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Peptide sequence mediated self-assembly of molybdenum blue nanowheel superstructures

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Abstract

The precise control over the formation of complex nanostructures, e.g. polyoxometalates (POMs), at the sub-nanoscale is challenging but critical if non-covalent architectures are to be designed. Combining biologically-evolved systems with inorganic nanostructures could lead to sequence-mediated assembly. Herein, we exploit oligopeptides as multidentate structure-directing ligands via metal-coordination and hydrogen bonded interactions to modulate the self-assembly of POM superstructures. Six oligopeptides (GH, AH, SH, G2H, G4H and G5H) are incorporated into the cavities of Molybdenum Blue (MB) POM nanowheels. It is found that the helicity of the nanowheel can be readily switched (Δ to Λ) by simply altering the N-terminal amino acid on the peptide chain rather than their overall stereochemistry. We also reveal a delicate balance between the Mo-coordination and the hydrogen bonds found within the internal cavity of the inorganic nanowheels which results in the sequence mediated formation of two unprecedented asymmetrical nanowheel frameworks: {Mo122Ce5} and {Mo126Ce4}.

Graphical abstract: Peptide sequence mediated self-assembly of molybdenum blue nanowheel superstructures

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Article information


Submitted
04 Nov 2020
Accepted
14 Dec 2020
First published
14 Dec 2020

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2021, Advance Article
Article type
Edge Article

Peptide sequence mediated self-assembly of molybdenum blue nanowheel superstructures

S. She, W. Xuan, N. L. Bell, R. Pow, E. G. Ribo, Z. Sinclair, D. Long and L. Cronin, Chem. Sci., 2021, Advance Article , DOI: 10.1039/D0SC06098D

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