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H-Bond Self-Assembly: Folding versus Duplex Formation

[Image: see text] Linear oligomers equipped with complementary H-bond donor (D) and acceptor (A) sites can interact via intermolecular H-bonds to form duplexes or fold via intramolecular H-bonds. These competing equilibria have been quantified using NMR titration and dilution experiments for seven s...

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Autores principales: Núñez-Villanueva, Diego, Iadevaia, Giulia, Stross, Alexander E., Jinks, Michael A., Swain, Jonathan A., Hunter, Christopher A.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2017
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5469522/
https://www.ncbi.nlm.nih.gov/pubmed/28470070
http://dx.doi.org/10.1021/jacs.7b01357
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author Núñez-Villanueva, Diego
Iadevaia, Giulia
Stross, Alexander E.
Jinks, Michael A.
Swain, Jonathan A.
Hunter, Christopher A.
author_facet Núñez-Villanueva, Diego
Iadevaia, Giulia
Stross, Alexander E.
Jinks, Michael A.
Swain, Jonathan A.
Hunter, Christopher A.
author_sort Núñez-Villanueva, Diego
collection PubMed
description [Image: see text] Linear oligomers equipped with complementary H-bond donor (D) and acceptor (A) sites can interact via intermolecular H-bonds to form duplexes or fold via intramolecular H-bonds. These competing equilibria have been quantified using NMR titration and dilution experiments for seven systems featuring different recognition sites and backbones. For all seven architectures, duplex formation is observed for homo-sequence 2-mers (AA·DD) where there are no competing folding equilibria. The corresponding hetero-sequence AD 2-mers also form duplexes, but the observed self-association constants are strongly affected by folding equilibria in the monomeric states. When the backbone is flexible (five or more rotatable bonds separating the recognition sites), intramolecular H-bonding is favored, and the folded state is highly populated. For these systems, the stability of the AD·AD duplex is 1–2 orders of magnitude lower than that of the corresponding AA·DD duplex. However, for three architectures which have more rigid backbones (fewer than five rotatable bonds), intramolecular interactions are not observed, and folding does not compete with duplex formation. These systems are promising candidates for the development of longer, mixed-sequence synthetic information molecules that show sequence-selective duplex formation.
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spelling pubmed-54695222017-06-14 H-Bond Self-Assembly: Folding versus Duplex Formation Núñez-Villanueva, Diego Iadevaia, Giulia Stross, Alexander E. Jinks, Michael A. Swain, Jonathan A. Hunter, Christopher A. J Am Chem Soc [Image: see text] Linear oligomers equipped with complementary H-bond donor (D) and acceptor (A) sites can interact via intermolecular H-bonds to form duplexes or fold via intramolecular H-bonds. These competing equilibria have been quantified using NMR titration and dilution experiments for seven systems featuring different recognition sites and backbones. For all seven architectures, duplex formation is observed for homo-sequence 2-mers (AA·DD) where there are no competing folding equilibria. The corresponding hetero-sequence AD 2-mers also form duplexes, but the observed self-association constants are strongly affected by folding equilibria in the monomeric states. When the backbone is flexible (five or more rotatable bonds separating the recognition sites), intramolecular H-bonding is favored, and the folded state is highly populated. For these systems, the stability of the AD·AD duplex is 1–2 orders of magnitude lower than that of the corresponding AA·DD duplex. However, for three architectures which have more rigid backbones (fewer than five rotatable bonds), intramolecular interactions are not observed, and folding does not compete with duplex formation. These systems are promising candidates for the development of longer, mixed-sequence synthetic information molecules that show sequence-selective duplex formation. American Chemical Society 2017-05-04 2017-05-17 /pmc/articles/PMC5469522/ /pubmed/28470070 http://dx.doi.org/10.1021/jacs.7b01357 Text en Copyright © 2017 American Chemical Society This is an open access article published under a Creative Commons Attribution (CC-BY) License (http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html) , which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.
spellingShingle Núñez-Villanueva, Diego
Iadevaia, Giulia
Stross, Alexander E.
Jinks, Michael A.
Swain, Jonathan A.
Hunter, Christopher A.
H-Bond Self-Assembly: Folding versus Duplex Formation
title H-Bond Self-Assembly: Folding versus Duplex Formation
title_full H-Bond Self-Assembly: Folding versus Duplex Formation
title_fullStr H-Bond Self-Assembly: Folding versus Duplex Formation
title_full_unstemmed H-Bond Self-Assembly: Folding versus Duplex Formation
title_short H-Bond Self-Assembly: Folding versus Duplex Formation
title_sort h-bond self-assembly: folding versus duplex formation
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5469522/
https://www.ncbi.nlm.nih.gov/pubmed/28470070
http://dx.doi.org/10.1021/jacs.7b01357
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