethylenediamine-N,N,N',N'-tetraacetic acid, EDTA, with single acetate pendant arm replaced by 6-carboxypyridin-2-yl-methyl group. The rigidified N-donor picolinate functionality shows profound impact on the ligand protonation, and trivalent f-element complexation equilibria as demonstrated using potentiometric, spectroscopic, liquid-liquid metal partitioning studies and molecular dynamics calculations. While the coordination pocket of EDTA-Mpic is somewhat hardened by the N-methylpicolinate the substantial amplification of its total acidity offers the advantage of sustaining metal complexation in aqueous mixtures of unprecedented acidity for this class of reagents. As a result the EDTA-Mpic complexant may be considered the best option for efficient f-element recovery and An3+/Ln3+ differentiation in acidic media.},
doi = {10.1002/chem.201804723},
journal = {Chemistry - A European Journal},
number = 10,
volume = 25,
place = {United States},
year = {2019},
month = {1}
}

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Works referenced in this record:

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

A new heptadentate picolinate-based ligand and its corresponding Gd( iii ) complex: the effect of pendant picolinate versus acetate on complex properties
journal, January 2018

  • Phukan, Bedika; Mukherjee, Chandan; Varshney, Raunak
  • Dalton Transactions, Vol. 47, Issue 1
  • DOI: 10.1039/C7DT04150K

Actinide Lanthanide Separation Process—ALSEP
journal, January 2014

  • Gelis, Artem V.; Lumetta, Gregg J.
  • Industrial & Engineering Chemistry Research, Vol. 53, Issue 4
  • DOI: 10.1021/ie403569e

A half-century of lanthanide aminopolycarboxylates
journal, February 1993


Projector augmented-wave method
journal, December 1994


Complexation kinetics of f-elements and polydentate ligands
journal, July 1995


Complexation of Actinide(III) and Lanthanide(III) with H 4 TPAEN for a Separation of Americium from Curium and Lanthanides
journal, June 2017


The absorption spectrum of aqueous curium (III)
journal, June 1958

  • Carnall, W. T.; Fields, P. R.; Stewart, D. C.
  • Journal of Inorganic and Nuclear Chemistry, Vol. 6, Issue 3
  • DOI: 10.1016/0022-1902(58)80150-5

A spectrophotometric study of Am( iii ) complexation with nitrate in aqueous solution at elevated temperatures
journal, January 2014


H 4 octapa: synthesis, solution equilibria and complexes with useful radiopharmaceutical metal ions
journal, January 2017

  • Jaraquemada-Peláez, María de Guadalupe; Wang, Xiaozhu; Clough, Thomas J.
  • Dalton Transactions, Vol. 46, Issue 42
  • DOI: 10.1039/C7DT02343J

Potentiometric titrations using Gran plots: A textbook omission
journal, July 1965

  • Rossotti, F. J. C.; Rossotti, Hazel
  • Journal of Chemical Education, Vol. 42, Issue 7
  • DOI: 10.1021/ed042p375

Chelate ring size and metal ion selection. The basis of selectivity for metal ions in open-chain ligands and macrocycles
journal, August 1992

  • Hancock, Robert D.
  • Journal of Chemical Education, Vol. 69, Issue 8
  • DOI: 10.1021/ed069p615

The Chemistry of TALSPEAK: A Review of the Science
journal, December 2014


Reaction Rate Theory in Coordination Number Space: An Application to Ion Solvation
journal, March 2016

  • Roy, Santanu; Baer, Marcel D.; Mundy, Christopher J.
  • The Journal of Physical Chemistry C, Vol. 120, Issue 14
  • DOI: 10.1021/acs.jpcc.6b00443

Stability, Water Exchange, and Anion Binding Studies on Lanthanide(III) Complexes with a Macrocyclic Ligand Based on 1,7-Diaza-12-crown-4: Extremely Fast Water Exchange on the Gd 3+ Complex
journal, September 2009

  • Pálinkás, Zoltán; Roca-Sabio, Adrián; Mato-Iglesias, Marta
  • Inorganic Chemistry, Vol. 48, Issue 18
  • DOI: 10.1021/ic9011197

Complexation thermodynamics and structural aspects of actinide–aminopolycarboxylates
journal, April 2006


Optical properties of Cm(III) in crystals and solutions and their application to Cm(III) speciation
journal, April 2006

  • Edelstein, Norman M.; Klenza, Reinhardt; Fanghanel, Thomas
  • Coordination Chemistry Reviews, Vol. 250, Issue 7-8, p. 948-973
  • DOI: 10.1016/j.ccr.2006.02.004

Lanthanide dota-like Complexes Containing a Picolinate Pendant: Structural Entry for the Design of Ln III -Based Luminescent Probes
journal, May 2011

  • Regueiro-Figueroa, Martín; Bensenane, Bachir; Ruscsák, Erika
  • Inorganic Chemistry, Vol. 50, Issue 9
  • DOI: 10.1021/ic2001915

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


A critical review on solvent extraction of rare earths from aqueous solutions
journal, February 2014


Fast Parallel Algorithms for Short-Range Molecular Dynamics
journal, March 1995


Determination of the Equivalent Point in Potentiometric Titrations.
journal, January 1950


Differentiating between Trivalent Lanthanides and Actinides
journal, June 2012

  • Polinski, Matthew J.; Grant, Daniel J.; Wang, Shuao
  • Journal of the American Chemical Society, Vol. 134, Issue 25
  • DOI: 10.1021/ja303804r

Luminescent lanthanide sensors for pH, pO2 and selected anions
journal, August 2000


Luminescence study on determination of the hydration number of Cm(III)
journal, October 1994


Using lanthanide ions in molecular bioimaging
journal, January 2015

  • Amoroso, Angelo J.; Pope, Simon J. A.
  • Chemical Society Reviews, Vol. 44, Issue 14
  • DOI: 10.1039/C4CS00293H

Solution Structures of Europium(Iii) Complexes of Ethylenediaminetetraacetic acid
journal, April 1996

  • Latva, Martti; Kankare, Jouko; Haapakka, Keijo
  • Journal of Coordination Chemistry, Vol. 38, Issue 1-2
  • DOI: 10.1080/00958979608022693

Covalency in f-element complexes
journal, January 2013

  • Neidig, Michael L.; Clark, David L.; Martin, Richard L.
  • Coordination Chemistry Reviews, Vol. 257, Issue 2
  • DOI: 10.1016/j.ccr.2012.04.029

Ab initiomolecular dynamics for liquid metals
journal, January 1993


Does Covalency Increase or Decrease across the Actinide Series? Implications for Minor Actinide Partitioning
journal, June 2012


Stable Mn 2+ , Cu 2+ and Ln 3+ complexes with cyclen-based ligands functionalized with picolinate pendant arms
journal, January 2015

  • Rodríguez-Rodríguez, Aurora; Garda, Zoltán; Ruscsák, Erika
  • Dalton Transactions, Vol. 44, Issue 11
  • DOI: 10.1039/C4DT02985B

An Ion-exchange Study of Possible Hybridized 5f Bonding in the Actinides 1
journal, March 1954

  • Diamond, R. M.; Street, K.; Seaborg, G. T.
  • Journal of the American Chemical Society, Vol. 76, Issue 6
  • DOI: 10.1021/ja01635a001

Luminescence study on determination of the hydration number of Sm(III) and Dy(III)
journal, July 1995


On the Origin of Covalent Bonding in Heavy Actinides
journal, July 2017

  • Kelley, Morgan P.; Su, Jing; Urban, Matthew
  • Journal of the American Chemical Society, Vol. 139, Issue 29
  • DOI: 10.1021/jacs.7b03251

Lanthanide ion probes of structure in biology. Laser-induced luminescence decay constants provide a direct measure of the number of metal-coordinated water molecules
journal, January 1979

  • Horrocks, William DeW.; Sudnick, Daniel R.
  • Journal of the American Chemical Society, Vol. 101, Issue 2
  • DOI: 10.1021/ja00496a010

Acid Dissociation Constants and Rare Earth Stability Constants for DTPA
journal, February 2014


A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010

  • Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
  • The Journal of Chemical Physics, Vol. 132, Issue 15
  • DOI: 10.1063/1.3382344

Pyridine-Based Lanthanide Complexes Combining MRI and NIR Luminescence Activities
journal, December 2011

  • Bonnet, Célia S.; Buron, Frédéric; Caillé, Fabien
  • Chemistry - A European Journal, Vol. 18, Issue 5
  • DOI: 10.1002/chem.201102310

Convergence acceleration of iterative sequences. the case of scf iteration
journal, July 1980


Trans‐Lanthanide Extraction Studies in the TALSPEAK System: Investigating the Effect of Acidity and Temperature
journal, April 2009


Thermodynamic and Spectroscopic Studies of Trivalent f -element Complexation with Ethylenediamine- N,N ′-di(acetylglycine)- N,N ′-diacetic Acid
journal, March 2016


[Gd(CyPic3A)(H2O)2]−: a stable, bis(aquated) and high-relaxivity Gd(iii) complex
journal, January 2013

  • Gale, Eric M.; Kenton, Nathaniel; Caravan, Peter
  • Chemical Communications, Vol. 49, Issue 73
  • DOI: 10.1039/c3cc44116d

Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)]
journal, February 1997


Ab Initio Calculations on Small Molecule Analogs of Polycarbonates
journal, April 1995

  • Sun, H.; Mumby, S. J.; Maple, J. R.
  • The Journal of Physical Chemistry, Vol. 99, Issue 16
  • DOI: 10.1021/j100016a022

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


GROMACS: A message-passing parallel molecular dynamics implementation
journal, September 1995

  • Berendsen, H. J. C.; van der Spoel, D.; van Drunen, R.
  • Computer Physics Communications, Vol. 91, Issue 1-3
  • DOI: 10.1016/0010-4655(95)00042-E

Optical Absorption Intensities of Rare-Earth Ions
journal, August 1962


Lanthanide Probes for Bioresponsive Imaging
journal, December 2013

  • Heffern, Marie C.; Matosziuk, Lauren M.; Meade, Thomas J.
  • Chemical Reviews, Vol. 114, Issue 8
  • DOI: 10.1021/cr400477t

Determination of the equivalence point in potentiometric titrations. Part II
journal, January 1952


Gadolinium(III) Chelates as MRI Contrast Agents:  Structure, Dynamics, and Applications
journal, September 1999

  • Caravan, Peter; Ellison, Jeffrey J.; McMurry, Thomas J.
  • Chemical Reviews, Vol. 99, Issue 9
  • DOI: 10.1021/cr980440x

Lanthanide Luminescence for Biomedical Analyses and Imaging
journal, May 2010

  • Bünzli, Jean-Claude G.
  • Chemical Reviews, Vol. 110, Issue 5
  • DOI: 10.1021/cr900362e

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Matching chelators to radiometals for radiopharmaceuticals
journal, January 2014


Syntheses, Characterization and Structural Determination of Nine Coordinated N2H5[Ce(edta)(H2O)3]·4H2O and N2H5[Eu(edta)(H2O)3]·4H2O
journal, May 2011


Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994


Trefoil-Shaped Outer-Sphere Ion Clusters Mediate Lanthanide(III) Ion Transport with Diglycolamide Ligands
journal, November 2017

  • Brigham, Derek M.; Ivanov, Alexander S.; Moyer, Bruce A.
  • Journal of the American Chemical Society, Vol. 139, Issue 48
  • DOI: 10.1021/jacs.7b07318

Optical Absorption Characteristics For  7F0'→5L6' and  7F0'→ 7F6' Transitions of Trivalent Americium Ion in Aqueous Electrolyte Mixtures
journal, July 2017

  • Zalupski, Peter R.; Grimes, Travis S.; Heathman, Colt R.
  • Applied Spectroscopy, Vol. 71, Issue 12
  • DOI: 10.1177/0003702817721528

Electronic energy level and intensity correlations in the spectra of the trivalent actinide aquo ions. II. Cm 3+
journal, October 1975

  • Carnall, W. T.; Rajnak, K.
  • The Journal of Chemical Physics, Vol. 63, Issue 8
  • DOI: 10.1063/1.431789

Luminescence study on hydration states of lanthanide(III)–polyaminopolycarboxylate complexes in aqueous solution
journal, July 1998


Trivalent Lanthanide/Actinide Separation Using Aqueous-Modified TALSPEAK Chemistry
journal, May 2014

  • Grimes, Travis S.; Tillotson, Richard D.; Martin, Leigh R.
  • Solvent Extraction and Ion Exchange, Vol. 32, Issue 4
  • DOI: 10.1080/07366299.2013.877754

Lanthanide Complexes of a Picolinate Ligand Derived from 1,4,7-Triazacyclononane with Potential Application in Magnetic Resonance Imaging and Time-Resolved Luminescence Imaging
journal, September 2006

  • Nonat, Aline; Gateau, Christelle; Fries, Pascal H.
  • Chemistry - A European Journal, Vol. 12, Issue 27
  • DOI: 10.1002/chem.200501390

Complexation of Curium(III) with DTPA at 10–70 °C: Comparison with Eu(III)–DTPA in Thermodynamics, Luminescence, and Coordination Modes
journal, January 2015

  • Tian, Guoxin; Zhang, Zhiyong; Martin, Leigh R.
  • Inorganic Chemistry, Vol. 54, Issue 4
  • DOI: 10.1021/ic5016934

H 4 octapa: Highly Stable Complexation of Lanthanide(III) Ions and Copper(II)
journal, February 2015

  • Kálmán, Ferenc Krisztián; Végh, Andrea; Regueiro-Figueroa, Martín
  • Inorganic Chemistry, Vol. 54, Issue 5
  • DOI: 10.1021/ic502966m

Coordination Chemistry and f-Element Complexation by Diethylenetriamine- N , N ″-bis(acetylglycine)- N , N ′, N ″-triacetic Acid
journal, October 2016


The complexation of lanthanides by aminocarboxylate ligands—I
journal, January 1977

  • Gritmon, T. F.; Goedken, M. P.; Choppin, G. R.
  • Journal of Inorganic and Nuclear Chemistry, Vol. 39, Issue 11
  • DOI: 10.1016/0022-1902(77)80538-1

VMD: Visual molecular dynamics
journal, February 1996


Critical stability constants, enthalpies and entropies for the formation of metal complexes of aminopolycarboxylic acids and carboxylic acids
journal, June 1987


The effect of pyridinecarboxylate chelating groups on the stability and electronic relaxation of gadolinium complexes
journal, January 2005

  • Chatterton, Nicholas; Gateau, Christelle; Mazzanti, Marinella
  • Dalton Trans., Issue 6
  • DOI: 10.1039/B416150E

Hydrothermal investigation of the lanthanide (Ln=La, Ce, Pr, Nd, Sm) 2,6-pyridinedicarboxylate system
journal, April 2002


Two-Dimensional and Three-Dimensional Lanthanide Coordination Polymers Built from 4-Hydroxypyridine-2,6-dicarboxylic Acid Ligand
journal, July 2009

  • Sun, Ya-Guang; Rong, Shu-Ting; Yu, Wan
  • Zeitschrift für anorganische und allgemeine Chemie
  • DOI: 10.1002/zaac.200900110