A bio-inspired approach to ligand design: folding single-chain peptoids to chelate a multimetallic cluster
Abstract
Synthesis of biomimetic multimetallic clusters is sought after for applications such as efficient storage of solar energy and utilization of greenhouse gases. However, synthetic efforts are hampered by a dearth of ligands that are developed for multimetallic clusters due to current limitations in rational design and organic synthesis. Peptoids, a synthetic sequence-defined oligomer, enable a biomimetic strategy to rapidly synthesize and optimize large, multifunctional ligands by structural design and combinatorial screening. Here we discover peptoid oligomers (≤7 residues) that fold into a single conformation to provide unprecedented tetra- and hexadentate chelation by carboxylates to a [Co4O4] cubane cluster. The structures of peptoid-bound cubanes were determined by 2D NMR spectroscopy, and their structures reveal key steric and side-chain-to-main chain interactions that work in concert to rigidify the peptoid ligand. This efficient ligand design strategy holds promise for creating new scaffolds for the abiotic synthesis and manipulation of multimetallic clusters.
- Authors:
-
[1];
[2];
[1]
- Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, USA
- Department of Chemistry, Department of Chemical Engineering & Materials Science, University of California, Irvine, USA
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1482267
- Alternate Identifier(s):
- OSTI ID: 1494083
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Published Article
- Journal Name:
- Chemical Science
- Additional Journal Information:
- Journal Name: Chemical Science Journal Volume: 9 Journal Issue: 47; Journal ID: ISSN 2041-6520
- Publisher:
- Royal Society of Chemistry (RSC)
- Country of Publication:
- United Kingdom
- Language:
- English
- Subject:
- 59 BASIC BIOLOGICAL SCIENCES; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 25 ENERGY STORAGE
Citation Formats
Nguyen, Andy I., Spencer, Ryan K., Anderson, Christopher L., and Zuckermann, Ronald N. A bio-inspired approach to ligand design: folding single-chain peptoids to chelate a multimetallic cluster. United Kingdom: N. p., 2018.
Web. doi:10.1039/C8SC04240C.
Nguyen, Andy I., Spencer, Ryan K., Anderson, Christopher L., & Zuckermann, Ronald N. A bio-inspired approach to ligand design: folding single-chain peptoids to chelate a multimetallic cluster. United Kingdom. https://doi.org/10.1039/C8SC04240C
Nguyen, Andy I., Spencer, Ryan K., Anderson, Christopher L., and Zuckermann, Ronald N. Wed .
"A bio-inspired approach to ligand design: folding single-chain peptoids to chelate a multimetallic cluster". United Kingdom. https://doi.org/10.1039/C8SC04240C.
@article{osti_1482267,
title = {A bio-inspired approach to ligand design: folding single-chain peptoids to chelate a multimetallic cluster},
author = {Nguyen, Andy I. and Spencer, Ryan K. and Anderson, Christopher L. and Zuckermann, Ronald N.},
abstractNote = {Synthesis of biomimetic multimetallic clusters is sought after for applications such as efficient storage of solar energy and utilization of greenhouse gases. However, synthetic efforts are hampered by a dearth of ligands that are developed for multimetallic clusters due to current limitations in rational design and organic synthesis. Peptoids, a synthetic sequence-defined oligomer, enable a biomimetic strategy to rapidly synthesize and optimize large, multifunctional ligands by structural design and combinatorial screening. Here we discover peptoid oligomers (≤7 residues) that fold into a single conformation to provide unprecedented tetra- and hexadentate chelation by carboxylates to a [Co4O4] cubane cluster. The structures of peptoid-bound cubanes were determined by 2D NMR spectroscopy, and their structures reveal key steric and side-chain-to-main chain interactions that work in concert to rigidify the peptoid ligand. This efficient ligand design strategy holds promise for creating new scaffolds for the abiotic synthesis and manipulation of multimetallic clusters.},
doi = {10.1039/C8SC04240C},
journal = {Chemical Science},
number = 47,
volume = 9,
place = {United Kingdom},
year = {Wed Dec 05 00:00:00 EST 2018},
month = {Wed Dec 05 00:00:00 EST 2018}
}
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https://doi.org/10.1039/C8SC04240C
https://doi.org/10.1039/C8SC04240C
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Cited by: 14 works
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Figures / Tables:
Fig. 1: To faithfully reproduce the multimetallic cluster active site in a simplified environment, chelating ligands must be developed to control the coordination and assembly of the cluster. Peptoids have biomimetic structural and synthetic properties that enable discovery of such clusterchelating ligands.
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Figures / Tables found in this record:
Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.