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Title: 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 [Co 4O 4] 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:
ORCiD logo [1]; ORCiD logo [2];  [1]; ORCiD logo [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
  2. Univ. of California, Irvine, CA (United States). Dept. of Chemistry. Dept. of Chemical Engineering & Materials Science
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
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 Volume: 9; Journal Issue: 47; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
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 States: 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 States. doi:10.1039/c8sc04240c.
Nguyen, Andy I., Spencer, Ryan K., Anderson, Christopher L., and Zuckermann, Ronald N. Thu . "A bio-inspired approach to ligand design: folding single-chain peptoids to chelate a multimetallic cluster". United States. doi: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 States},
year = {2018},
month = {11}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1039/c8sc04240c

Citation Metrics:
Cited by: 3 works
Citation information provided by
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Figures / Tables:

Fig. 1 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 have been extracted from DOE-funded journal article accepted manuscripts.