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Title: Synthesis and characterization of a novel aminopolycarboxylate complexant for efficient trivalent f-element differentiation: N-butyl-2-acetamide-diethylenetriamine- N, N', N", N"-tetraacetic acid

Abstract

The novel metal ion complexant N-butyl-2-acetamide-diethylenetriamine-N,N',N",N"-tetraacetic acid (DTTA-BuA) uses an amide functionalization to increase the total ligand acidity and attain efficient 4f/5f differentiation in low pH conditions. The amide, when located on the diethylenetriamine platform containing four acetate pendant arms maintains the octadentate coordination sphere for all investigated trivalent f-elements. This compact coordination environment inhibits the protonation of LnL- complexes, as indicated by lower K 111 constants relative to the corresponding protonation site of the free ligand. For actinide ions, the enhanced stability of AnL- lowers the K 111 for americium and curium beyond the aptitude of potentiometric detection. Density functional theory computations indicate the difference in the back-donation ability of Am 3+ and Eu 3+ f-orbitals is mainly responsible for stronger proton affinity of EuL- compared to AmL-. The measured stability constants for the formation of AmL- and CmL- complexes are consistently higher, relative to ML- complexes with lanthanides of similar charge density. When compared with the conventional aminopolycarboxylate diethylenetriamine pentaacetic acid (DTPA), the modified DTTA-BuA complexant features higher ligand acidity and the important An 3+/Ln 3+ differentiation when deployed on a liquid–liquid distribution platform.

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 Dept.
  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:
1427624
Alternate Identifier(s):
OSTI ID: 1499585
Report Number(s):
INL/JOU-17-43032-Rev001
Journal ID: ISSN 1477-9226; ICHBD9
Grant/Contract Number:  
AC05-00OR22725; AC07-05ID14517; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Dalton Transactions
Additional Journal Information:
Journal Volume: 47; Journal Issue: 4; Journal ID: ISSN 1477-9226
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; 11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS; Fuel Cycle; Chelates; DTPA; f-element; complexant; TALSPEAK; ALSEP

Citation Formats

Heathman, Colt R., Grimes, Travis S., Jansone-Popova, Santa, Ivanov, Alexander S., Bryantsev, Vyacheslav S., and Zalupski, Peter R. Synthesis and characterization of a novel aminopolycarboxylate complexant for efficient trivalent f-element differentiation: N-butyl-2-acetamide-diethylenetriamine-N,N',N",N"-tetraacetic acid. United States: N. p., 2017. Web. doi:10.1039/c7dt04104g.
Heathman, Colt R., Grimes, Travis S., Jansone-Popova, Santa, Ivanov, Alexander S., Bryantsev, Vyacheslav S., & Zalupski, Peter R. Synthesis and characterization of a novel aminopolycarboxylate complexant for efficient trivalent f-element differentiation: N-butyl-2-acetamide-diethylenetriamine-N,N',N",N"-tetraacetic acid. United States. doi:10.1039/c7dt04104g.
Heathman, Colt R., Grimes, Travis S., Jansone-Popova, Santa, Ivanov, Alexander S., Bryantsev, Vyacheslav S., and Zalupski, Peter R. Thu . "Synthesis and characterization of a novel aminopolycarboxylate complexant for efficient trivalent f-element differentiation: N-butyl-2-acetamide-diethylenetriamine-N,N',N",N"-tetraacetic acid". United States. doi:10.1039/c7dt04104g. https://www.osti.gov/servlets/purl/1427624.
@article{osti_1427624,
title = {Synthesis and characterization of a novel aminopolycarboxylate complexant for efficient trivalent f-element differentiation: N-butyl-2-acetamide-diethylenetriamine-N,N',N",N"-tetraacetic acid},
author = {Heathman, Colt R. and Grimes, Travis S. and Jansone-Popova, Santa and Ivanov, Alexander S. and Bryantsev, Vyacheslav S. and Zalupski, Peter R.},
abstractNote = {The novel metal ion complexant N-butyl-2-acetamide-diethylenetriamine-N,N',N",N"-tetraacetic acid (DTTA-BuA) uses an amide functionalization to increase the total ligand acidity and attain efficient 4f/5f differentiation in low pH conditions. The amide, when located on the diethylenetriamine platform containing four acetate pendant arms maintains the octadentate coordination sphere for all investigated trivalent f-elements. This compact coordination environment inhibits the protonation of LnL- complexes, as indicated by lower K111 constants relative to the corresponding protonation site of the free ligand. For actinide ions, the enhanced stability of AnL- lowers the K111 for americium and curium beyond the aptitude of potentiometric detection. Density functional theory computations indicate the difference in the back-donation ability of Am3+ and Eu3+ f-orbitals is mainly responsible for stronger proton affinity of EuL- compared to AmL-. The measured stability constants for the formation of AmL- and CmL- complexes are consistently higher, relative to ML- complexes with lanthanides of similar charge density. When compared with the conventional aminopolycarboxylate diethylenetriamine pentaacetic acid (DTPA), the modified DTTA-BuA complexant features higher ligand acidity and the important An3+/Ln3+ differentiation when deployed on a liquid–liquid distribution platform.},
doi = {10.1039/c7dt04104g},
journal = {Dalton Transactions},
number = 4,
volume = 47,
place = {United States},
year = {2017},
month = {12}
}

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