Preprint Article Version 2 Preserved in Portico This version is not peer-reviewed

Effect of Acetylation on the Nanofibril Formation of Chitosan

Version 1 : Received: 15 December 2023 / Approved: 18 December 2023 / Online: 18 December 2023 (12:21:29 CET)
Version 2 : Received: 18 December 2023 / Approved: 21 December 2023 / Online: 21 December 2023 (09:29:18 CET)

A peer-reviewed article of this Preprint also exists.

Romany, A.; Payne, G.F.; Shen, J. Effect of Acetylation on the Nanofibril Formation of Chitosan from All-Atom De Novo Self-Assembly Simulations. Molecules 2024, 29, 561. Romany, A.; Payne, G.F.; Shen, J. Effect of Acetylation on the Nanofibril Formation of Chitosan from All-Atom De Novo Self-Assembly Simulations. Molecules 2024, 29, 561.

Abstract

Chitosan is a copolymer of β-glucosamine and N-acetylglucosamine. Recent experiments showed that the degree and pattern of acetylation along the chitosan chain modulate the biological and physicochemical properties; however, the molecular mechanism is unknown. Here we apply the de novo all-atom molecular dynamics (MD) simulations to study chitosan’s self-assembly process at different degrees of acetylation and two different acetylation patterns. The simulations revealed that the 10-mer chitosan chains with 50% acetylation in either block or alternating patterns associate to form ordered nanofibrils comprised of mainly antiparallel chains in agreement with the fiber diffraction data of deacetylated chitosan. Surprisingly, regardless of the acetylation pattern, the same intermolecular hydrogen bonds mediate the fibril sheet formation while water-mediated interactions stabilize the sheet-sheet stacking. Moreover, the acetylated units are involved in forming the strong intermolecular hydrogen bonds (NH–O6 and O6H–O7), which offers an explanation for the experimental observation that increased acetylation lowers chitosan’s solubility. Taken together, the present study provides the atomic-level understanding the role of acetylation plays in modulating chitosan’s physiochemical properties, contributing to the rational design of chitosan-based materials with the ability to tune by its degree and pattern of acetylation. Additionally, we disseminate the improved molecular mechanics parameters that can be applied in MD studies to further understand chitosan-based materials.

Keywords

Chitosan; chitin/chitosan-based systems; chitin

Subject

Chemistry and Materials Science, Biomaterials

Comments (1)

Comment 1
Received: 21 December 2023
Commenter: Jana Shen
Commenter's Conflict of Interests: Author
Comment: There was a mistake in the author list order. This has been corrected.
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