Water as an Intrinsic Structural Element in Cellulose Fibril Aggregates

[Image: see text] While strong water association with cellulose in plant cell walls and man-made materials is well-established, its molecular scale aspects are not fully understood. The thermodynamic consequences of having water molecules located at the microfibril–microfibril interfaces in cellulose fibril aggregates are therefore analyzed by molecular dynamics simulations. We find that a thin layer of water molecules at those interfaces can be in a state of thermal equilibrium with water surrounding the fibril aggregates because such an arrangement lowers the free energy of the total system. The main reason is enthalpic: water at the microfibril–microfibril interfaces enables the cellulose surface hydroxyls to experience a more favorable electrostatic environment. This enthalpic gain overcomes the entropic penalty from strong immobilization of water molecules. Hence, those particular water molecules stabilize the cellulose fibril aggregates, akin to the role of water in some proteins. Structural and functional hypotheses related to this finding are presented.