2021
DOI: 10.1038/s41467-020-20640-z
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Unravelling an oxygen-mediated reductive quenching pathway for photopolymerisation under long wavelengths

Abstract: Photomediated-reversible-deactivation radical polymerisation (photo-RDRP) has a limited scope of available photocatalysts (PCs) due to multiple stringent requirements for PC properties, limiting options for performing efficient polymerisations under long wavelengths. Here we report an oxygen-mediated reductive quenching pathway (O-RQP) for photoinduced electron transfer reversible addition-fragmentation chain transfer (PET-RAFT) polymerisation. The highly efficient polymerisations that are performed in the pre… Show more

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Cited by 65 publications
(90 citation statements)
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“…Such “oxygen‐acceleration” behavior was observed indeed in Boyer's group as stated above, however, in a reductive quenching cycle in the presence of sacrificial reducing agents. [ 60 ] This rather counterintuitive “oxygen‐acceleration” behavior was similarly observed for a variety of acrylate and acrylamide monomers (Figure 2e). To understand the origin of this phenomenon, kinetics of PET‐RAFT polymerizations of oligo(ethylene glycol) methyl ether acrylate (OEGA) were monitored by 1 H NMR and gel‐permeation chromatography (GPC) for 3DP‐MSDP‐IPN (5 ppm) under air and N 2 atmosphere (Figure 2b,c; Figure S8, Supporting Information); here, OEGA was chosen as a model system of the kinetics studies for the comparison to PET‐RAFT polymerizations in aqueous environment.…”
Section: Resultssupporting
confidence: 54%
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“…Such “oxygen‐acceleration” behavior was observed indeed in Boyer's group as stated above, however, in a reductive quenching cycle in the presence of sacrificial reducing agents. [ 60 ] This rather counterintuitive “oxygen‐acceleration” behavior was similarly observed for a variety of acrylate and acrylamide monomers (Figure 2e). To understand the origin of this phenomenon, kinetics of PET‐RAFT polymerizations of oligo(ethylene glycol) methyl ether acrylate (OEGA) were monitored by 1 H NMR and gel‐permeation chromatography (GPC) for 3DP‐MSDP‐IPN (5 ppm) under air and N 2 atmosphere (Figure 2b,c; Figure S8, Supporting Information); here, OEGA was chosen as a model system of the kinetics studies for the comparison to PET‐RAFT polymerizations in aqueous environment.…”
Section: Resultssupporting
confidence: 54%
“…[ 70 ] Given the concentration of CDTPA and oxygen in the polymerization conditions (11.3 × 10 −3 and 0.67 × 10 −3 m , respectively; here, dissolved oxygen concentration was calculated for the mixed solutions of DMSO and monomers with a 1:1 volume ratio), the rate of electron/energy transfer between 3 PC * and oxygen is calculated to be ≈1.0 × 10 6 s −1 , which is faster than that between 3 PC * and CDTPA (≈7.9 × 10 5 s −1 ), implying that direct electron transfer from 3 PC * to CDTPA (and/or dormant species) might not be favored in the presence of oxygen. Very recently, Boyer and co‐workers proposed the oxygen‐mediated reductive quenching pathway (O‐RQP) as a new mechanism to rationalize the “oxygen‐acceleration” behavior observed for carefully chosen PCs in the presence of triethylamine (TEA) as a sacrificial reducing agent, [ 60 ] where the author demonstrated the thermodynamic feasibility of O‐RQP through quantum‐chemical (QC) calculations and studies of structure–property–performance relationships. Here, oxygen acts as an electron shuttle to catalyze the electron transfer between TEA and CTA (and/or dormant species) in the overall reductive quenching cycle.…”
Section: Resultsmentioning
confidence: 99%
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“…13 Whilst it has been shown that the generic reducing environment of bacteria can be used to produce organic radicals from the reduction of an aryl diazonium salt, which initiates the RAFT process, 10 this has been achieved so far only under anoxic conditions, hindering translation to biological applications. Conversely, many oxygen tolerant RAFT polymerisations have been reported, 14 either by polymerizing directly through oxygen [15][16][17] or utilising a scavenger such as an enzyme [18][19][20] or oxygen trap [21][22][23][24][25] , which has enabled ultralow reaction volumes, 17,19,22 3D/4D printing 21,26 and high throughput platforms, 22 but to the best of our knowledge have not been applied in a bacterially initiated RAFT polymerisation.…”
Section: Introductionmentioning
confidence: 99%