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Enzymatically Degassed Surface-Initiated Atom Transfer Radical Polymerization with Real-Time Monitoring.

Publication ,  Journal Article
Navarro, LA; Enciso, AE; Matyjaszewski, K; Zauscher, S
Published in: Journal of the American Chemical Society
February 2019

Polymer brush coatings are frequently prepared by radical polymerization, a notoriously oxygen sensitive process. Glucose oxidase (GOx) can inexpensively enable radical polymerization in solution by enzymatically consuming oxygen as it oxidizes glucose. Here, we report the growth of polymeric brushes using GOx-assisted atom transfer radical polymerization (ATRP) from a surface while open to air. Specifically, we grew a set of biomedically relevant polymer brushes, including poly(oligo(ethylene glycol) methacrylate) (POEGMA), poly(2-dimethylaminoethyl methacrylate) (PDMAEMA), poly(sulfobetaine methacrylate) (PSBMA), and poly(2-(methylsulfinyl)ethyl acrylate (PMSEA). For each of these polymers, we monitored GOx-assisted and GOx-free ATRP reaction kinetics in real time using quartz crystal microbalance (QCM) and verified findings with localized surface plasmon resonance (LSPR). We modeled brush growth kinetics considering bimolecular termination. This model fit our data well ( r2 > 0.987 for all samples) and shows the addition of GOx increased effective kinetic chain lengths, propagation rates, and reproducibility. We tested the antifouling properties of the polymer brush coatings against human blood plasma and were surprised to find that coatings prepared with GOx repelled more plasma proteins in all cases than their GOx-free counterparts.

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Published In

Journal of the American Chemical Society

DOI

EISSN

1520-5126

ISSN

0002-7863

Publication Date

February 2019

Volume

141

Issue

7

Start / End Page

3100 / 3109

Related Subject Headings

  • Surface Plasmon Resonance
  • Quartz Crystal Microbalance Techniques
  • Polymethacrylic Acids
  • Polymerization
  • Plasma
  • Oxygen
  • Humans
  • Glucose Oxidase
  • Glucose
  • General Chemistry
 

Citation

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Navarro, L. A., Enciso, A. E., Matyjaszewski, K., & Zauscher, S. (2019). Enzymatically Degassed Surface-Initiated Atom Transfer Radical Polymerization with Real-Time Monitoring. Journal of the American Chemical Society, 141(7), 3100–3109. https://doi.org/10.1021/jacs.8b12072
Navarro, Luis A., Alan E. Enciso, Krzysztof Matyjaszewski, and Stefan Zauscher. “Enzymatically Degassed Surface-Initiated Atom Transfer Radical Polymerization with Real-Time Monitoring.Journal of the American Chemical Society 141, no. 7 (February 2019): 3100–3109. https://doi.org/10.1021/jacs.8b12072.
Navarro LA, Enciso AE, Matyjaszewski K, Zauscher S. Enzymatically Degassed Surface-Initiated Atom Transfer Radical Polymerization with Real-Time Monitoring. Journal of the American Chemical Society. 2019 Feb;141(7):3100–9.
Navarro, Luis A., et al. “Enzymatically Degassed Surface-Initiated Atom Transfer Radical Polymerization with Real-Time Monitoring.Journal of the American Chemical Society, vol. 141, no. 7, Feb. 2019, pp. 3100–09. Epmc, doi:10.1021/jacs.8b12072.
Navarro LA, Enciso AE, Matyjaszewski K, Zauscher S. Enzymatically Degassed Surface-Initiated Atom Transfer Radical Polymerization with Real-Time Monitoring. Journal of the American Chemical Society. 2019 Feb;141(7):3100–3109.
Journal cover image

Published In

Journal of the American Chemical Society

DOI

EISSN

1520-5126

ISSN

0002-7863

Publication Date

February 2019

Volume

141

Issue

7

Start / End Page

3100 / 3109

Related Subject Headings

  • Surface Plasmon Resonance
  • Quartz Crystal Microbalance Techniques
  • Polymethacrylic Acids
  • Polymerization
  • Plasma
  • Oxygen
  • Humans
  • Glucose Oxidase
  • Glucose
  • General Chemistry