Xylan adsorption on cellulose: Preferred alignment and local surface immobilizing effect

Emilia Heinonen; Gunnar Henriksson; Mikael E Lindström; Francisco Vilaplana; Jakob Wohlert

doi:10.1016/j.carbpol.2022.119221

Xylan adsorption on cellulose: Preferred alignment and local surface immobilizing effect

Carbohydr Polym. 2022 Jun 1:285:119221. doi: 10.1016/j.carbpol.2022.119221. Epub 2022 Feb 17.

Authors

Emilia Heinonen¹, Gunnar Henriksson², Mikael E Lindström³, Francisco Vilaplana⁴, Jakob Wohlert⁵

Affiliations

¹ Wallenberg Wood Science Center, KTH Royal Institute of Technology, Teknikringen 56-58, Stockholm 10044, Sweden; Division of Glycoscience, Department of Chemistry, KTH Royal Institute of Technology, AlbaNova University Centre, Roslagstullsbacken 21, Stcokholm 10691, Sweden. Electronic address: sehei@kth.se.
² Wallenberg Wood Science Center, KTH Royal Institute of Technology, Teknikringen 56-58, Stockholm 10044, Sweden; Department of Fibre and Polymer Technology, KTH Royal Institute of Technology, Teknikringen 56-58, Stockholm 10044, Sweden. Electronic address: ghenrik@kth.se.
³ Department of Fibre and Polymer Technology, KTH Royal Institute of Technology, Teknikringen 56-58, Stockholm 10044, Sweden. Electronic address: mil@kth.se.
⁴ Wallenberg Wood Science Center, KTH Royal Institute of Technology, Teknikringen 56-58, Stockholm 10044, Sweden; Division of Glycoscience, Department of Chemistry, KTH Royal Institute of Technology, AlbaNova University Centre, Roslagstullsbacken 21, Stcokholm 10691, Sweden. Electronic address: franvila@kth.se.
⁵ Wallenberg Wood Science Center, KTH Royal Institute of Technology, Teknikringen 56-58, Stockholm 10044, Sweden; Department of Fibre and Polymer Technology, KTH Royal Institute of Technology, Teknikringen 56-58, Stockholm 10044, Sweden. Electronic address: jacke@kth.se.

PMID: 35287851
DOI: 10.1016/j.carbpol.2022.119221

Abstract

Interaction between xylan and cellulose microfibrils is required to maintain the integrity of secondary cell walls. However, the mechanisms governing their assembly and the effects on cellulose surface polymers are not fully clear. Here, molecular dynamics simulations are used to study xylan adsorption onto hydrated cellulose fibrils. Based on multiple spontaneous adsorption simulations it is shown that an antiparallel orientation is thermodynamically preferred over a parallel one, and that adsorption is accompanied by the formation of regular but orientation-dependent hydrogen bond patterns. Furthermore, xylan adsorption restricts the local dynamics of the adjacent glucose residues in the surface layer to a level of the crystalline core, which is manifested as a three-fold increase in their ¹³C NMR T₁ relaxation time. These results suggest that xylan forms a rigid and ordered layer around the cellulose fibril that functions as a transition phase to more flexible and disordered polysaccharide and lignin domains.

Keywords: Adsorption; Cell wall,; Cellulose; Conformation; Molecular dynamics; Xylan.