Issue 4, 2021

Light-fueled dynamic covalent crosslinking of single polymer chains in non-equilibrium states

Abstract

While polymer synthesis proceeds predominantly towards the thermodynamic minimum, living systems operate on the reverse principle – consuming fuel to maintain a non-equilibrium state. Herein, we report the controlled formation of 3D macromolecular architectures based on light-fueled covalent non-equilibrium chemistry. In the presence of green light (525 nm) and a bivalent triazolinedione (TAD) crosslinker, naphthalene-containing polymers can be folded into single chain nanoparticles (SCNPs). At ambient temperature, the cycloaddition product of TAD with naphthalene reverts and the SCNP unfolds into its linear parent polymer. The reported SCNP is the first example of a reversible light triggered folding of single polymer chains and can readily be repeated for several cycles. The folded state of the SCNP can either be preserved through a constant supply of light fuel, kinetic trapping or through a chemical modification that makes the folded state thermodynamically favored. Whereas small molecule bivalent TAD/naphthalene cycloaddition products largely degraded after 3 days in solution, even in the presence of fuel, the SCNP entities were found to remain intact, thereby indicating the light-fueled stabilization of the SCNP to be an inherent feature of the confined macromolecular environment.

Graphical abstract: Light-fueled dynamic covalent crosslinking of single polymer chains in non-equilibrium states

Supplementary files

Article information

Article type
Edge Article
Submitted
22 10 2020
Accepted
17 11 2020
First published
17 11 2020
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2021,12, 1302-1310

Light-fueled dynamic covalent crosslinking of single polymer chains in non-equilibrium states

D. Kodura, H. A. Houck, F. R. Bloesser, A. S. Goldmann, F. E. Du Prez, H. Frisch and C. Barner-Kowollik, Chem. Sci., 2021, 12, 1302 DOI: 10.1039/D0SC05818A

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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