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Title: Siderophore-inspired chelator hijacks uranium from aqueous medium

Abstract

Over millennia, nature has evolved an ability to selectively recognize and sequester specific metal ions by employing a wide variety of supramolecular chelators. Iron-specific molecular carriers—siderophores—are noteworthy for their structural elegance, while exhibiting some of the strongest and most selective binding towards a specific metal ion. Development of simple uranyl (UO 2 2+) recognition motifs possessing siderophore-like selectivity, however, presents a challenge. Herein we report a comprehensive theoretical, crystallographic and spectroscopic studies on the UO 2 2+ binding with a non-toxic siderophore-inspired chelator, 2,6-bis[hydroxy(methyl)amino]-4-morpholino-1,3,5-triazine (H 2BHT). The optimal pK a values and structural preorganization endow H 2BHT with one of the highest uranyl binding affinity and selectivity among molecular chelators. The results of small-molecule standards are validated by a proof-of-principle development of the H 2BHT-functionalized polymeric adsorbent material that affords high uranium uptake capacity even in the presence of competing vanadium (V) ions in aqueous medium.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3]; ORCiD logo [4];  [4]; ORCiD logo [4];  [1];  [2];  [1]; ORCiD logo [1]; ORCiD logo [1];  [3]; ORCiD logo [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  4. Univ. of South Florida, Tampa, FL (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Nuclear Energy (NE); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1495975
Alternate Identifier(s):
OSTI ID: 1559186
Grant/Contract Number:  
AC05-00OR22725; AC02-05CH11231; NE0008281
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Ivanov, Alexander S., Parker, Bernard F., Zhang, Zhicheng, Aguila, Briana, Sun, Qi, Ma, Shengqian, Jansone-Popova, Santa, Arnold, John, Mayes, Richard T., Dai, Sheng, Bryantsev, Vyacheslav S., Rao, Linfeng, and Popovs, Ilja. Siderophore-inspired chelator hijacks uranium from aqueous medium. United States: N. p., 2019. Web. doi:10.1038/s41467-019-08758-1.
Ivanov, Alexander S., Parker, Bernard F., Zhang, Zhicheng, Aguila, Briana, Sun, Qi, Ma, Shengqian, Jansone-Popova, Santa, Arnold, John, Mayes, Richard T., Dai, Sheng, Bryantsev, Vyacheslav S., Rao, Linfeng, & Popovs, Ilja. Siderophore-inspired chelator hijacks uranium from aqueous medium. United States. doi:10.1038/s41467-019-08758-1.
Ivanov, Alexander S., Parker, Bernard F., Zhang, Zhicheng, Aguila, Briana, Sun, Qi, Ma, Shengqian, Jansone-Popova, Santa, Arnold, John, Mayes, Richard T., Dai, Sheng, Bryantsev, Vyacheslav S., Rao, Linfeng, and Popovs, Ilja. Mon . "Siderophore-inspired chelator hijacks uranium from aqueous medium". United States. doi:10.1038/s41467-019-08758-1. https://www.osti.gov/servlets/purl/1495975.
@article{osti_1495975,
title = {Siderophore-inspired chelator hijacks uranium from aqueous medium},
author = {Ivanov, Alexander S. and Parker, Bernard F. and Zhang, Zhicheng and Aguila, Briana and Sun, Qi and Ma, Shengqian and Jansone-Popova, Santa and Arnold, John and Mayes, Richard T. and Dai, Sheng and Bryantsev, Vyacheslav S. and Rao, Linfeng and Popovs, Ilja},
abstractNote = {Over millennia, nature has evolved an ability to selectively recognize and sequester specific metal ions by employing a wide variety of supramolecular chelators. Iron-specific molecular carriers—siderophores—are noteworthy for their structural elegance, while exhibiting some of the strongest and most selective binding towards a specific metal ion. Development of simple uranyl (UO22+) recognition motifs possessing siderophore-like selectivity, however, presents a challenge. Herein we report a comprehensive theoretical, crystallographic and spectroscopic studies on the UO22+ binding with a non-toxic siderophore-inspired chelator, 2,6-bis[hydroxy(methyl)amino]-4-morpholino-1,3,5-triazine (H2BHT). The optimal pKa values and structural preorganization endow H2BHT with one of the highest uranyl binding affinity and selectivity among molecular chelators. The results of small-molecule standards are validated by a proof-of-principle development of the H2BHT-functionalized polymeric adsorbent material that affords high uranium uptake capacity even in the presence of competing vanadium (V) ions in aqueous medium.},
doi = {10.1038/s41467-019-08758-1},
journal = {Nature Communications},
issn = {2041-1723},
number = 1,
volume = 10,
place = {United States},
year = {2019},
month = {2}
}

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Figures / Tables:

Fig. 1 Fig. 1: Structures of ligands for selective recognition of metal ions. a Glutaroimide-dioxime (H3IDO) ligand, which is the major functional unit of polyamidoxime adsorbents for uranium recovery from seawater. b Cartoon representation of the ferric hydroxamate uptake (FhuA) protein (image from the RCSB PDB (www.rcsb.org) of PDB ID 1BY5) withmore » the highlighted structure of ferrichrome—a natural siderophore. c Bis-(hydroxylamino)-1,3,5-triazine (H2BHT)—an artificial siderophore investigated in this study« less

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Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.