Preserving Native Cellulose–Xylan Architecture Enables Structure–Property Control in Holocellulose Nanofibrils and High-Performance Sustainable Materials
Year: 2026
Type: preprint
Abstract: The hierarchical organization of cellulose microfibrils and their intimate interactions with hemicelluloses such as xylan underpin the exceptional mechanical performance of plant cell walls. However, translating these biological design principles into sustainable nanocellulosic materials remains limited by conventional cellulose nanofibril production routes, which rely on harsh chemical treatments that disrupt the native cellulose–hemicellulose architecture. Here, we present an optimized isolation strategy for holocellulose nanofibrils (hCNFs) that preserves native cellulose structure, xylan substitution and conformation, and cellulose–xylan interactions. Using wild-type Arabidopsis thaliana , a xylan glucuronidation-deficient gux1/2 mutant, and Brassica napus straw as model systems, we systematically elucidate how xylan content and substitution pattern govern nanofibril isolation, interfacial interactions, and macroscopic properties. Two-dimensional 13 C magic-angle spinning NMR demonstrates retention of native cellulose glucosyl environments, the presence of two-fold and three-fold helical xylan conformations, and cellulose-associated two-fold helical xylan. Cryogenic transmission electron microscopy reveals fibril widths of ∼3 nm, consistent with elementary cellulose Iβ microfibrils. We show that xylan glucuronidation regulates colloidal stability, hydration behavior, and interfibrillar cohesion, whereas xylan content controls nanofibrillation efficiency. These multiscale structural features translate directly into moisture sorption, thermal behavior, and mechanical performance. Notably, Brassica napus hCNF films exhibit exceptional strength and extensibility, surpassing many chemically modified CNF systems. This work demonstrates that preserving the native cellulose–hemicellulose architecture enables high-performance, sustainable nanocellulosic materials without chemical reconstruction.
Authors: Parveen Kumar Deralia, Rosalie Cresswell, Yoshihisa Yoshimi, Tomohiro Kuga, Alberto Echevarría-Poza, Phil Howell, Alan Dickson, Marie Joo Le Guen, Edward Wagner, Amadeus C. S. de Alcântara, Carlos Guilherme Tissi Batista, Nadège Follain, Alyssa Miller, Michele Vendruscolo, Stefan J. Hill, Johnny Beaugrand, Munir S. Skaf, Daniel J. Cosgrove, Steven P. Brown, James A. Elliott, Ray Dupree, Paul Dupree
Institutions: University of Cambridge, University of Warwick, The University of Tokyo, National Institute of Agricultural Botany, Bioeconomy Science Institute, Pennsylvania State University, Universidade Estadual de Campinas (UNICAMP), Centre National de la Recherche Scientifique, Polymères, Biopolymères, Surfaces, Université de Rouen Normandie, Institut National des Sciences Appliquées Rouen Normandie, Institut National de Recherche pour l'Agriculture, l'Alimentation et l'Environnement, Biopolymères Interactions Assemblages
Language: English
Subfield: Biomaterials
Field: Materials Science
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W7164383722