Issue 32, 2023

A study across scales to unveil microstructural regimes in the multivalent metal driven self-assembly of cellulose nanocrystals

Abstract

Understanding the behaviour of self-assembled systems, from nanoscale building blocks to bulk materials, is a central theme for the rational design of high-performance materials. Herein, we revealed, at different length scales, how the self-assembly of TEMPO-oxidised cellulose nanocrystals (TOCNCs) into rod fractal gels is directed by the complexation of Fe3+ ions on the surface of colloidal particles. Different specificities in Fe3+ binding on the TOCNC surface and conformational changes of the nanocellulose chain were unveiled by paramagnetic NMR spectroscopy. The macroscopic properties of systems presenting different concentrations of TOCNCs and Fe3+ ions were investigated by rheology and microscopy, demonstrating the tunability of the self-assembly of cellulose nanorods driven by Fe3+ complexation. Near-atomistic coarse-grained molecular dynamics simulations were developed to gain microscopic insight into the behaviour of this colloidal system. We found that the formation of different self-assembled architectures is driven by metal–nanocellulose complexation combined with the attenuation of electrostatic repulsion and water structuration around cellulose, leading to different microstructural regimes, from isolated nanorods to disconnected rod fractal clusters and rod fractal gels. These findings lay the foundation to unlock the full potential of cellulose nanocrystals as sustainable building blocks to develop self-assembled materials with defined structural control for a range of advanced applications.

Graphical abstract: A study across scales to unveil microstructural regimes in the multivalent metal driven self-assembly of cellulose nanocrystals

Supplementary files

Article information

Article type
Paper
Submitted
27 Mar 2023
Accepted
14 Jul 2023
First published
15 Jul 2023
This article is Open Access
Creative Commons BY license

Nanoscale, 2023,15, 13384-13392

A study across scales to unveil microstructural regimes in the multivalent metal driven self-assembly of cellulose nanocrystals

V. Gabrielli, A. Ferrarini and M. Frasconi, Nanoscale, 2023, 15, 13384 DOI: 10.1039/D3NR01418E

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements