Modeling the cholesteric pitch of apolar cellulose nanocrystal suspensions using a chiral hard-bundle model.

Autor: Chiappini M; Soft Condensed Matter, Debye Institute for Nanomaterials Sciences, Utrecht University, Princetonplein 5, 3584 CC Utrecht, The Netherlands., Dussi S; Physical Chemistry and Soft Matter, Wageningen University, Stippeneng 4, 6708 WE Wageningen, The Netherlands., Frka-Petesic B; Melville Laboratory for Polymer Synthesis, Yusuf Hamied Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom., Vignolini S; Melville Laboratory for Polymer Synthesis, Yusuf Hamied Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom., Dijkstra M; Soft Condensed Matter, Debye Institute for Nanomaterials Sciences, Utrecht University, Princetonplein 5, 3584 CC Utrecht, The Netherlands.
Jazyk: angličtina
Zdroj: The Journal of chemical physics [J Chem Phys] 2022 Jan 07; Vol. 156 (1), pp. 014904.
DOI: 10.1063/5.0076123
Abstrakt: Cellulose nanocrystals (CNCs) are naturally sourced elongated nanocolloids that form cholesteric phases in water and apolar solvents. It is well accepted that CNCs are made of bundles of crystalline microfibrils clustered side-by-side, and there is growing evidence that each individual microfibril is twisted. Yet, the origin of the chiral interactions between CNCs remains unclear. In this work, CNCs are described with a simple model of chiral hard splinters, enabling the prediction of the pitch using density functional theory and Monte Carlo simulations. The predicted pitch P compares well with experimental observations in cotton-based CNC dispersions in apolar solvents using surfactants but also with qualitative trends caused by fractionation or tip sonication in aqueous suspensions. These results suggest that the bundle shape induces an entropy-driven chiral interaction between CNCs, which is the missing link in explaining how chirality is transferred from the molecular scale of cellulose chains to the cholesteric order.
Databáze: MEDLINE