Native Structure of the Plant Cell Wall Utilized for Top‐Down Assembly of Aligned Cellulose Nanocrystals into Micrometer‐Sized Nanoporous Particles

Despite their sustainable appeal, biomass components are currently undervalued in nanotechnology because means to control the assembly of bio-based nanoparticles are lagging behind the synthetic counterparts. Here, micrometer-sized particles consisting of aligned cellulose nanocrystals (CNCs) are prepared by crosslinking cellulose in cotton linter fibers that are prehydrolyzed with gaseous HCl, resulting in chemical cleavage necessary for CNC formation but retaining the morphology of the native fibers. That way, the intrinsic alignment of cellulose microfibrils within the fiber cell wall can be retained and utilized for top-down CNC alignment. Subsequent crosslinking with citric acid cements the alignment and preserves it, following the dispersion of CNCs trapped end-to-end, connected, and crosslinked within the colloidally stable micrometer-sized particles. Furthermore, thermoporosimetry and cryogenic transmission electron microscopy (Cryo TEM) shows that the particles possess mainly nanoporous (<2 nm) character in water. The approach challenges the current paradigm of predominantly bottom-up methods for nanoparticle assembly.