Understanding the Structure and Assembly of Dense, Solvent-Free Cellulose Derivatives through Atomistic Force-Field Comparisons
Year: 2026
Type: preprint
Abstract: Cellulose and its derivatives are promising sustainable alternatives to conventional synthetic polymers due to their abundance, renewability, and biodegradability. However, how molecular-scale interactions–particularly hydrogen bonding (H-bond) and van der Waals (vdW) interactionsand the conformational behavior of cellulose chains govern their hierarchical organization remains poorly understood. Establishing these relationships is essential for the rational design and predictive modeling of cellulose-based materials. In this work, we investigate the structural organization and self-assembly of bulk cellulose and its derivatives using large-scale molecular dynamics simulations. We study systems of up to one million atoms with cumulative trajectories exceeding 25 µs, covering amorphous, semi-crystalline, and a preassembled-crystalline-cellulose test case, as well as amorphous cellulose acetate and carboxymethyl cellulose. To elucidate the cellulose assembly, we compare three widely used all-atom force-fields–GLYCAM06, OPLS-AA, and GROMOS-54a7–and analyze conformations, backbone-twist persistence, H-bond dynamics, chain packing, and crystallization. By linking microscopic structural and dynamical features to macroscopic polymer organization, this work provides molecular insight into cellulose self-assembly and systematically benchmark the ability of the three force-fields to reproduce key structural properties of carbohydrate-based materials.
Source: ChemRxiv
Language: English
Subfield: Biomaterials
Field: Materials Science
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W7212295512