The cellulose/lignin assembly assessed by molecular modeling. Part 1: adsorption of a threo guaiacyl β-O-4 dimer onto a Iβ cellulose whisker

The assembly of the two major cell wall components, cellulose and lignin, were investigated at the atomistic scale using molecular dynamics simulations. To this end, a molecular model of a cellulose crystal corresponding to the allomorph Iβ and exhibiting different surfaces was considered to mimic the carbohydrate matrix present in native wood cell wall. The lignin model compound considered here is a threo guaiacyl β-O-4 dimer. The dynamical process of adsorption of the lignin dimer onto the different surfaces of the cellulose crystal was examined. The modes of association between the two constituents were analyzed; energies of adsorption of the dimer are calculated favorable and of the same order of magnitude on all sides of the cellulosic model, suggesting that the deposition of lignin precursors onto cellulose fibers is non-specific from an enthalpic point of view. Interestingly, geometrical characteristics and energetical details of the adsorption are surface-dependent. Computed data have underlined the predominant contribution of van der Waals interactions for adsorption onto the (200) face, as well as the major influence of H-bonding interactions in the dynamical process of adsorption onto (110) and (1-10) faces. A large number of adsorption sites have been identified and a noticeable "flat" geometry of adsorption of the lignin dimer has been observed, as a consequence of the stacking interactions between lignin aromatic rings and C–H groups of cellulose. Importantly, these dispersive interactions lead to a preferential parallel orientation of lignin aromatic rings relative to the cellulose surface, notably on the (200) face. Such a parallel orientation is consistent with previously reported experimental observations.