A tendril perversion in a helical oligomer: trapping and characterizing a mobile screw-sense reversal

Michael Tomsett, Irene Maffucci, Bryden A F Le Bailly, Liam Byrne, Stefan M. Bijvoets, M. Giovanna Lizio, James Raftery, Craig P. Butts, Simon J. Webb, Alessandro Contini, Jonathan Clayden*

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)

17 Citations (Scopus)
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Abstract

Helical oligomers of achiral monomers adopt domains of uniform screw sense, which are occasionally interrupted by screw-sense reversals. These rare, elusive, and fast-moving features have eluded detailed characterization. We now describe the structure and habits of a screw-sense reversal trapped within a fragment of a helical oligoamide foldamer of the achiral quaternary amino acid 2-aminoisobutyric acid (Aib). The reversal was enforced by compelling the amide oligomer to adopt a right-handed screw sense at one end and a left-handed screw sense at the other. The trapped reversal was characterized by X-ray crystallography, and its dynamic properties were monitored by NMR and circular dichroism, and modelled computationally. Raman spectroscopy indicated that a predominantly helical architecture was maintained despite the reversal. NMR and computational results indicated a stepwise shift from one screw sense to another on moving along the helical chain, indicating that in solution the reversal is not localised at a specific location, but is free to migrate across a number of residues. Analogous unconstrained screw-sense reversals that are free to move within a helical structure are likely to provide the mechanism by which comparable helical polymers and foldamers undergo screw-sense inversion.

Original languageEnglish
Pages (from-to)3007-3018
Number of pages12
JournalChemical Science
Volume8
Issue number4
Early online date25 Jan 2017
DOIs
Publication statusPublished - 1 Apr 2017

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    Tomsett, M., Maffucci, I., Le Bailly, B. A. F., Byrne, L., Bijvoets, S. M., Lizio, M. G., Raftery, J., Butts, C. P., Webb, S. J., Contini, A., & Clayden, J. (2017). A tendril perversion in a helical oligomer: trapping and characterizing a mobile screw-sense reversal. Chemical Science, 8(4), 3007-3018. https://doi.org/10.1039/c6sc05474a