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Polymers 2018, 10(7), 741;

Investigating the Mechanism of Horseradish Peroxidase as a RAFT-Initiase

Department of Chemistry and Biochemistry Miami University 651 E High St, Oxford, OH 45056, USA
Department of Chemical, Paper and Biomedical Engineering Miami University 650 E High St, Oxford, OH 45056, USA
Author to whom correspondence should be addressed.
Received: 20 June 2018 / Revised: 28 June 2018 / Accepted: 3 July 2018 / Published: 5 July 2018
(This article belongs to the Special Issue Polymerization Kinetics)
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A detailed mechanistic and kinetic study of enzymatically initiated RAFT polymerization is performed by combining enzymatic assays and polymerization kinetics analysis. Horseradish peroxidase (HRP) initiated RAFT polymerization of dimethylacrylamide (DMAm) was studied. This polymerization was controlled by 2-(propionic acid)ylethyl trithiocarbonate (PAETC) in the presence of H2O2 as a substrate and acetylacetone (ACAC) as a mediator. In general, well controlled polymers with narrow molecular weight distributions and good agreement between theoretical and measured molecular weights are consistently obtained by this method. Kinetic and enzymatic assay analyses show that HRP loading accelerates the reaction, with a critical concentration of ACAC needed to effectively generate polymerization initiating radicals. The PAETC RAFT agent is required to control the reaction, although the RAFT agent also has an inhibitory effect on enzymatic performance and polymerization. Interestingly, although H2O2 is the substrate for HRP there is an optimal concentration near 1 mM, under the conditions studies, with higher or lower concentrations leading to lower polymerization rates and poorer enzymatic activity. This is explained through a competition between the H2O2 acting as a substrate, but also an inhibitor of HRP at high concentrations. View Full-Text
Keywords: RAFT polymerization; enzymatic polymerization; reaction kinetics; horseradish peroxidase; polymerization mechanism RAFT polymerization; enzymatic polymerization; reaction kinetics; horseradish peroxidase; polymerization mechanism

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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).

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Danielson, A.P.; Van-Kuren, D.B.; Bornstein, J.P.; Kozuszek, C.T.; Berberich, J.A.; Page, R.C.; Konkolewicz, D. Investigating the Mechanism of Horseradish Peroxidase as a RAFT-Initiase. Polymers 2018, 10, 741.

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