Quantifying the binding strength of salicylaldoxime–uranyl complexes relative to competing salicylaldoxime–transition metal ion complexes in aqueous solution: a combined experimental and computational study

Mehio, Nada; Ivanov, Alexander S.; Williams, Neil J.; Mayes, Richard T.; Bryantsev, Vyacheslav S.; Hancock, Robert D.; Dai, Sheng

doi:10.1039/c6dt00116e

Title: Quantifying the binding strength of salicylaldoxime–uranyl complexes relative to competing salicylaldoxime–transition metal ion complexes in aqueous solution: a combined experimental and computational study

Journal Article · Mon Mar 07 00:00:00 EST 2016 · Dalton Transactions

DOI:https://doi.org/10.1039/c6dt00116e· OSTI ID:1462912

Mehio, Nada ^[1]; Ivanov, Alexander S. ^[2];

^[3];

^[2];

^[2]; Hancock, Robert D. ^[4];

^[3]

Univ. of Tennessee, Knoxville, TN (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Univ. of North Carolina, Wilmington, NC (United States)

Here, the design of new ligands and investigation of UO₂²⁺ complexations are an essential aspect of reducing the cost of extracting uranium from seawater, improving the sorption efficiency for uranium and the selectivity for uranium over competing ions (such as the transition metal cations). The binding strengths of salicylaldoxime–UO₂²⁺ complexes were quantified for the first time and compared with the binding strengths of salicylic acid–UO₂²⁺ and representative amidoxime–UO₂²⁺ complexes. We found that the binding strengths of salicylaldoxime–UO₂²⁺ complexes are ~2–4 log β₂ units greater in magnitude than their corresponding salicylic acid–UO₂²⁺ and representative amidoxime–UO₂²⁺ complexes; moreover, the selectivity of salicylaldoxime towards the UO₂²⁺ cation over competing Cu²⁺ and Fe³⁺ cations is far greater than those reported for salicylic acid and glutarimidedioxime in the literature. The higher UO₂²⁺ selectivity can likely be attributed to the different coordination modes observed for salicylaldoxime–UO₂²⁺ and salicylaldoxime–transition metal complexes. Density functional theory calculations indicate that salicylaldoxime can coordinate with UO₂²⁺ as a dianion species formed by η² coordination of the aldoximate and monodentate binding of the phenolate group. In contrast, salicylaldoxime coordinates with transition metal cations as a monoanion species via a chelate formed between phenolate and the oxime N; the complexes are stabilized via hydrogen bonding interactions between the oxime OH group and phenolate. By coupling the experimentally determined thermodynamic constants and the results of theoretical computations, we are able to derive a number of ligand design principles to further improve the UO₂²⁺ cation affinity, and thus further increase the selectivity of salicylaldoxime derivatives.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Nuclear Energy (NE)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1462912

Journal Information:: Dalton Transactions, Vol. 45, Issue 22; ISSN 1477-9226

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 23 works

Citation information provided by
Web of Science

References (57)

Vanadium speciation and cycling in coastal waters Wang, Deli; Sañudo Wilhelmy, Sergio A. Marine Chemistry, Vol. 117, Issue 1-4 https://doi.org/10.1016/j.marchem.2009.06.001	journal	December 2009
Relativistic and correlation effects for element 105 (hahnium, Ha): a comparative study of M and MO (M = Nb, Ta, Ha) using energy-adjusted ab initio pseudopotentials Dolg, Michael; Stoll, Hermann; Preuss, Heinzwerner The Journal of Physical Chemistry, Vol. 97, Issue 22 https://doi.org/10.1021/j100124a012	journal	June 1993
Predicting Stability Constants for Uranyl Complexes Using Density Functional Theory Vukovic, Sinisa; Hay, Benjamin P.; Bryantsev, Vyacheslav S. Inorganic Chemistry, Vol. 54, Issue 8 https://doi.org/10.1021/acs.inorgchem.5b00264	journal	March 2015
IronIII and aluminiumIII complexes with substituted salicyl-aldehydes and salicylic acids Nurchi, Valeria M.; Crespo-Alonso, Miriam; Toso, Leonardo Journal of Inorganic Biochemistry, Vol. 128 https://doi.org/10.1016/j.jinorgbio.2013.07.016	journal	November 2013
Removal of Toxic Uranium from Synthetic Nuclear Power Reactor Effluents Using Uranyl Ion Imprinted Polymer Particles Preetha, Chandrika Ravindran; Gladis, Joseph Mary; Rao, Talasila Prasada Environmental Science & Technology, Vol. 40, Issue 9 https://doi.org/10.1021/es052195m	journal	May 2006
Insight into Technetium Amidoxime Complex: Oxo Technetium(V) Complex of N- Substituted Benzamidoxime as New Basic Structure for Molecular Imaging Thipyapong, Khajadpai; Uehara, Tomoya; Tooyama, Yuji Inorganic Chemistry, Vol. 50, Issue 3 https://doi.org/10.1021/ic101714q	journal	February 2011
Some theoretical and practical problems in the use of organic reagents in chemical analysis—V Burger, K.; Egyed, I. Journal of Inorganic and Nuclear Chemistry, Vol. 27, Issue 11 https://doi.org/10.1016/0022-1902(65)80128-2	journal	November 1965
Metal complexes of purine-N-oxides. I. The crystal structure of a copper(II) complex of doubly deprotonated adenine-N1-oxide Sletten, Einar; Marthinsen, Terje; Sletten, Jorunn Inorganica Chimica Acta, Vol. 93, Issue 1 https://doi.org/10.1016/S0020-1693(00)85955-1	journal	September 1984
Sequestering uranium from seawater: binding strength and modes of uranyl complexes with glutarimidedioxime Tian, Guoxin; Teat, Simon J.; Zhang, Zhiyong Dalton Transactions, Vol. 41, Issue 38 https://doi.org/10.1039/c2dt30978e	journal	January 2012
Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G. The Journal of Physical Chemistry B, Vol. 113, Issue 18, p. 6378-6396 https://doi.org/10.1021/jp810292n	journal	May 2009
Coordination chemistry of polyoxomolybdates: The versatile behavior of amidoximes Roh, Soo-Gyun; Proust, Anna; Robert, Francis Journal of Cluster Science, Vol. 7, Issue 4 https://doi.org/10.1007/BF01165804	journal	December 1996
Acidity of the Amidoxime Functional Group in Aqueous Solution: A Combined Experimental and Computational Study Mehio, Nada; Lashely, Mark A.; Nugent, Joseph W. The Journal of Physical Chemistry B, Vol. 119, Issue 8 https://doi.org/10.1021/jp512778x	journal	February 2015
The structures of phenolic oximes and their complexes Smith, A. Coordination Chemistry Reviews, Vol. 241, Issue 1-2 https://doi.org/10.1016/S0010-8545(02)00310-7	journal	June 2003
The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals Zhao, Yan; Truhlar, Donald G. Theoretical Chemistry Accounts, Vol. 120, Issue 1-3 https://doi.org/10.1007/s00214-007-0310-x	journal	July 2007
Surface Coordination Chemistry: Corrosion Inhibition by Tetranuclear Cluster Formation of Iron with Salicylaldoxime Thorpe, Jacqueline M.; Beddoes, Roy L.; Collison, David Angewandte Chemie International Edition, Vol. 38, Issue 8 https://doi.org/10.1002/(SICI)1521-3773(19990419)38:8<1119::AID-ANIE1119>3.0.CO;2-4	journal	April 1999
Raman spectroscopic determination of the acidity constants of salicylaldoxime in aqueous solution Elbagerma, M. A.; Edwards, H. G. M.; Azimi, Gholamhassan Journal of Raman Spectroscopy, Vol. 42, Issue 3 https://doi.org/10.1002/jrs.2716	journal	March 2011
Development of Sorbers for the Recovery of Uranium from Seawater. 1. Assessment of Key Parameters and Screening Studies of Sorber Materials Schenk, H. J.; Astheimer, L.; Witte, E. G. Separation Science and Technology, Vol. 17, Issue 11 https://doi.org/10.1080/01496398208056103	journal	August 1982
Extraction of Uranium from Sea Water Davies, R. V.; Kennedy, J.; McILROY, R. W. Nature, Vol. 203, Issue 4950 https://doi.org/10.1038/2031110a0	journal	September 1964
Complexation of glutarimidedioxime with Fe(iii), Cu(ii), Pb(ii), and Ni(ii), the competing ions for the sequestration of U(vi) from seawater Sun, Xiaoqi; Xu, Chao; Tian, Guoxin Dalton Transactions, Vol. 42, Issue 40 https://doi.org/10.1039/c3dt51767e	journal	January 2013
A Dimeric Copper(II) Complex of Oxalate and Oxamide Dioxime Ligands: Synthesis, Crystal Structure, Thermal Stability, and Magnetic Properties Nenwa, Justin; Djonwouo, Patrick L.; Nfor, Emmanuel N. Zeitschrift für Naturforschung B, Vol. 69, Issue 3 https://doi.org/10.5560/znb.2014-3309	journal	March 2014
Amidoximes as ligand functionalities for braided polymeric materials for the recovery of uranium from seawater Lashley, Mark A.; Mehio, Nada; Nugent, Joseph W. Polyhedron, Vol. 109 https://doi.org/10.1016/j.poly.2016.01.026	journal	April 2016
The Salicylate Method for Determining Microgram Amounts of Uranium Thomason, P. F.; Nutting, L. A.; Koskela, U. https://doi.org/10.2172/4380814	report	March 1955
Supramolecular chemistry in metal recovery; H-bond buttressing to tune extractant strength Forgan, Ross S.; Wood, Peter A.; Campbell, John Chemical Communications, Issue 46 https://doi.org/10.1039/b712278k	journal	January 2007
How Amidoximate Binds the Uranyl Cation Vukovic, Sinisa; Watson, Lori A.; Kang, Sung Ok Inorganic Chemistry, Vol. 51, Issue 6 https://doi.org/10.1021/ic300062s	journal	February 2012
Novel Dinuclear Uranyl Complexes with Asymmetric Schiff Base Ligands: Synthesis, Structural Characterization, Reactivity, and Extraction Studies Bharara, Mohan S.; Strawbridge, Kara; Vilsek, Jonah Z. Inorganic Chemistry, Vol. 46, Issue 20 https://doi.org/10.1021/ic7010315	journal	October 2007
Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint Reed, Alan E.; Curtiss, Larry A.; Weinhold, Frank Chemical Reviews, Vol. 88, Issue 6 https://doi.org/10.1021/cr00088a005	journal	September 1988
Seawater Uranium Sorbents: Preparation from a Mesoporous Copolymer Initiator by Atom-Transfer Radical Polymerization Yue, Yanfeng; Mayes, Richard T.; Kim, Jungseung Angewandte Chemie, Vol. 125, Issue 50 https://doi.org/10.1002/ange.201307825	journal	October 2013
Determination of copper complexation in sea water by cathodic stripping voltammetry and ligand competition with salicylaldoxime Lucia, M.; Campos, A. M.; van den Berg, Constant M. G. Analytica Chimica Acta, Vol. 284, Issue 3 https://doi.org/10.1016/0003-2670(94)85055-0	journal	January 1994
Spectrophotometric determination of acidity constants of salicylaldoxime in aqueous solution at 25°C and ionic strength of 0.5M controlled with NaCl Tshuma, Joel; Alarcón-Ángeles, Georgina; Palacios-Beas, Elia Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 66, Issue 4-5 https://doi.org/10.1016/j.saa.2006.05.004	journal	April 2007
Development of Sorbers for the Recovery of Uranium from Seawater. Part 2. The Accumulation of Uranium from Seawater by Resins Containing Amidoxime and Imidoxime Functional Groups Astheimer, L.; Schenk, H. J.; Witte, E. G. Separation Science and Technology, Vol. 18, Issue 4 https://doi.org/10.1080/01496398308068568	journal	April 1983
Use of Solution-Phase Vibrational Frequencies in Continuum Models for the Free Energy of Solvation Ribeiro, Raphael F.; Marenich, Aleksandr V.; Cramer, Christopher J. The Journal of Physical Chemistry B, Vol. 115, Issue 49 https://doi.org/10.1021/jp205508z	journal	December 2011
Density‐functional thermochemistry. III. The role of exact exchange Becke, Axel D. The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652 https://doi.org/10.1063/1.464913	journal	April 1993
New Insight of Coordination and Extraction of Uranium(VI) with N-Donating Ligands in Room Temperature Ionic Liquids: N , N ′-Diethyl- N , N ′-ditolyldipicolinamide as a Case Study Yuan, Li-Yong; Sun, Man; Mei, Lei Inorganic Chemistry, Vol. 54, Issue 4 https://doi.org/10.1021/ic502890w	journal	January 2015
Chemical Forms of Uranium in Artificial Seawater Saito, Kyoichi; Miyauchi, Terukatsu Journal of Nuclear Science and Technology, Vol. 19, Issue 2 https://doi.org/10.1080/18811248.1982.9734126	journal	February 1982
Reaction of oxomolybdenum complexes with amidoximes. Synthesis and structure of a nitrosylacetamidoximato(1-) complex with a N,O-side-on bonded acetamidoximate(1-) ligand: [Mo(acac)2 (CH3C(NH2)NO) (no)] Chilou, Valérie; Gouzerh, Pierre; Jeannin, Yves Inorganica Chimica Acta, Vol. 133, Issue 2 https://doi.org/10.1016/S0020-1693(00)87766-X	journal	October 1987
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density Lee, Chengteh; Yang, Weitao; Parr, Robert G. Physical Review B, Vol. 37, Issue 2 https://doi.org/10.1103/PhysRevB.37.785	journal	January 1988
Chemical Speciation of Uranium(VI) in Marine Environments: Complexation of Calcium and Magnesium Ions with [(UO ₂ )(CO ₃ ) ₃ ] ⁴⁻ and the Effect on the Extraction of Uranium from Seawater Endrizzi, Francesco; Rao, Linfeng Chemistry - A European Journal, Vol. 20, Issue 44 https://doi.org/10.1002/chem.201403262	journal	September 2014
Probing the Nature of Chemical Bonding in Uranyl(VI) Complexes with Quantum Chemical Methods Vallet, Valérie; Wahlgren, Ulf; Grenthe, Ingmar The Journal of Physical Chemistry A, Vol. 116, Issue 50 https://doi.org/10.1021/jp3091123	journal	November 2012
Natural hybrid orbitals Foster, J. P.; Weinhold, F. Journal of the American Chemical Society, Vol. 102, Issue 24 https://doi.org/10.1021/ja00544a007	journal	September 1980
Recovery of Uranium from Seawater: A Review of Current Status and Future Research Needs Kim, Jungseung; Tsouris, Costas; Mayes, Richard T. Separation Science and Technology, Vol. 48, Issue 3 https://doi.org/10.1080/01496395.2012.712599	journal	January 2013
Crystal structures of bis[2,2'-iminobis(acetamidoxime)]nickel(II) chloride dihydrate and bis[2,2'-iminobis(acetamidoxime)]copper(II) chloride Cullen, David L.; Lingafelter, Edward C. Inorganic Chemistry, Vol. 9, Issue 8 https://doi.org/10.1021/ic50090a017	journal	August 1970
Bis[N-(2,6-dimethylphenyl)aminoglyoximato-N,N']nickel(II) Ülkü, D.; Ercan, F.; Macit, M. Acta Crystallographica Section C Crystal Structure Communications, Vol. 52, Issue 11 https://doi.org/10.1107/S0108270196009407	journal	November 1996
Crystal structure of bis(acetato-κ O )bis(pyridine-2-carboxamide oxime-κ ² N , N ′)cadmium ethanol disolvate Liu, Jiyong Acta Crystallographica Section E Structure Reports Online, Vol. 70, Issue 9 https://doi.org/10.1107/S1600536814017978	journal	August 2014
Hyperquad simulation and speciation (HySS): a utility program for the investigation of equilibria involving soluble and partially soluble species Alderighi, Lucia; Gans, Peter; Ienco, Andrea Coordination Chemistry Reviews, Vol. 184, Issue 1 https://doi.org/10.1016/S0010-8545(98)00260-4	journal	April 1999
Soluble rare earth and actinide species in seawater Choppin, Gregory R. Marine Chemistry, Vol. 28, Issue 1-3 https://doi.org/10.1016/0304-4203(89)90184-9	journal	December 1989
The crystal structure of bis(5-chlorosalicylaldoximato)copper(II) Orioli, P. L.; Lingafelter, E. C.; Brown, B. W. Acta Crystallographica, Vol. 17, Issue 9 https://doi.org/10.1107/S0365110X64002912	journal	September 1964
Using the Outer Coordination Sphere to Tune the Strength of Metal Extractants Forgan, Ross S.; Roach, Benjamin D.; Wood, Peter A. Inorganic Chemistry, Vol. 50, Issue 10 https://doi.org/10.1021/ic200154y	journal	May 2011
Electronic Structure and Bonding in Actinyl Ions and their Analogs Denning, Robert G. The Journal of Physical Chemistry A, Vol. 111, Issue 20 https://doi.org/10.1021/jp071061n	journal	May 2007
The Cambridge Structural Database: a quarter of a million crystal structures and rising Allen, Frank H. Acta Crystallographica Section B Structural Science, Vol. 58, Issue 3 https://doi.org/10.1107/S0108768102003890	journal	May 2002
Computational Study of Copper(II) Complexation and Hydrolysis in Aqueous Solutions Using Mixed Cluster/Continuum Models Bryantsev, Vyacheslav S.; Diallo, Mamadou S.; Goddard, William A. The Journal of Physical Chemistry A, Vol. 113, Issue 34 https://doi.org/10.1021/jp904816d	journal	August 2009
Preparation of hydrophilic amidoxime fibers by cografting acrylonitrile and methacrylic acid from an optimized monomer composition Kawai, Tomomi; Saito, Kyoichi; Sugita, Kazuyuki Radiation Physics and Chemistry, Vol. 59, Issue 4, p. 405-411 https://doi.org/10.1016/S0969-806X(00)00298-X	journal	October 2000
Fractional Elution and Determination of Uranium and Vanadium Adsorbed on Amidoxime Fiber from Seawater. Suzuki, Toshihiro; Saito, Kyoichi; Sugo, Takanobu Analytical Sciences, Vol. 16, Issue 4 https://doi.org/10.2116/analsci.16.429	journal	January 2000
Protonation Constants of Some N-Substituted Amidoximes in a 50% Ethanol-Water Mixture (v/v). DÜRÜSt, Nedime; Abdülkadir AKAY, M.; DÜRÜSt, Yasar Analytical Sciences, Vol. 16, Issue 8 https://doi.org/10.2116/analsci.16.825	journal	January 2000
Comparison of Amidoxime Adsorbents Prepared by Cografting Methacrylic Acid and 2-Hydroxyethyl Methacrylate with Acrylonitrile onto Polyethylene Kawai, Tomomi; Saito, Kyoichi; Sugita, Kazuyuki Industrial & Engineering Chemistry Research, Vol. 39, Issue 8 https://doi.org/10.1021/ie990474a	journal	August 2000
Stereochemistry of nucleic acids and their constituents. XXI. The crystal and molecular structure of bis-(4-aminoimidazole-5-carboxamidoxime)copper(II) perchlorate, a degradation product of adenine N ¹ -oxide Stout, C. D.; Sundaralingam, M.; Lin, G. H. -Y. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 28, Issue 7 https://doi.org/10.1107/S0567740872005679	journal	July 1972
Thermodynamic studies of U(vi) complexation with glutardiamidoxime for sequestration of uranium from seawater Tian, Guoxin; Teat, Simon J.; Rao, Linfeng Dalton Transactions, Vol. 42, Issue 16 https://doi.org/10.1039/c3dt32940b	journal	January 2013
catena -Poly{[bis(2-amino-2-methyl-1-propanol)copper(II)-μ-salicylato(2–)- O : O ', O '']-copper(II)-μ-[salicylato(2–)- O ', O '': O ]} tetrakis(2-propanol) Muhonen, H. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 38, Issue 7 https://doi.org/10.1107/S0567740882007870	journal	July 1982

Cited By (5)

Origin of the unusually strong and selective binding of vanadium by polyamidoximes in seawater Ivanov, Alexander S.; Leggett, Christina J.; Parker, Bernard F. Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-01443-1	journal	November 2017
Bio-inspired nano-traps for uranium extraction from seawater and recovery from nuclear waste Sun, Qi; Aguila, Briana; Perman, Jason Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-04032-y	journal	April 2018
Siderophore-inspired chelator hijacks uranium from aqueous medium Ivanov, Alexander S.; Parker, Bernard F.; Zhang, Zhicheng Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-08758-1	journal	February 2019
Paper-Based Analytical Device for Zinc Ion Quantification in Water Samples with Power-Free Analyte Concentration Kudo, Hiroko; Yamada, Kentaro; Watanabe, Daiki Micromachines, Vol. 8, Issue 4 https://doi.org/10.3390/mi8040127	journal	April 2017
Predicting Stability Constants for Terbium(III) Complexes with Dipicolinic Acid and 4-Substituted Dipicolinic Acid Analogues using Density Functional Theory Chen, Hsieh; Shi, Rena; Ow, Hooisweng ACS Omega, Vol. 4, Issue 24 https://doi.org/10.1021/acsomega.9b02851	journal	November 2019

Similar Records

Quantitative Prediction of Uranium Speciation and Amidoxime Binding in Seawater from Advanced Simulation Techniques

Technical Report · Sat Dec 29 00:00:00 EST 2018 · OSTI ID:1462912

Jiang, De-en

Theoretical study of the coordination behavior of formate and formamidoximate with dioxovanadium( v ) cation: implications for selectivity towards uranyl

Journal Article · Wed Oct 28 00:00:00 EDT 2015 · Physical Chemistry Chemical Physics. PCCP · OSTI ID:1462912

Mehio, Nada; Johnson, J. Casey; Dai, Sheng; +1 more

Theoretical Study of Oxovanadium(IV) Complexation with Formamidoximate: Implications for the Design of Uranyl-Selective Adsorbents

Journal Article · Sun Nov 22 00:00:00 EST 2015 · Industrial and Engineering Chemistry Research · OSTI ID:1462912

Mehio, Nada; Ivanov, Alexander S.; Ladshaw, Austin P.; +2 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Title: Quantifying the binding strength of salicylaldoxime–uranyl complexes relative to competing salicylaldoxime–transition metal ion complexes in aqueous solution: a combined experimental and computational study

Citation Formats

References (57)

Cited By (5)

Similar Records

Related Subjects