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Sequence-Selective Formation of Synthetic H-Bonded Duplexes

[Image: see text] Oligomers equipped with a sequence of phenol and pyridine N-oxide groups form duplexes via H-bonding interactions between these recognition units. Reductive amination chemistry was used to synthesize all possible 3-mer sequences: AAA, AAD, ADA, DAA, ADD, DAD, DDA, and DDD. Pairwise...

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Autores principales: Stross, Alexander E., Iadevaia, Giulia, Núñez-Villanueva, Diego, 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/PMC5627343/
https://www.ncbi.nlm.nih.gov/pubmed/28857551
http://dx.doi.org/10.1021/jacs.7b06619
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author Stross, Alexander E.
Iadevaia, Giulia
Núñez-Villanueva, Diego
Hunter, Christopher A.
author_facet Stross, Alexander E.
Iadevaia, Giulia
Núñez-Villanueva, Diego
Hunter, Christopher A.
author_sort Stross, Alexander E.
collection PubMed
description [Image: see text] Oligomers equipped with a sequence of phenol and pyridine N-oxide groups form duplexes via H-bonding interactions between these recognition units. Reductive amination chemistry was used to synthesize all possible 3-mer sequences: AAA, AAD, ADA, DAA, ADD, DAD, DDA, and DDD. Pairwise interactions between the oligomers were investigated using NMR titration and dilution experiments in toluene. The measured association constants vary by 3 orders of magnitude (10(2) to 10(5) M(–1)). Antiparallel sequence-complementary oligomers generally form more stable complexes than mismatched duplexes. Mismatched duplexes that have an excess of H-bond donors are stabilized by the interaction of two phenol donors with one pyridine N-oxide acceptor. Oligomers that have a H-bond donor and acceptor on the ends of the chain can fold to form intramolecular H-bonds in the free state. The 1,3-folding equilibrium competes with duplex formation and lowers the stability of duplexes involving these sequences. As a result, some of the mismatch duplexes are more stable than some of the sequence-complementary duplexes. However, the most stable mismatch duplexes contain DDD and compete with the most stable sequence-complementary duplex, AAA·DDD, so in mixtures that contain all eight sequences, sequence-complementary duplexes dominate. Even higher fidelity sequence selectivity can be achieved if alternating donor–acceptor sequences are avoided.
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spelling pubmed-56273432017-10-05 Sequence-Selective Formation of Synthetic H-Bonded Duplexes Stross, Alexander E. Iadevaia, Giulia Núñez-Villanueva, Diego Hunter, Christopher A. J Am Chem Soc [Image: see text] Oligomers equipped with a sequence of phenol and pyridine N-oxide groups form duplexes via H-bonding interactions between these recognition units. Reductive amination chemistry was used to synthesize all possible 3-mer sequences: AAA, AAD, ADA, DAA, ADD, DAD, DDA, and DDD. Pairwise interactions between the oligomers were investigated using NMR titration and dilution experiments in toluene. The measured association constants vary by 3 orders of magnitude (10(2) to 10(5) M(–1)). Antiparallel sequence-complementary oligomers generally form more stable complexes than mismatched duplexes. Mismatched duplexes that have an excess of H-bond donors are stabilized by the interaction of two phenol donors with one pyridine N-oxide acceptor. Oligomers that have a H-bond donor and acceptor on the ends of the chain can fold to form intramolecular H-bonds in the free state. The 1,3-folding equilibrium competes with duplex formation and lowers the stability of duplexes involving these sequences. As a result, some of the mismatch duplexes are more stable than some of the sequence-complementary duplexes. However, the most stable mismatch duplexes contain DDD and compete with the most stable sequence-complementary duplex, AAA·DDD, so in mixtures that contain all eight sequences, sequence-complementary duplexes dominate. Even higher fidelity sequence selectivity can be achieved if alternating donor–acceptor sequences are avoided. American Chemical Society 2017-08-31 2017-09-13 /pmc/articles/PMC5627343/ /pubmed/28857551 http://dx.doi.org/10.1021/jacs.7b06619 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 Stross, Alexander E.
Iadevaia, Giulia
Núñez-Villanueva, Diego
Hunter, Christopher A.
Sequence-Selective Formation of Synthetic H-Bonded Duplexes
title Sequence-Selective Formation of Synthetic H-Bonded Duplexes
title_full Sequence-Selective Formation of Synthetic H-Bonded Duplexes
title_fullStr Sequence-Selective Formation of Synthetic H-Bonded Duplexes
title_full_unstemmed Sequence-Selective Formation of Synthetic H-Bonded Duplexes
title_short Sequence-Selective Formation of Synthetic H-Bonded Duplexes
title_sort sequence-selective formation of synthetic h-bonded duplexes
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5627343/
https://www.ncbi.nlm.nih.gov/pubmed/28857551
http://dx.doi.org/10.1021/jacs.7b06619
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