Bioinspired Iron‐Based Catalyst for Atom Transfer Radical Polymerization

Simakova, Antonina; Mackenzie, Matthew; Averick, Saadyah; Park, Sangwoo; Matyjaszewski, Krzysztof

doi:10.1002/ange.201306337

Cited by 9 publications

(4 citation statements)

References 49 publications

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“…Only a handful of alternative metal catalysts at low concentration showed appreciable activity under these more challenging conditions, with stark differences in polymerization rate between S. oneidensis MR-1 and the Δ mtrC Δ omcA knockout ( Figure 4c ). Consistent with previous reports 19 , 20 , aerobic polymerization rates for FeCl 3 , cyanocobalamin, and CuSO 4 were lower compared to optimized Cu-based catalysts. Although fewer metals were active under aerobic conditions, our results indicate that additional ligand optimization or increasing catalyst concentration could significantly improve activity, as was the case when Cu(II)-EDTA was replaced with Cu(II)-TPMA 13 .…”

Section: Resultssupporting

confidence: 92%

“…Because our polymerization is driven by EET flux to a metal catalyst, we predicted that other metals besides Cu would show appreciable polymerization activity under both anaerobic and aerobic conditions. Indeed, metal catalysts comprised of Fe 19 , 20 , Co 21 , 22 , Ni 23 , 24 , and Ru 25 have all been reported to exhibit ATRP-like activity. Although alternative metal catalysts are generally less active than Cu, they are potentially advantageous due to their lower toxicity.…”

Section: Resultsmentioning

confidence: 99%

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Aerobic radical polymerization mediated by microbial metabolism

et al. 2020

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Performing radical polymerizations under ambient conditions is a significant challenge because molecular oxygen is an effective radical quencher. Here we show that the facultative electrogen Shewanella oneidensis can control metal-catalyzed living radical polymerizations under apparent aerobic conditions by first consuming dissolved oxygen via aerobic respiration, then directing extracellular electron flux to a metal catalyst. In both open and closed containers, S. oneidensis enabled living radical polymerizations without requiring the pre-removal of oxygen. Polymerization activity was closely tied to S. oneidensis anaerobic metabolism through specific extracellular electron transfer (EET) proteins and was effective for a variety of monomers using low (ppm) concentrations of metal catalysts. Finally, polymerizations survived repeated challenges of oxygen exposure and could be initiated using lyophilized or spent (recycled) cells. Overall, our results demonstrate how the unique ability of S. oneidensis to use both oxygen and metals as respiratory electron acceptors can be leveraged to address salient challenges in polymer synthesis.

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Section: Resultssupporting

confidence: 92%

Section: Resultsmentioning

confidence: 99%

Aerobic radical polymerization mediated by microbial metabolism

et al. 2020

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“…[49][50][51][52][53][54] Moreover, biocatalytic ATRP with iron-containing proteins and bioinspired ironbased catalysts is especially advantageous to synthesize polymers for biological applications because iron has low toxicity and high biocompatibility compared to copper. 55 In addition to synthetic applications, biocatalytic ATRP can be used to detect clinically relevant biocatalysts via polymerization-based signal amplification. Bruns and coworkers recently proposed a new method to diagnose malaria using hemozoincatalyzed ATRP (Fig.…”

Section: Biocatalytic Atrpmentioning

confidence: 99%

Radical polymerization reactions for amplified biodetection signals

Kim

Sikes

2020

Polym. Chem.

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“…During the last decades, the design of well-tailored polymers molecules with predetermined number average chain length, high end-group functionality (EGF), controlled topology and low dispersity has been the topic of many research activities [1][2][3][4][5][6][7][8][9][10][11][12][13][14]. These advanced macromolecular architectures are typically acquired via controlled radical polymerization (CRP), which is also known as reversible deactivation radical polymerization (RDRP).…”

Section: Introductionmentioning

confidence: 99%

Fed-Batch Control and Visualization of Monomer Sequences of Individual ICAR ATRP Gradient Copolymer Chains

et al. 2014

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Based on kinetic Monte Carlo simulations of the monomer sequences of a representative number of copolymer chains (≈ 150,000), optimal synthesis procedures for linear gradient copolymers are proposed, using bulk Initiators for Continuous Activator Regeneration Atom Transfer Radical Polymerization (ICAR ATRP). Methyl methacrylate and n-butyl acrylate are considered as comonomers with CuBr 2 /PMDETA (N,N,N′,N′′,N′′-pentamethyldiethylenetriamine) as deactivator at 80 °C. The linear gradient quality is determined in silico using the recently introduced gradient deviation () polymer property. Careful selection or fed-batch addition of the conventional radical initiator I 2 allows a reduction of the polymerization time with ca. a factor 2 compared to the corresponding batch case, while preserving control over polymer properties ( ≈ 0.30; dispersity ≈ 1.1) . Fed-batch addition of not only I 2 , but also comonomer and deactivator (50 ppm) under starved conditions yields a below 0.25 and, hence, an excellent linear gradient quality for the dormant polymer molecules, albeit at the expense of an increase of the overall polymerization time. The excellent control is confirmed by the visualization of the monomer sequences of ca. 1000 copolymer chains.

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Bioinspired Iron‐Based Catalyst for Atom Transfer Radical Polymerization

Cited by 9 publications

References 49 publications

Aerobic radical polymerization mediated by microbial metabolism

Aerobic radical polymerization mediated by microbial metabolism

Radical polymerization reactions for amplified biodetection signals

Fed-Batch Control and Visualization of Monomer Sequences of Individual ICAR ATRP Gradient Copolymer Chains

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