Issue 48, 2020

Temperature-mediated molecular ladder self-assembly employing Diels–Alder cycloaddition

Abstract

Dynamic covalent self-assembly processes often exhibit poor capacities for error-correction owing to the relatively low connectivity rearrangement rates of dynamic covalent interactions and the common use of reaction conditions where the equilibrium state remains fixed. Here, we report a dynamic covalent self-assembly technique employing temperature, a conventional, externally-applied stimulus, to mediate the hybridization of peptoid oligomers bearing maleimide- and furan-based pendant groups to afford molecular ladders incorporating Diels–Alder adduct-based rungs. By raising or lowing the reaction temperature, this system enables the equilibrium state to be readily varied without altering reagent concentrations. Both triethylamine and the Lewis acidic scandium triflate were examined as candidate reaction catalysts; however, only scandium triflate increased the rate of single strand conversion. As the Diels–Alder cycloaddition reaction does not liberate a small molecule, a registry-dependent mass change was effected by employing a base-catalyzed thiol-Michael addition reaction between any un-reacted maleimide pendant groups and a low molecular weight thiol to enable the number of Diels–Alder adduct rungs to be readily determined by mass spectrometry. Finally, by employing a slow temperature ramp from high to low temperature, approximating the thermal cycle employed for nucleic acid hybridization, sequence-selective hybridization between model, tetra-functional precursor strands was demonstrated.

Graphical abstract: Temperature-mediated molecular ladder self-assembly employing Diels–Alder cycloaddition

Supplementary files

Article information

Article type
Paper
Submitted
10 sen 2020
Accepted
17 noy 2020
First published
18 noy 2020

Polym. Chem., 2020,11, 7714-7720

Author version available

Temperature-mediated molecular ladder self-assembly employing Diels–Alder cycloaddition

S. C. Leguizamon, A. F. Alqubati and T. F. Scott, Polym. Chem., 2020, 11, 7714 DOI: 10.1039/D0PY01296C

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements