Materials Horizons 2018-04-07

Photochemical Ligation Meets Nanocellulose: A Versatile Platform for Self-Reporting Functional Materials

Daniel Hoenders, Jiaqi Guo, Anja S. Goldmann, Christopher Barner-Kowollik, Andreas Walther

Index: 10.1039/C8MH00241J

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Abstract

The sustainable origin and highly promising mechanical and functional properties of cellulose nanofibrils (CNFs) attract significant interest for the construction of advanced functional materials. One key aspects to promote functionality of CNF-based materials is to implement sophisticated, facile and versatile chemical functionalization principles for application-targeted modification of CNF properties, independent on whether aiming for functional surfaces, hydrogels or bulk materials. We herein merge for the first time a self-reporting photo-induced modular ligation, the UV-induced nitrile imine-mediated tetrazole/ene cycloaddition, with CNFs to control chemical functionality in space and time with the possibility for a macroscopic fluorescence readout of the reaction progress. We discuss this hetero-complimentary photo-conjugation with respect to immobilization of the photoactive tetrazole units on CNFs in bulk and dispersion, and demonstrate the application for the three important CNF-based material classes (surfaces, hydrogels and bioinspired nanocomposites) by modification with photo-complementary maleimide-tethered functional moieties. In addition to realizing selective biorecognition patterns on transparent nanopapers, we showcase photo-induced hydrogelation relevant for biomaterials, as well as mechanical stiffening in bioinspired nanocomposites in bulk. The photochemical ligation proceeds smoothly in all three materials of vastly different dynamics (solution to bulk) and hence establishes a platform methodology to promote self-reporting functionalization of diverse CNF-based materials.