Building blocks for recognition-encoded oligoesters that form H-bonded duplexes.
Royal Society of Chemistry (RSC)
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Szczypinski, F., & Hunter, C. (2019). Building blocks for recognition-encoded oligoesters that form H-bonded duplexes.. Chemical science, 10 (8), 2444-2451. https://doi.org/10.1039/c8sc04896g
Competition from intramolecular folding is a major challenge in the design of synthetic oligomers that form intermolecular duplexes in a sequence-selective manner. One strategy is to use very rigid backbones that prevent folding, but this design can prejudice duplex formation if the ge- ometry is not exactly right. The alternative approach found in nucleic acids is to use bases (or recognition units) that have different dimensions. A long-short base-pairing scheme makes folding geometrically difficult and is compatible with the flexible backbones that are required to guarantee duplex formation. A monomer building block equipped with a long hydrogen bond donor (phenol, D) recognition unit and a monomer building block equipped with a short hydrogen bond acceptor (phosphine oxide, A) recognition unit were prepared with differentially protected alcohol and car- boxylic acid groups. These compounds were used to synthesise the homo and hetero-sequence 2-mers AA, DD and AD. 19F and 31P NMR experiments were used to characterize the assembly properties of these compounds in toluene solution. AA and DD form a stable doubly-hydrogen- bonded duplex with an effective molarity of 20 mM for formation of the second intramolecular hy- drogen bond. AD forms a duplex of similar stability. There is no evidence of intramolecular folding in the monomeric state of this compound, which shows that the long-short base-pairing scheme is effective. The ester coupling chemistry used here is an attractive method for the synthesis of long oligomers, and the properties of the 2-mers indicate that this molecular architecture should give longer mixed sequence oligomers that show high fidelity sequence-selective duplex formation.
European Research Council (ERC-2012-AdG 320539-DUPLEX)
European Research Council (320539)
External DOI: https://doi.org/10.1039/c8sc04896g
This record's URL: https://www.repository.cam.ac.uk/handle/1810/288732
Attribution 4.0 International
Licence URL: https://creativecommons.org/licenses/by/4.0/