Lignin hygroexpansion in compression and opposite wood - a molecular dynamics study

Abstract Softwood branches develop compression wood (CW) in the lower parts of the branch, while opposite wood (OW) develops on the upper. These wood types differ in structure at several length scales, among others in the chemical composition of their lignin matrix. While OW mostly contains guaiacyl (G) units, CW is known to contain a substantial fraction of 4-hydroxyphenyl (H) lignin. In this study, the impact this difference has on lignin hygroexpansion and interaction with water is studied by the means of atomistic models and molecular dynamics computer simulations of lignin systems at different levels of hydration. It was found that, despite the minor difference in chemical composition, there are differences in swelling, structure and water dynamics. CW lignin is found to have a higher uniaxial swelling coefficient, since the phase separation between lignin and water is more pronounced. This behavior is linked to structural differences, where intermolecular $${\pi -\pi }$$ <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:mrow> <mml:mi>π</mml:mi> <mml:mo>-</mml:mo> <mml:mi>π</mml:mi> </mml:mrow> </mml:math> stacking is more common in CW lignin and hydrogen bonding to water more pronounced in OW lignin. These findings are of interest for understanding the role of lignin in CW, and general understanding of moisture interaction with lignin inside wood cell walls.