Non‐natural Photoenzymatic Controlled Radical Polymerization Inspired by DNA Photolyase

Abstract

Inspired by DNAp hotolyase,an on-natural photoenzymatic catalysis of common flavoproteins is developed for controlled radical polymerization under irradiation of visible light. This photoenzymatic polymerization is highly efficient under mild conditions,a pplicable to various monomer families,suitable for both homogeneous and heterogeneous media, and can be externally modulated by switching light on and off. Aunique combination of the natural enzymatic deoxygenation with the non-natural photoenzymatic process enables an unprecedented oxygen-tolerant, visible-light-controlled radical polymerization using asingle enzyme to be developed. Visible light activation of non-natural catalytic functions of the widely distributed flavoproteins is an exciting conceptual advance and may uncover ahitherto underexplored field of photoenzymatic catalysis.

Emerging Trends in Polymerization-Induced Self-Assembly

“…112 Very recently, the same group also utilized the flavin active site within GOx to conduct photoenzymatic initiation of RAFT dispersion polymerization. 113 These GOxbased initiation methods allow PISA to be performed without prior deoxygenation of the reaction medium; such oxygentolerant PISA formulations will be discussed further later in this paper.…”

Deazaflavin reductive photocatalysis involves excited semiquinone radicals

“…Inspired by nature, artificial Fl derivatives as well as flavoenzymes have been applied in photoredox catalysis and photobiocatalysis, mainly in oxidative transformations or in energy transfer processes 6,20,[30][31][32][33][34][35][36][37][38][39][40][41][42][43][44] . Photoenzymatic radical polymerisation employing highly reducing excited FADH* − known from photolyases is rare and a very recent example of a photoreductive process with Fl 45 . In the dFl series, dFl red has been found to be generated from dFl by PET from ethylenediaminetetraacetic acid used as sacrificial reductant 46 .…”

Progress and Perspectives Beyond Traditional RAFT Polymerization

“…[ 91 ] An innovative interfacing of oxidoreductase enzymes with photocatalysis has also emerged recently, where the photoexcitation of the enzyme's flavin cofactor can be directly harnessed to induce PET‐RAFT. [ 92 ]…”