Schematic model
of a cellulose microfibril with a hydrated matrix
and the changes occurring during the drying and rehydration processes
as interpreted from the experimental solid-state NMR and MD simulations.
(a) Transversal section of a cellulose microfibril with a 2-3-4-4-3-2
habit surrounded by the hemicellulose and lignin matrix. The cellulose
is surrounded by a continuum of water molecules due to the presence
of hydronium ions as the pH of the softwood cell wall is around 5.5.
The water molecules present at the cellulose xylan interface (outlined
in red) are tightly bound and exchange with the bulk of the water
molecules at a slow rate. AGX and GGM molecules close to the cellulose
microfibrils are in a two-fold screw configuration. GGM is divided
into two categories (Man/Glc/Gal = 3:1:1.2 and DSAc = 0.1)
and (Man/Glc/Gal = 4:1:0.3 and DSAc = 0.4).26 Glucuronic acid interacts with the lignin complex
via electrostatic interactions. (b) Upon complete dehydration, a general
collapse of the matrix surrounding the cellulose microfibril is observed.
It leads to shrinkage in size with the lignin moving closer to the
cellulose. The xylose now directly interacts with the cellulose surface
and GGM moves closer to the cellulose surface. While the xylose residues
of xylan are barely affected, the arabinose side chains start interacting
with surrounding molecules in an aspecific manner. (c) Upon rehydration
as the lignin–cellulose and hemicellulose–cellulose
distances increase, the microfibril unit expands with its size becoming
comparable to its original value. However, some changes are observed
between the never-dried state and rehydrated state. The changes are
highlighted with red dashed circles. ① The xylan–cellulose
interface is not rehydrated. ② The rewetting of the cellulose
is almost complete, but some of the cellulose does not revert to a
domain 2 conformation. ③ The GGM regains its original position.
However, a fraction of the GGM molecules becomes more mobile with
a configuration similar to that in solution. ④ The arabinose
side chains become more ordered and some arabinose becomes more mobile.