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Combining polymer-bound catalyst with polymeric substrate for reproducible pH oscillations in palladium-catalysed oxidative carbonylation of alkynes

Lookup NU author(s): Dr Anna Isakova, Dr Billy Murdoch, Dr Katarina Novakovic



This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License (CC BY-NC-ND).


Palladium-catalysed oxidative carbonylation (PCOC) of alkynes is a promising engine for building smart pulsatile polymeric systems, as it has demonstrated (in certain configurations) sustained regular oscillations in pH and redox potential for up to one month of monitoring in a batch reactor. Recent developments in polymer-supported palladium catalysts allowed to demonstrate the full capacity of this reaction - in a macrogel that experienced oscillations in volume, while releasing a drug load. In this work, we demonstrate reproducible oscillations (more than 100 h duration) in proline-functionalised chitosan-palladium system (Chi-Pro-Pd), using both small molecule (phenylacetylene) and polymeric (pegylated dialkyne) substrate, for the first time. Moreover, by functionalising chitosan with proline ligands, we dramatically reduced halide-mediated leaching of palladium, which readily occurred in non-functionalised chitosan-palladium catalysts (Chi-Pd). Oscillatory patterns for both systems confirm the need for fabricating functionalised chitosan supports to improve catalyst reusability and minimise loss of palladium.

Publication metadata

Author(s): Isakova A, Parkes GE, Murdoch BJ, Topham PD, Novakovic K

Publication type: Article

Publication status: Published

Journal: European Polymer Journal

Year: 2018

Volume: 109

Pages: 537-543

Print publication date: 01/12/2018

Online publication date: 25/10/2018

Acceptance date: 24/10/2018

Date deposited: 17/12/2018

ISSN (print): 0014-3057

ISSN (electronic): 1873-1945

Publisher: Elsevier


DOI: 10.1016/j.eurpolymj.2018.10.038


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