Issue 31, 2022

Fluorogenic monomer activation for protein-initiated atom transfer radical polymerization

Abstract

Fluorogenic atom transfer radical polymerization (ATRP) directly detects initiator-dependent polymer formation, as initially non-fluorescent polycyclic aromatic probe monomers reveal visible fluorescence upon polymerization in real time. Advancement of this initial proof-of-concept toward biodetection applications requires both a more detailed mechanistic understanding of probe fluorescence activation, and the ability to initiate fluorogenic polymerization directly from a biomolecule surface. Here, we show that simple monomer hydrogenation, independent of polymerization, reveals probe fluorescence, supporting the critical role of covalent enone attachment in fluorogenic probe quenching and subsequent fluorescence activation. We next demonstrate bioorthogonal, protein-initiated fluorogenic ATRP by the surface conjugation and characterization of protein–initiator conjugates of a model protein, bovine serum albumin (BSA). Fluorogenic ATRP from initiator-modified protein allows for real-time visualization of polymer formation with negligible background fluorescence from unmodified BSA controls. We further probe the bioorthogonality of this fluorogenic ATRP assay by assessing polymer formation in a complex biological environment, spiked with fetal bovine serum. Taken together, we demonstrate the potential of aqueous fluorogenic ATRP as a robust, bioorthogonal method for biomolecular-initiated polymerization by real-time fluorescence activation.

Graphical abstract: Fluorogenic monomer activation for protein-initiated atom transfer radical polymerization

  • This article is part of the themed collection: New Talent

Supplementary files

Article information

Article type
Paper
Submitted
27 1月 2022
Accepted
06 6月 2022
First published
08 6月 2022

Org. Biomol. Chem., 2022,20, 6257-6262

Author version available

Fluorogenic monomer activation for protein-initiated atom transfer radical polymerization

D. Tahseen, J. R. Sackey-Addo, Z. T. Allen, J. T. Anderson, J. B. McMurry and C. B. Cooley, Org. Biomol. Chem., 2022, 20, 6257 DOI: 10.1039/D2OB00175F

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