The Influence of Irradiation Wavelength on the Growth of Polymer Brushes by SI-PET-RAFT Polymerization

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Author(s)Mérai, László
Author(s)Rymsha, Khrystyna
Author(s)Yadav, Jyoti
Author(s)Pester, Christian W.
Author(s)Fery, Andreas
Author(s)Besford, Quinn A.
Date Accessioned2025-04-10T19:59:05Z
Date Available2025-04-10T19:59:05Z
Publication Date2025-02-22
DescriptionThis article was originally published in Journal of Polymer Science. The version of record is available at: https://doi.org/10.1002/pol.20241148. © 2025 The Author(s). Journal of Polymer Science published by Wiley Periodicals LLC. This is an open access article under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0/), which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
AbstractAn effective method to produce well-defined polymer brushes with high spatial, temporal, and sequence control is to employ a photoredox catalyst in photo-mediated polymerization. Generally, the excitation wavelength is chosen as the absorption maximum of the photocatalyst, however, it is not clear if that corresponds to the best photochemical activity for producing polymer brushes. Herein, we systematically examine wavelength-by-wavelength resolved polymer brush growth using surface-initiated photoinduced electron transfer-reversible addition-fragmentation chain transfer polymerization (SI-PET-RAFT), of four monomer types. The absorption spectra of the water-soluble photocatalyst (ZnTPPS44−) and the brush growth at each irradiation wavelength were examined as photochemical activity plots. Our results show a striking disparity between the absorbance of the photoredox catalyst and the maximum brush height. Moreover, the photochemical activity with wavelength was highly dependent on the nature of the monomer used. In addition to displaying a strong wavelength selectivity, a characteristic red-shift in the brush height relative to the lowest possible energy transition of the photocatalyst's absorbance spectrum was observed. We anticipate this work will better inform on wavelength choice for SI-PET-RAFT polymerization of polymer brushes. Graphical Abstract available at: https://doi.org/10.1002/pol.20241148 The use of SI-PET-RAFT has been gaining momentum for producing thick, homogenous, functional polymer brushes, in an oxygen-tolerant manner. However, the connection between irradiation wavelength and the brush height has not been clear. Herein, we systematically explore the effect of irradiation wavelength on the resulting brush properties, finding a disconnection between photocatalyst absorption and brush thicknesses.
SponsorThe authors gratefully acknowledge the Deutsche Forschungsgemeinschaft (DFG) for funding project 496201730 ((BE 7737/2-1) (Q.A.B., K.R., L.M.)), and the Alexander von Humboldt Foundation (J.Y.). The first three authors (L.M., K.R., and J.Y.) contributed equally to this work. We gratefully acknowledge Dr. Eva Bittrich for assistance with in situ ellipsometry, and Prof. Christopher Barner-Kowollik for enlightening discussions.
CitationMérai, L., Rymsha, K., Yadav, J., Pester, C.W., Fery, A. and Besford, Q.A. (2025), The Influence of Irradiation Wavelength on the Growth of Polymer Brushes by SI-PET-RAFT Polymerization. J Polym Sci. https://doi.org/10.1002/pol.20241148
ISSN2642-4169
URLhttps://udspace.udel.edu/handle/19716/36019
Languageen_US
PublisherJournal of Polymer Science
dc.rightsAttribution 4.0 Internationalen
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/
Keywordsphotochemical action plots
Keywordsphotopolymerisation
Keywordspolymer brushes
KeywordsSI-PET-RAFT
Keywordswavelength- dependence
TitleThe Influence of Irradiation Wavelength on the Growth of Polymer Brushes by SI-PET-RAFT Polymerization
TypeArticle
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