Well-Defined Macromolecules Using Horseradish Peroxidase as a RAFT Initiase

Danielson, Alex; Kuren, Dylan Bailey Van; Lucius, Melissa E.; Makaroff, Katherine; Williams, Cameron; Page, Richard C.; Berberich, Jason A.; Konkolewicz, Dominik

doi:10.1002/marc.201500633

Cited by 72 publications

(45 citation statements)

References 39 publications

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“…[24] Well defined and high molecular weight homopolymers and di-/tri-block copolymers with low values and high monomer conversions were readily achieved in aqueous buffer solution (pH 7) at low HRP concentrations via this ternary enzymatic redox-RAFT polymerization. [23] Independently, Konkolewicz and co-workers [25] also demonstrated the use of this enzymatic redox initiating system for the RAFT polymerization of DMA, NIPAM, and oligo(ethylene oxide) methyl ether acrylate (OEOA) in the presence of (2-propionic acid)yl ethyl trithiocarbonate (PAETC) as CTA in a buffer solution (pH 5.5) at room temperature. Although high monomer conversion values were achieved, the values were above 1.25.…”

Section: Redox Pairs For Raft Initiationmentioning

confidence: 99%

Redox-Initiated Reversible Addition–Fragmentation Chain Transfer (RAFT) Polymerization

Reyhani

McKenzie

et al. 2019

Aust. J. Chem.

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Reversible addition–fragmentation chain transfer (RAFT) polymerization initiated by a radical-forming redox reaction between a reducing and an oxidizing agent (i.e. ‘redox RAFT’) represents a simple, versatile, and highly useful platform for controlled polymer synthesis. Herein, the potency of a wide range of redox initiation systems including enzyme-mediated redox reactions, the Fenton reaction, peroxide-based reactions, and metal-catalyzed redox reactions, and their application in initiating RAFT polymerization, are reviewed. These redox-RAFT polymerization methods have been widely studied for synthesizing a broad range of homo- and co-polymers with tailored molecular weights, compositions, and (macro)molecular structures. It has been demonstrated that redox-RAFT polymerization holds particular promise due to its excellent performance under mild conditions, typically operating at room temperature. Redox-RAFT polymerization is therefore an important and core part of the RAFT methodology handbook and may be of particular importance going forward for the fabrication of polymeric biomaterials under biologically relevant conditions or in biological systems, in which naturally occurring redox reactions are prevalent.

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Section: Redox Pairs For Raft Initiationmentioning

confidence: 99%

Redox-Initiated Reversible Addition–Fragmentation Chain Transfer (RAFT) Polymerization

Reyhani

McKenzie

et al. 2019

Aust. J. Chem.

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“…Horseradish peroxidase (HRP) can oxidize several classes of substrates with H 2 O 2 to generate radicals, which in turn can either initiate polymerization of vinyl monomers or generate substrate‐based polymers as in the case of phenol‐based compounds . Since the CCS polymer has phenol units on its periphery, we anticipate that the emulsions can be covalently crosslinked into emulsion gels via HRP‐catalyzed radical polymerization of the phenol units (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

Enzymatically Crosslinked Emulsion Gels Using Star-Polymer Stabilizers

2016

Macromol. Rapid Commun.

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A novel type of emulsion gel based on star-polymer-stabilized emulsions is highlighted, which contains discrete hydrophobic oil and hydrophilic aqueous solution domains. Well-defined phenol-functionalized core-crosslinked star polymers are synthesized via reversible addition-fragmentation chain transfer (RAFT)-mediated dispersion polymerization and are used as stabilizers for oil-in-water emulsions. Horseradish-peroxidase-catalyzed polymerization of the phenol moieties in the presence of H O enables rapid formation of crosslinked emulsion gels under mild conditions. The crosslinked emulsion gels exhibit enhanced mechanical strength, as well as widely tunable composition.

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“…In fact, RAFT CTAs aid in achieving control of the radical polymerization via reversible addition of the thiocarbonylthio group and rapid fragmentation reactions . Therefore, relatively analogous activation/initiation systems such as thermal, photo, enzyme, and redox based radical formation can be employed to initiate both FRP and RAFT processes. Despite the huge advances made in this field, new techniques that can overcome some of the drawbacks of these systems are continuously sought.…”

Section: Redox Reaction In Initiating Polymerizationsmentioning

confidence: 99%

“…Peroxide initiators including tert‐butyl hydroperoxide (TBHP), benzol peroxide (BPO), and hydrogen peroxide (H 2 O 2 ) have also been widely used to initiate radical polymerization. The TBHP/ascorbic acid (AsAc) pair has been used to initiate the aqueous RAFT polymerization of VP at ambient conditions in the presence of a xanthate RAFT agent without any observable side reactions .…”

Section: Redox Reaction In Initiating Polymerizationsmentioning

confidence: 99%

Fenton‐Chemistry‐Mediated Radical Polymerization

Reyhani

McKenzie

et al. 2019

Macromol. Rapid Commun.

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have been developed for the synthesis of polymers with diverse structures (linear, star, cyclic, etc.), compositions ( • mopolymer, gradient, alternating, block, etc.), and functionalities (thiol, amine, etc.). [11] The main mechanism of RDRP which results in controllable polymerization is the establishment of a dynamic equilibrium between the propagating radicals (active polymers) and the dormant species via a reversible activation-deactivation process with rate constants k act. and k deact. , respectively. [7,12] With the emergence of RDRP methods such as atom transfer radical polymerization (ATRP), [13][14][15] nitroxide-mediated polymerization (NMP), [16] and reversible addition-fragmentation transfer (RAFT) [11,17,18] there has been significant effort to control these techniques via different physical and chemical stimuli. [19][20][21][22][23][24][25][26][27] Of these, RAFT holds particular promise due to its compatibility with a diverse range of solvents, monomers, and operating conditions. [11,24,[28][29][30][31][32][33][34][35] Among RDRP methods, one might argue that RAFT is the most similar to traditional FRP, with the simple addition of a thiocarbonylthio-containing compound chain transfer agent (CTA, termed as RAFT agent) [36] that can mediate the polymerization, allowing the synthesis of well-defined polymers (Scheme 1). In fact, RAFT CTAs aid in achieving control of the radical polymerization via reversible addition of the thiocarbonylthio group and rapid fragmentation reactions. [37,38] Therefore, relatively analogous activation/initiation systems such as thermal, [4,11,[28][29][30][31][39][40][41] photo, [2,24,[32][33][34][42][43][44][45][46][47][48][49] enzyme, [5,23,[50][51][52][53][54] and redox [3,[55][56][57][58][59] based radical formation can be employed to initiate both FRP and RAFT processes. Despite the huge advances made in this field, new techniques that can overcome some of the drawbacks of these systems are continuously sought. For example, using a thermal initiator requires a high operating temperature, limiting the possibility for in situ FRP/RAFT methods in biological systems, where temperature control is limited. The rate of visible light-activated RAFT polymerization without using photocatalysts is relatively slow, [34,60] while photocatalysts, e.g. iridium and rutheniumbased ones, [24,61] employed in photo-activated processes are expensive. Moreover, photo-mediated polymerization faces difficulties in terms of the equipment requisite to perform photoinitiation at scale. [29] Redox-responsive polymerization systems have many advantages, including a low activation energy (40-85 kJ mol −1 ), easy and facile control over the polymerization at ambient temperatures, very short induction periods, etc. [56,62] Polymerizations initiated by a redox reaction between an oxidizing and a reducing agent are referred to as "redox polymerizations." [63] Use of Radical PolymerizationIn this review, the power of a classical chemical reaction, the Fenton reaction for initiating radical polymeriza...

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Well-Defined Macromolecules Using Horseradish Peroxidase as a RAFT Initiase

Cited by 72 publications

References 39 publications

Redox-Initiated Reversible Addition–Fragmentation Chain Transfer (RAFT) Polymerization

Redox-Initiated Reversible Addition–Fragmentation Chain Transfer (RAFT) Polymerization

Enzymatically Crosslinked Emulsion Gels Using Star-Polymer Stabilizers

Fenton‐Chemistry‐Mediated Radical Polymerization

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