Show simple item record

dc.contributor.authorStross, AE
dc.contributor.authorIadevaia, G
dc.contributor.authorNunez-Villanueva, D
dc.contributor.authorHunter, CA
dc.date.accessioned2017-10-18T14:56:57Z
dc.date.available2017-10-18T14:56:57Z
dc.date.issued2017-09-13
dc.identifier.issn0002-7863
dc.identifier.urihttps://www.repository.cam.ac.uk/handle/1810/267878
dc.description.abstractOligomers 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 (102 to 105 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.
dc.description.sponsorshipWe thank the Engineering and Physical Sciences Research Council (EP/J008044/2) and European Research Council (ERC-2012-AdG 320539-duplex) for funding.
dc.publisherAmerican Chemical Society
dc.rightsAttribution 4.0 International
dc.rightsAttribution 4.0 International
dc.rightsAttribution 4.0 International
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/
dc.titleSequence-Selective Formation of Synthetic H-Bonded Duplexes
dc.typeArticle
prism.endingPage12663
prism.issueIdentifier36
prism.publicationDate2017
prism.publicationNameJournal of the American Chemical Society
prism.startingPage12655
prism.volume139
dc.identifier.doi10.17863/CAM.13800
dcterms.dateAccepted2017-08-14
rioxxterms.versionofrecord10.1021/jacs.7b06619
rioxxterms.versionVoR
rioxxterms.licenseref.urihttp://creativecommons.org/licenses/by/4.0/
rioxxterms.licenseref.startdate2017-09-13
dc.contributor.orcidIadevaia, Giulia [0000-0002-1182-0341]
dc.contributor.orcidNunez-Villanueva, Diego [0000-0002-1005-1464]
dc.contributor.orcidHunter, Christopher [0000-0002-5182-1859]
dc.identifier.eissn1520-5126
rioxxterms.typeJournal Article/Review
pubs.funder-project-idEuropean Research Council (320539)
pubs.funder-project-idEPSRC (EP/J008044/4)
pubs.funder-project-idEngineering and Physical Sciences Research Council (EP/K039520/1)
cam.issuedOnline2017-08-31


Files in this item

Thumbnail
Thumbnail
Thumbnail

This item appears in the following Collection(s)

Show simple item record

Attribution 4.0 International
Except where otherwise noted, this item's licence is described as Attribution 4.0 International