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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...
Autores principales: | , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical
Society
2017
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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. |
format | Online Article Text |
id | pubmed-5627343 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2017 |
publisher | American Chemical
Society |
record_format | MEDLINE/PubMed |
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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