Light-Induced Inverse Electron Demand Diels-Alder Reaction as an Approach for Grafting Macromolecules to Glass Surfaces

Nagihan Özbek, Elif L. Sahkulubey Kahveci, Muhammet Ubeydullah Kahveci*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

1 Citation (Scopus)

Abstract

This study aims to develop a grafting technique for glass surfaces by light-induced inverse electron demand Diels-Alder (photo-IEDDA) reaction. The approach depends on the in situ formation of tetrazine molecule in the reaction medium and a subsequent IEDDA reaction of tetrazine moieties with trans-cyclooctene groups. First, light-induced formation of a tetrazine derivative from a precursor, 6-(6-(pyridin-2-yl)-1,4-dihydro-1,2,4,5-tetrazin-3-yl)pyridin-3-amine (PPA-dHTz), in the presence of a photosensitizer under visible light irradiation was evaluated by nuclear magnetic resonance (NMR) spectroscopy. For grafting glass surfaces, dihydrotetrazine (dHTz) end-functionalized poly(N-isopropylacrylamide) (PNIPAAm-dHTz) and poly(dl-lactide) (PLA-dHTz) were prepared by reversible addition-fragmentation chain-transfer (RAFT) polymerization and ring-opening polymerization (ROP), respectively, and postpolymerization functionalization with a dihydrotetrazine molecule (PPA-dHTz). However, glass surfaces were decorated with trans-cyclooctenol (TCO) groups by functionalization with 3-aminopropyltriethoxysilane, succinic anhydride, and TCO successively. Then, photo-IEDDA was performed between the dHTz end-functionalized polymers and TCO-decorated glass surface in the presence of methylene blue and under visible light irradiation. To extend the applicability of the approach, grafting TCO-functionalized protein, namely, Concanavalin A-TCO, to dHTz-modified glass surface was achieved as well. In this case, glass surfaces were functionalized with PPA-dHTz. The successful polymer and protein grafting to glass surfaces were shown with X-ray photoelectron spectroscopy, contact angle measurement, scanning electron microscopy, atomic force microscopy, and Fourier transform infrared (FT-IR) spectroscopy.

Original languageEnglish
Pages (from-to)3721-3732
Number of pages12
JournalACS Applied Polymer Materials
Volume3
Issue number8
DOIs
Publication statusPublished - 13 Aug 2021

Bibliographical note

Publisher Copyright:
© 2021 American Chemical Society.

Funding

The authors thank The Scientific and Technological Research Council of Turkey for the financial support. E.L.S.K. is grateful to Council of Higher Education of Turkey (YOK 100/2000 PhD Scholarship) and to TUBITAK (2211-C PhD Scholarship) for financial support. This work was financially supported by The Scientific and Technological Research Council of Turkey (TUBITAK, Project # 217Z057).

FundersFunder number
Council of Higher Education of Turkey
TUBITAK217Z057
Türkiye Bilimsel ve Teknolojik Araştirma Kurumu

    Keywords

    • glass surface
    • IEDDA
    • light-induced click
    • photooxidation
    • polymer
    • protein
    • surface grafting
    • tetrazine

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