Effect of Acetylation Patterns of Xylan on Interactions with Cellulose

The present study demonstrates that the change in the degree of xylan acetylation significantly alters the 2-fold screw population that effectively interacts with the (100) hydrophobic cellulose, while such effects are less prominent for the (110) hydrophilic surface. All of the acetylated xylans reveal an ≈10-40% higher 2-fold population on the hydrophobic cellulose due to higher xylan-cellulose contacts. Deviations from periodic acetylation result in much lower 2-fold conformations, despite a comparable number of xylan-cellulose hydrogen bonds and contacts. Thus, it can be hypothesized that a specific and unique set of xylan: cellulose interactions mediate the formation of 2-fold xylan to interact with cellulose, which is also a 2-fold screw. Highly acetylated xylans desorb from cellulose, while low acetylated xylans show dependence on the topology of the cellulose surface. These findings provide additional insights into plant cell wall microstructure dynamics and inform future strategies for efficient biomass deconstruction in biofuel production.