Orthogonal, metal-free surface modification by strain-promoted azide–alkyne and nitrile oxide–alkene/alkyne cycloadditions

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Wendeln, Christian and Singh, Ishwar and Rinnen, Stefan and Schulz, Christian and Arlinghaus, Heinrich F and Burley, Glenn A and Ravoo, Bart Jan (2012) Orthogonal, metal-free surface modification by strain-promoted azide–alkyne and nitrile oxide–alkene/alkyne cycloadditions. Chemical Science, 3 (8). pp. 2479-2484. ISSN 2041-6539 (https://doi.org/10.1039/c2sc20555f)

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Abstract

In this article we present a fast and efficient methodology for biochemical surface patterning under extremely mild conditions. Micropatterned azide/benzaldoxime-surfaces were prepared by microcontact printing of a heterobifunctional cyclooctyne oxime linker on azide-terminated self-assembled monolayers (SAMs). Strain-promoted azide–alkyne cycloaddition (SPAAC) in combination with microcontact printing allows fast and effective surface patterning. The resulting bifunctional azide/oxime substrates could successfully be used for metal-free, orthogonal immobilization of various biomolecules by 1,3-dipolar cycloadditions at room temperature. Azide-decorated areas were modified by reaction with a cyclooctyne-conjugate using SPAAC, while benzaldoxime-decorated areas were activated by in situ oxidation to the reactive nitrile oxides and subsequent nitrile oxide cycloaddition with alkene- and alkyne-functionalized bioconjugates. In addition, orthogonal double immobilization was achieved by consecutive and independent SPAAC and nitrile oxide cycloadditions.

ORCID iDs

Wendeln, Christian, Singh, Ishwar, Rinnen, Stefan, Schulz, Christian, Arlinghaus, Heinrich F, Burley, Glenn A ORCID logoORCID: https://orcid.org/0000-0002-4896-113X and Ravoo, Bart Jan;
CORE (COnnecting REpositories)