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Folding and duplex formation in mixed sequence recognition-encoded m-phenylene ethynylene polymers

Oligomers equipped with complementary recognition units have the potential to encode and express chemical information in the same way as nucleic acids. The supramolecular assembly properties of m-phenylene ethynylene polymers equipped with H-bond donor (D = phenol) and H-bond acceptor (A = phosphine...

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Autores principales: Iadevaia, Giulia, Swain, Jonathan A., Núñez-Villanueva, Diego, Bond, Andrew D., Hunter, Christopher A.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8336474/
https://www.ncbi.nlm.nih.gov/pubmed/34377409
http://dx.doi.org/10.1039/d1sc02288a
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author Iadevaia, Giulia
Swain, Jonathan A.
Núñez-Villanueva, Diego
Bond, Andrew D.
Hunter, Christopher A.
author_facet Iadevaia, Giulia
Swain, Jonathan A.
Núñez-Villanueva, Diego
Bond, Andrew D.
Hunter, Christopher A.
author_sort Iadevaia, Giulia
collection PubMed
description Oligomers equipped with complementary recognition units have the potential to encode and express chemical information in the same way as nucleic acids. The supramolecular assembly properties of m-phenylene ethynylene polymers equipped with H-bond donor (D = phenol) and H-bond acceptor (A = phosphine oxide) side chains have been investigated in chloroform solution. Polymerisation of a bifunctional monomer in the presence of a monofunctional chain stopper was used for the one pot synthesis of families of m-phenylene ethynylene polymers with sequences ADnA or DAnD (n = 1–5), which were separated by chromatography. All of the oligomers self-associate due to intermolecular H-bonding interactions, but intramolecular folding of the monomeric single strands can be studied in dilute solution. NMR and fluorescence spectroscopy show that the 3-mers ADA and DAD do not fold, but there are intramolecular H-bonding interactions for all of the longer sequences. Nevertheless, 1 : 1 mixtures of sequence complementary oligomers all form stable duplexes. Duplex stability was quantified using DMSO denaturation experiments, which show that the association constant for duplex formation increases by an order of magnitude for every base-pairing interaction added to the chain, from 10(3) M(−1) for ADA·DAD to 10(5) M(−1) for ADDDA·DAAAD. Intramolecular folding is the major pathway that competes with duplex formation between recognition-encoded oligomers and limits the fidelity of sequence-selective assembly. The experimental approach described here provides a practical strategy for rapid evaluation of suitability for the development of programmable synthetic polymers.
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spelling pubmed-83364742021-08-09 Folding and duplex formation in mixed sequence recognition-encoded m-phenylene ethynylene polymers Iadevaia, Giulia Swain, Jonathan A. Núñez-Villanueva, Diego Bond, Andrew D. Hunter, Christopher A. Chem Sci Chemistry Oligomers equipped with complementary recognition units have the potential to encode and express chemical information in the same way as nucleic acids. The supramolecular assembly properties of m-phenylene ethynylene polymers equipped with H-bond donor (D = phenol) and H-bond acceptor (A = phosphine oxide) side chains have been investigated in chloroform solution. Polymerisation of a bifunctional monomer in the presence of a monofunctional chain stopper was used for the one pot synthesis of families of m-phenylene ethynylene polymers with sequences ADnA or DAnD (n = 1–5), which were separated by chromatography. All of the oligomers self-associate due to intermolecular H-bonding interactions, but intramolecular folding of the monomeric single strands can be studied in dilute solution. NMR and fluorescence spectroscopy show that the 3-mers ADA and DAD do not fold, but there are intramolecular H-bonding interactions for all of the longer sequences. Nevertheless, 1 : 1 mixtures of sequence complementary oligomers all form stable duplexes. Duplex stability was quantified using DMSO denaturation experiments, which show that the association constant for duplex formation increases by an order of magnitude for every base-pairing interaction added to the chain, from 10(3) M(−1) for ADA·DAD to 10(5) M(−1) for ADDDA·DAAAD. Intramolecular folding is the major pathway that competes with duplex formation between recognition-encoded oligomers and limits the fidelity of sequence-selective assembly. The experimental approach described here provides a practical strategy for rapid evaluation of suitability for the development of programmable synthetic polymers. The Royal Society of Chemistry 2021-07-06 /pmc/articles/PMC8336474/ /pubmed/34377409 http://dx.doi.org/10.1039/d1sc02288a Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by/3.0/
spellingShingle Chemistry
Iadevaia, Giulia
Swain, Jonathan A.
Núñez-Villanueva, Diego
Bond, Andrew D.
Hunter, Christopher A.
Folding and duplex formation in mixed sequence recognition-encoded m-phenylene ethynylene polymers
title Folding and duplex formation in mixed sequence recognition-encoded m-phenylene ethynylene polymers
title_full Folding and duplex formation in mixed sequence recognition-encoded m-phenylene ethynylene polymers
title_fullStr Folding and duplex formation in mixed sequence recognition-encoded m-phenylene ethynylene polymers
title_full_unstemmed Folding and duplex formation in mixed sequence recognition-encoded m-phenylene ethynylene polymers
title_short Folding and duplex formation in mixed sequence recognition-encoded m-phenylene ethynylene polymers
title_sort folding and duplex formation in mixed sequence recognition-encoded m-phenylene ethynylene polymers
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8336474/
https://www.ncbi.nlm.nih.gov/pubmed/34377409
http://dx.doi.org/10.1039/d1sc02288a
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