Photoresponsive Cellulose Nanocrystals

Abstract

In this communication a method for the creation of fluorescent cellulose nanoparticles using click chemistry and subsequent photodimerization of the installed side-chains is demonstrated. In the first step, the primary hydroxyl groups on the surface of the CNCs were converted to carboxylic acids by using TEMPO-mediated hypohalite oxidation. The alkyne groups, essential for the click reaction, were introduced into the surface of TEMPO-oxidized CNCs via carbodiimide-mediated formation of an amide linkage between monomers carrying an amine functionality and carboxylic acid groups on the surface of the TEMPO-oxidized CNCs. Finally, the reaction of surface-modified TEMPO-oxidized cellulose nanocrystals and azido-bearing coumarin and anthracene monomers were carried out by means of a click chemistry, i.e., Copper(I)-catalyzed Azide-Alkyne Cycloaddition (CuAAC) to produce highly photo-responsive and fluorescent cellulose nanoparticles. Most significantly, the installed coumarin and/or anthracene side-chains were shown to undergo UV-induced [2+2] and [4+4] cycloaddition reactions, bringing and locking the cellulose nanocrystals together. This effort paves the way towards creating, cellulosic photo responsive nano-arrays with the potential of photo reversibility since these reactions are known to be reversible at varying wavelengths.