Chemistry Publications

Document Type

Article

Publication Date

10-13-2020

Journal

Macromolecules

Volume

53

Issue

19

First Page

8600

Last Page

8609

URL with Digital Object Identifier

10.1021/acs.macromol.0c01197

Abstract

Polyglyoxylates are a class of self-immolative polymers that depolymerize in solution and the solid state. The glyoxylic acid degradation product is a metabolite in the glyoxylate cycle and can also be processed in the liver in humans, making polyglyoxylates attractive for applications in the environment and in medicine. Although expanding the scope of available polyglyoxylates would enable new properties and applications, highly pure glyoxylate monomers are required for polymerization, and this level of purity is difficult to achieve for many potential monomers. To address this challenge, we report here the 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD)-catalyzed post-polymerization transesterification of poly(ethyl glyoxylate) (PEtG) as a general method for the synthesis of directly inaccessible polyglyoxylates. Using a new end-capping strategy, PEtG compatible with the transesterification reaction was developed. n-Propanol, i-propanol, n-butanol, t-butanol, n-pentanol, n-hexanol, n-octanol, and benzyl alcohol were employed and the reactivities of these different alcohols were investigated. The resulting polyglyoxylates were characterized chemically and their thermal properties were compared. In all cases, the transesterified polyglyoxylates retained the stimuli-responsive depolymerization properties of the parent PEtG. In addition, functional polyglyoxylates based on allyl, propargyl, and furfuryl esters, which are suitable for subsequent click reactions, were prepared. The propargyl-functionalized polyglyoxylate was used to conjugate pyrene, and the resulting molecules underwent a change in fluorescence properties upon depolymerization.

Notes

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Macromolecules, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.macromol.0c01197

Available for download on Wednesday, October 13, 2021

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