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Eu(III) and Cm(III) Complexation by the Aminocarboxylates NTA, EDTA, and EGTA Studied with NMR, TRLFS, and ITC—An Improved Approach to More Robust Thermodynamics

Journal Article · · Molecules
 [1];  [1];  [1];  [2];  [1];  [1];  [1];  [1]
  1. Helmholtz-Zentrum Dresden-Rossendorf (Germany)
  2. Helmholtz-Zentrum Dresden-Rossendorf (Germany); Tokyo Institute of Technology (Japan)
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The complex formation of Eu(III) and Cm(III) was studied via tetradentate, hexadentate, and octadentate coordinating ligands of the aminopolycarboxylate family, viz., nitrilotriacetate (NTA3-), ethylenediaminetetraacetate (EDTA4-), and ethylene glycol-bis(2-aminoethyl ether)-N,N,N',N'-tetraacetate (EGTA4-), respectively. Based on the complexones’ pKa values obtained from 1H nuclear magnetic resonance (NMR) spectroscopic pH titration, complex formation constants were determined by means of the parallel-factor-analysis-assisted evaluation of Eu(III) and Cm(III) time-resolved laser-induced fluorescence spectroscopy (TRLFS). This was complemented by isothermal titration calorimetry (ITC), providing the enthalpy and entropy of the complex formation. This allowed us to obtain genuine species along with their molecular structures and corresponding reliable thermodynamic data. The three investigated complexones formed 1:1 complexes with both Eu(III) and Cm(III). Besides the established Eu(III)–NTA 1:1 and 1:2 complexes, we observed, for the first time, the existence of a Eu(III)–NTA 2:2 complex of millimolar metal and ligand concentrations. Demonstrated for thermodynamic studies on Eu(III) and Cm(III) interaction with complexones, the utilized approach is commonly applicable to many other metal–ligand systems, even to high-affinity ligands.
Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
2471368
Journal Information:
Molecules, Journal Name: Molecules Journal Issue: 12 Vol. 28; ISSN 1420-3049
Publisher:
MDPICopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
calorimetry
complex formation constant
high-affinity ligand
molecular structure
spectroscopy