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Outer-Sphere Water Clusters Tune the Lanthanide Selectivity of Diglycolamides
[Image: see text] Fundamental understanding of the selective recognition and separation of f-block metal ions by chelating agents is of crucial importance for advancing sustainable energy systems. Current investigations in this area are mostly focused on the study of inner-sphere interactions betwee...
Autores principales: | , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2018
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6026780/ https://www.ncbi.nlm.nih.gov/pubmed/29974069 http://dx.doi.org/10.1021/acscentsci.8b00223 |
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author | Baldwin, Anna G. Ivanov, Alexander S. Williams, Neil J. Ellis, Ross J. Moyer, Bruce A. Bryantsev, Vyacheslav S. Shafer, Jenifer C. |
author_facet | Baldwin, Anna G. Ivanov, Alexander S. Williams, Neil J. Ellis, Ross J. Moyer, Bruce A. Bryantsev, Vyacheslav S. Shafer, Jenifer C. |
author_sort | Baldwin, Anna G. |
collection | PubMed |
description | [Image: see text] Fundamental understanding of the selective recognition and separation of f-block metal ions by chelating agents is of crucial importance for advancing sustainable energy systems. Current investigations in this area are mostly focused on the study of inner-sphere interactions between metal ions and donor groups of ligands, while the effects on the selectivity resulting from molecular interactions in the outer-sphere region have been largely overlooked. Herein, we explore the fundamental origins of the selectivity of the solvating extractant N,N,N′,N′-tetraoctyl diglycolamide (TODGA) for adjacent lanthanides in a liquid–liquid extraction system, which is of relevance to nuclear fuel reprocessing and rare-earth refining technologies. Complementary investigations integrating distribution studies, quantum mechanical calculations, and classical molecular dynamics simulations establish a relationship between coextracted water and lanthanide extraction by TODGA across the series, pointing to the importance of the hydrogen-bonding interactions between outer-sphere nitrate ions and water clusters in a nonpolar environment. Our findings have significant implications for the design of novel efficient separation systems and processes, emphasizing the importance of tuning both inner- and outer-sphere interactions to obtain total control over selectivity in the biphasic extraction of lanthanides. |
format | Online Article Text |
id | pubmed-6026780 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2018 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-60267802018-07-04 Outer-Sphere Water Clusters Tune the Lanthanide Selectivity of Diglycolamides Baldwin, Anna G. Ivanov, Alexander S. Williams, Neil J. Ellis, Ross J. Moyer, Bruce A. Bryantsev, Vyacheslav S. Shafer, Jenifer C. ACS Cent Sci [Image: see text] Fundamental understanding of the selective recognition and separation of f-block metal ions by chelating agents is of crucial importance for advancing sustainable energy systems. Current investigations in this area are mostly focused on the study of inner-sphere interactions between metal ions and donor groups of ligands, while the effects on the selectivity resulting from molecular interactions in the outer-sphere region have been largely overlooked. Herein, we explore the fundamental origins of the selectivity of the solvating extractant N,N,N′,N′-tetraoctyl diglycolamide (TODGA) for adjacent lanthanides in a liquid–liquid extraction system, which is of relevance to nuclear fuel reprocessing and rare-earth refining technologies. Complementary investigations integrating distribution studies, quantum mechanical calculations, and classical molecular dynamics simulations establish a relationship between coextracted water and lanthanide extraction by TODGA across the series, pointing to the importance of the hydrogen-bonding interactions between outer-sphere nitrate ions and water clusters in a nonpolar environment. Our findings have significant implications for the design of novel efficient separation systems and processes, emphasizing the importance of tuning both inner- and outer-sphere interactions to obtain total control over selectivity in the biphasic extraction of lanthanides. American Chemical Society 2018-06-14 2018-06-27 /pmc/articles/PMC6026780/ /pubmed/29974069 http://dx.doi.org/10.1021/acscentsci.8b00223 Text en Copyright © 2018 American Chemical Society This is an open access article published under an ACS AuthorChoice License (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html) , which permits copying and redistribution of the article or any adaptations for non-commercial purposes. |
spellingShingle | Baldwin, Anna G. Ivanov, Alexander S. Williams, Neil J. Ellis, Ross J. Moyer, Bruce A. Bryantsev, Vyacheslav S. Shafer, Jenifer C. Outer-Sphere Water Clusters Tune the Lanthanide Selectivity of Diglycolamides |
title | Outer-Sphere Water Clusters Tune the Lanthanide Selectivity
of Diglycolamides |
title_full | Outer-Sphere Water Clusters Tune the Lanthanide Selectivity
of Diglycolamides |
title_fullStr | Outer-Sphere Water Clusters Tune the Lanthanide Selectivity
of Diglycolamides |
title_full_unstemmed | Outer-Sphere Water Clusters Tune the Lanthanide Selectivity
of Diglycolamides |
title_short | Outer-Sphere Water Clusters Tune the Lanthanide Selectivity
of Diglycolamides |
title_sort | outer-sphere water clusters tune the lanthanide selectivity
of diglycolamides |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6026780/ https://www.ncbi.nlm.nih.gov/pubmed/29974069 http://dx.doi.org/10.1021/acscentsci.8b00223 |
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