Issue 38, 2019

A sequential native chemical ligation – thiol-Michael addition strategy for polymer–polymer ligation

Abstract

We systematically investigate sequential native chemical ligation (NCL)-thiol Michael addition as an efficient strategy for the dual modification of polymers. Polymers containing terminal cysteine functional groups were shown to undergo efficient NCL in the presence of amino acid-based and polymeric thioesters. The retention of the native cysteine side chain present at the NCL-junction distinguishes this approach from related multi-step strategies and was exploited for subsequent thiol-Michael additions providing access to diverse polymer architectures and polymer-peptide (single amino acid in this case) conjugates. Careful evaluation of model reactions involving a terminal cysteine functional poly(ethylene glycol), an amino acid thioester, i.e. phenylalanine thioester, and trifluoroethyl acrylate by NMR, SEC and MALDI-ToF MS revealed highly efficient modifications. Expansion of this concept towards oligomeric acrylates based on, e.g. N-acylated poly(amino ester)s (NPAEs) yielded Y-shape (co)polymers with quantitative conversions. The versatility and potential of the sequential modification was further demonstrated by employing a thioester-functionalised poly(2-ethyl-2-oxazoline) (PEtOx) to prepare a 3-arm mikto-arm star terpolymer.

Graphical abstract: A sequential native chemical ligation – thiol-Michael addition strategy for polymer–polymer ligation

Supplementary files

Article information

Article type
Paper
Submitted
08 Aug 2019
Accepted
06 Sep 2019
First published
09 Sep 2019

Polym. Chem., 2019,10, 5242-5250

A sequential native chemical ligation – thiol-Michael addition strategy for polymer–polymer ligation

A. Rajakanthan, P. A. J. M. D. Jongh, J. S. Town, P. Wilson and K. Kempe, Polym. Chem., 2019, 10, 5242 DOI: 10.1039/C9PY01198F

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