SI-bioATRP in mesoporous silica for size-exclusion driven local polymer placement

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Wondra, Oleksandr and Ornati, Eleonora and Lehn, Robert and Mikolei, Joanna J. and Breitzke, Hergen and Pardehkhorram, Raheleh and Buntkowski, Gerd and Bruns, Nico and Andrieu-Brunsen, Annette (2025) SI-bioATRP in mesoporous silica for size-exclusion driven local polymer placement. Advanced Functional Materials. e22240. ISSN 1616-301X (https://doi.org/10.1002/adfm.202522240)

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Abstract

Controlling the size-exclusion driven localized placement of polymer chains within nanopores is essential for improving nanopore performance and bridging the gap between artificial and biological pores. While surface-initiated reversible-deactivation radical polymerizations are successfully employed for polymerization within nanopores, achieving simultaneous spatial control over polymer placement and minimizing catalyst usage remains a challenge. The study presents an example of enzyme-catalyzed surface-initiated atom transfer radical polymerization (SI-bioATRP) conducted within mesoporous particles requiring only minimal catalyst amounts. It is demonstrated that the mesostructure of the host material can be utilized to guide the polymer placement. Hemoglobin serves as the catalyst for the polymerization of the negatively charged monomer potassium 3-sulfopropyl methacrylate (KSPMA). The amount of grafted polymer is controlled by adjusting the density of silanol groups and the diameter of the mesopores. By employing mesoporous particles with pore neck diameters of 3.7 nm, polymer growth is predominantly restricted to the outer surface of the particles due to restricted accessibility of the catalyst and small molecules toward the mesoporous structure after initiator grafting, an effect confirmed by confocal laser scanning microscopy (CLSM). This work highlights the potential of SI-bioATRP for polymer grafting and the size-exclusion driven local polymer formation in mesoporous particles.

ORCID iDs

Wondra, Oleksandr, Ornati, Eleonora, Lehn, Robert, Mikolei, Joanna J., Breitzke, Hergen, Pardehkhorram, Raheleh, Buntkowski, Gerd, Bruns, Nico ORCID logoORCID: https://orcid.org/0000-0001-6199-9995 and Andrieu-Brunsen, Annette;
  • Item type:Article
    ID code:94911
    Dates:
    Date
    Event
    5 December 2025
    Published
    5 December 2025
    Published Online
    24 November 2025
    Accepted
    Subjects:Technology > Manufactures
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:08 Dec 2025 11:46
    Last modified:22 Jan 2026 09:42
    URI:https://strathprints.strath.ac.uk/id/eprint/94911
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