A supramolecular lanthanide separation approach based on multivalent cooperative enhancement of metal ion selectivity

Li, Xiaozhen; Zhou, Lixin; Yan, Lingling; Dong, Yamin; Bai, Zhuanling; Sun, Xiaoqi; Diwu, Juan; Wang, Shuao; Bünzli, Jean‐Claude G.; Sun, Qing‐Fu

doi:10.1038/s41467-018-02940-7

Cited by 120 publications

(75 citation statements)

References 67 publications

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“…2 A particular advantage of LanM is the cooperative metal binding exhibited by its EF hand pairs, which could allow for greater selectivities for adjacent REs than is possible at a single metal-binding site (as in currently used ligands), a general principle highlighted by recent synthetic ligands for size-based separations. 12,14,92…”

Section: Lanthanide Recognition In Cellsmentioning

confidence: 99%

The Chemistry of Lanthanides in Biology: Recent Discoveries, Emerging Principles, and Technological Applications

2019

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The essential biological role of rare earth elements lay hidden until the discovery in 2011 that lanthanides are specifically incorporated into a bacterial methanol dehydrogenase. Only recently has this observation gone from a curiosity to a major research area, with the appreciation for the widespread nature of lanthanide-utilizing organisms in the environment and the discovery of other lanthanide-binding proteins and systems for selective uptake. While seemingly exotic at first glance, biological utilization of lanthanides is very logical from a chemical perspective. The early lanthanides (La, Ce, Pr, Nd) primarily used by biology are abundant in the environment, perform similar chemistry to other biologically useful metals and do so more efficiently due to higher Lewis acidity, and possess sufficiently distinct coordination chemistry to allow for selective uptake, trafficking, and incorporation into enzymes. Indeed, recent advances in the field illustrate clear analogies with the biological coordination chemistry of other metals, particularly CaII and FeIII, but with unique twists—including cooperative metal binding to magnify the effects of small ionic radius differences—enabling selectivity. This Outlook summarizes the recent developments in this young but rapidly expanding field and looks forward to potential future discoveries, emphasizing continuity with principles of bioinorganic chemistry established by studies of other metals. We also highlight how a more thorough understanding of the central chemical question—selective lanthanide recognition in biology—may impact the challenging problems of sensing, capture, recycling, and separations of rare earths.

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Section: Lanthanide Recognition In Cellsmentioning

confidence: 99%

The Chemistry of Lanthanides in Biology: Recent Discoveries, Emerging Principles, and Technological Applications

2019

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“…Only a handful of neutral ligands that exhibit high selectivity for light lanthanides in solvent extraction systems have been previously described . The majority of the known ligands exhibit the reverse trend, that is, by being more selective towards heavy lanthanides.…”

Section: Introductionmentioning

confidence: 99%

Efficient Separation of Light Lanthanides(III) by Using Bis‐Lactam Phenanthroline Ligands

Healy

Ivanov

Karslyan

et al. 2019

Chemistry A European J

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Due to the ever‐increasing demand for high‐purity individual rare‐earth elements, novel and highly selective separation processes are increasingly sought after. Herein, we report a separation protocol that employs shape‐persistent 2,9‐bis‐lactam‐1,10‐phenanthroline (BLPhen) ligands exhibiting unparalleled selectivity for light trivalent lanthanides. The highly preorganised binding pockets of the ligands allowed for the separation of lanthanides with high fidelity, even in the presence of competing transition metals, in a biphasic separation system. Notably, the selectivity trends of the BLPhen ligands towards metal ions across the lanthanide series can be chemically modulated by altering the molecular rigidity of the extractant.

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“…This encapsulation ability of biological cages has recently been applied to recycling rare elements, mineralization, and catalysis . Inspired by this, artificial nanometer‐sized molecular cages, constructed by the self‐assembly of metal ions and organic ligands through coordination bonds, have received increasing interest because of their applications in metal‐ion storage, exchange, and mineralization inside the cage structures . The chemistry of this class of metal‐organic cage compounds was originally developed as molecular hosts for molecular recognition, catalysis, and drug delivery .…”

Section: Introductionmentioning

confidence: 99%

A 116‐Nuclear Metallosupramolecular Cage‐of‐Cage Showing Multistep Single‐Crystal‐to‐Single‐Crystal Transformation

Imanishi

Wahyudianto

Kojima

et al. 2020

Chemistry A European J

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Here au nique single-crystal-to-single-crystal (SCSC) transformationo fa116-nuclear Au I 72 Cd II 40 Na I 4 cageof-cage( 2 CdNa )i sreported, which was created from at rigold(I) metalloligand with d-penicillamine by way of a9 -nuclear Au I 6 Cd II 3 cage (1). Cage-of-cage 2 CdNa is composedo f1 2 cages of 1 that are linked by 4C d 2 + and 4N a + ions, with its surface being covered by 12 NO 3 À ions to form ad iscrete, spherical molecule with ad iameter ca. 4.7 nm. In crystal 2 CdNa ,t he cage-of-cage molecules are packed in ac ubic lattice with ah uge cell volumeo fc a. 4.5 10 5 3 , so as to have large interstices with diameters of more than 3nm. Upon soakingc rystals 2 CdNa in aqueous Cu(NO 3 ) 2 ,a ll Cd 2 + and Na + were quicklye xchanged by Cu 2 + to producea na nalogous Au I 72 Cu II 44 cage-of-cage (2 Cu )i naSCSC manner.P rolonged soakingl ed to the SCSC transformation to anothers upramolecular structure (2' Cu )c onsisting of 152-nuclear Au I 72 Cu II 80 cage-of-cages that are alternately H-bonded with the Au I 72 Cu II 44 cage-of-cages. 2' Cu showed the accommodationo f MoO 4 2À and the conversion of MoO 4 2À to b-Mo 8 O 26 4À in the crystal, with retention of single-crystallinity. Supporting information and the ORCID identification number(s) for the author(s) of this articlecan be found under: https://doi.org/10.1002/chem.201904275.Scheme1.Synthetic routes to 1 and 2 CdNa .C olor codes: red,A u; cream, Cd; purple, Na.

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A supramolecular lanthanide separation approach based on multivalent cooperative enhancement of metal ion selectivity

Cited by 120 publications

References 67 publications

The Chemistry of Lanthanides in Biology: Recent Discoveries, Emerging Principles, and Technological Applications

The Chemistry of Lanthanides in Biology: Recent Discoveries, Emerging Principles, and Technological Applications

Efficient Separation of Light Lanthanides(III) by Using Bis‐Lactam Phenanthroline Ligands

A 116‐Nuclear Metallosupramolecular Cage‐of‐Cage Showing Multistep Single‐Crystal‐to‐Single‐Crystal Transformation

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