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Title: Thermodynamic and Spectroscopic Studies of Trivalent f -element Complexation with Ethylenediamine- N,N '-di(acetylglycine)- N,N '-diacetic Acid

Abstract

In this study, the coordination behavior and thermodynamic features of complexation of trivalent lanthanides and americium by ethylenediamine- N,N'-di(acetylglycine)- N,N'-diacetic acid (EDDAG-DA) (bisamide-substituted-EDTA) were investigated by potentiometric and spectroscopic techniques. Acid dissociation constants (K a) and complexation constants (β) of lanthanides (except Pm) were determined by potentiometric analysis. Absorption spectroscopy was used to determine stability constants for the binding of trivalent americium and neodymium by EDDAG-DA under similar conditions. The potentiometry revealed 5 discernible protonation constants and 3 distinct metal–ligand complexes (identified as ML , MHL, and MH 2L +). Time-resolved fluorescence studies of Eu-(EDDAG-DA) solutions (at varying pH) identified a constant inner-sphere hydration number of 3, suggesting that glycine functionalities contained in the amide pendant arms are not involved in metal complexation and are protonated under more acidic conditions. The thermodynamic studies identified that f-element coordination by EDDAG-DA is similar to that observed for ethylenediamine- N,N,N',N'-tetraacetic acid (EDTA). However, coordination via two amidic oxygens of EDDAG-DA lowers its trivalent f-element complex stability by roughly 3 orders of magnitude relative to EDTA.

Authors:
; ;
Publication Date:
Research Org.:
Idaho National Lab. (INL), Idaho Falls, ID (United States)
Sponsoring Org.:
USDOE Office of Nuclear Energy (NE)
OSTI Identifier:
1303373
Report Number(s):
INL/JOU-15-37469
Journal ID: ISSN 0020-1669
Grant/Contract Number:  
AC07-05ID14517
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 55; Journal Issue: 6; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; coordination; actinide; lanthanide; TALSPEAK; ALSEP; separations; nuclear fuel cycle; f-elements; chelate; EDTA; thermodynamics; metal coordination; aminopolycarboxylatel aqueous complexants

Citation Formats

Heathman, Colt R., Grimes, Travis S., and Zalupski, Peter R. Thermodynamic and Spectroscopic Studies of Trivalent f -element Complexation with Ethylenediamine- N,N '-di(acetylglycine)- N,N '-diacetic Acid. United States: N. p., 2016. Web. doi:10.1021/acs.inorgchem.5b02865.
Heathman, Colt R., Grimes, Travis S., & Zalupski, Peter R. Thermodynamic and Spectroscopic Studies of Trivalent f -element Complexation with Ethylenediamine- N,N '-di(acetylglycine)- N,N '-diacetic Acid. United States. doi:10.1021/acs.inorgchem.5b02865.
Heathman, Colt R., Grimes, Travis S., and Zalupski, Peter R. Mon . "Thermodynamic and Spectroscopic Studies of Trivalent f -element Complexation with Ethylenediamine- N,N '-di(acetylglycine)- N,N '-diacetic Acid". United States. doi:10.1021/acs.inorgchem.5b02865. https://www.osti.gov/servlets/purl/1303373.
@article{osti_1303373,
title = {Thermodynamic and Spectroscopic Studies of Trivalent f -element Complexation with Ethylenediamine- N,N '-di(acetylglycine)- N,N '-diacetic Acid},
author = {Heathman, Colt R. and Grimes, Travis S. and Zalupski, Peter R.},
abstractNote = {In this study, the coordination behavior and thermodynamic features of complexation of trivalent lanthanides and americium by ethylenediamine-N,N'-di(acetylglycine)-N,N'-diacetic acid (EDDAG-DA) (bisamide-substituted-EDTA) were investigated by potentiometric and spectroscopic techniques. Acid dissociation constants (Ka) and complexation constants (β) of lanthanides (except Pm) were determined by potentiometric analysis. Absorption spectroscopy was used to determine stability constants for the binding of trivalent americium and neodymium by EDDAG-DA under similar conditions. The potentiometry revealed 5 discernible protonation constants and 3 distinct metal–ligand complexes (identified as ML–, MHL, and MH2L+). Time-resolved fluorescence studies of Eu-(EDDAG-DA) solutions (at varying pH) identified a constant inner-sphere hydration number of 3, suggesting that glycine functionalities contained in the amide pendant arms are not involved in metal complexation and are protonated under more acidic conditions. The thermodynamic studies identified that f-element coordination by EDDAG-DA is similar to that observed for ethylenediamine-N,N,N',N'-tetraacetic acid (EDTA). However, coordination via two amidic oxygens of EDDAG-DA lowers its trivalent f-element complex stability by roughly 3 orders of magnitude relative to EDTA.},
doi = {10.1021/acs.inorgchem.5b02865},
journal = {Inorganic Chemistry},
issn = {0020-1669},
number = 6,
volume = 55,
place = {United States},
year = {2016},
month = {3}
}

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Works referencing / citing this record:

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