Modulating the chiral nanoarchitecture of cellulose nanocrystals through interaction with salts and polymer.

HYPOTHESIS: The conditions to allow self-assembly of cellulose nanocrystal (CNC) suspensions into chiral nematic structures are based on aspect ratio, surface charge density and a balance between repulsive and attractive forces between CNC particles. EXPERIMENTS: Three types of systems were characterized in suspensions and subsequently in their solid dried films: 1) neat water dialyzed CNC, 2) CNC combined with polyethylene glycol(PEG) (CNC/PEG), and 3) CNC with added salt (CNC/Salt). All suspensions were characterized by polarized optical microscope (POM) and small angle X-ray scattering (SAXS), while the resultant dried films were analyzed by reflectance spectrometer, scanning electron microscope (SEM) and SAXS. FINDINGS: The presence of chiral nematic (CN*) structures was not observed in dialyzed aqueous suspensions of CNC during water evaporation. By introducing salts or a non-adsorbing polymer, chirality was apparent in both suspensions and films. The interaxial angle between CNC rods increased when the suspensions of CNC/PEG and CNC/salt were dried to solid films. The angle was found to be dependent on both species of ions and ionic strength, while the inter-particle distance was only related to the salt concentration, as explained in terms of interaction energies. The CNC suspensions/film chirality can be modulated by controlling the colloidal forces.

Grafting Nature-Inspired and Bio-Based Phenolic Esters onto Cellulose Nanocrystals Gives Biomaterials with Photostable Anti-UV Properties.

Invited for this month's cover is the international collaborative work from the Bioresource Processing Research Institute of Australia (BioPRIA)-Monash University and URD Agro-Biotechnologies Industrielles (ABI)-AgroParisTech. The cover image shows how the grafting of Nature-inspired and bio-based phenolic esters on cellulose nanocrystals through click-chemistry provides materials with highly photostable UV-blocking properties. Cover art by David Mendoza. The Full Paper itself is available at 10.1002/cssc.202002017.

Grafting Nature-Inspired and Bio-Based Phenolic Esters onto Cellulose Nanocrystals Gives Biomaterials with Photostable Anti-UV Properties.

New nature-inspired and plant-derived p-hydroxycinnamate esters and p-hydroxycinnamate diesters provide excellent protection against UV radiation when incorporated into a matrix. Herein, an efficient and sustainable pathway is reported to graft these phenolic compounds onto cellulose nanocrystals (CNCs) via click-type copper-catalyzed azide/alkyne cycloaddition (CuAAC) reaction. The successful grafting of the phenolic esters on CNC surface was evidenced by a range of chemical analyses, and the degrees of substitution (DS) of the CNC were found to depend on the structure of the phenolic ester grafted. Moreover, aqueous suspensions of the phenolic ester-grafted CNCs not only strongly absorb in both the UVA and UVB regions, but they also exhibit average to very high photostability. Their wide spectrum UV-absorbing properties and their stability upon exposure to UV are highly influenced by the structure of the phenolic ester, particularly by the extra ester group in p-hydroxycinnamate diesters. These findings demonstrate that cellulose nanocrystals decorated with such plant-derived and nature-inspired phenolic esters are promising sustainable nanomaterials for anti-UV applications.