Divergent growth of poly(amidoamine) dendrimer-like branched polymers at the reducing end of cellulose nanocrystals.

This paper presents the growth of dendritic polymers at the reducing ends of cellulose nanocrystals by the "grafting from" approach. We took advantage of the chemically differentiated ends of cellulose nanocrystals to specifically synthesize dendrimers at their reducing end by the divergent approach. We used acid-amine coupling reactions in aqueous media to synthesize the carboxylic acid- or amine-terminated poly(amidoamine) dendrimers. The growth of dendrimer generations was monitored by UV and FTIR spectroscopies, and we successfully introduced up to 4 generations. The dendrimer growth at reducing ends was demonstrated by the nanocrystal adsorption driven by the peripheral amino groups onto gold surfaces. Hence, the results from quartz crystal microbalance with dissipation (QCM-D) pointed to a rather upright orientation of the dendrimer-modified cellulose nanocrystals. As the generation increased, the adsorbed layers appeared to be more flexible, which demonstrated that the functionality at the reducing end can successfully tune the properties of cellulose nanocrystals.