The effect of shape, polydispersity, charge, and fraction of crystallite bundles on the cholesteric pitch of cellulose nanocrystal suspensions.

Using Onsager-Straley's second-virial theory, we investigate the cholesteric pitch of cellulose nanocrystal (CNC) suspensions. We model the CNCs as hard chiral bundles of microfibrils and examine the effect of the shape of these chiral bundles, characterized by aspect ratio and chirality, on the cholesteric pitch. Additionally, we explore the impact of length polydispersity and surface charge on the cholesteric phase of CNCs. Furthermore, we consider binary mixtures of twisted bundles and achiral primary crystallites to provide a more realistic representation of CNC suspensions. Our findings reveal that the degree of bundle twisting significantly affects the helical twisting of the cholesteric phase. We also observe that the average particle length and length polydispersity have substantial effects on strongly twisted bundles but minimal effects on weakly twisted ones. Finally, our study indicates that as the range of electrostatic interactions increases, the transfer of chirality from the microscopic to macroscopic length scales becomes masked, resulting in an increase in the cholesteric pitch. In the case of binary mixtures, the bundles act as chiral dopants, and an increasing fraction of bundles progressively enhances the helical twisting of the cholesteric phase.