Recrystallization and size distribution of dislocated segments in cellulose microfibrils—a molecular dynamics perspective

Abstract: The arrangement of cellulose molecules in natural environment on the nanoscale is still not fully resolved, with longitudinal disorder in cellulose microfibrils (CMF) being one relevant question. Particularly the length of the dislocated cellulose segments in CMFs is still under debate. Using molecular dynamics simulations, we are first investigating the phenomenon of pseudo-recrystallization of dislocated cellulose regions after cleavage of CMFs. Based on our simulations we propose that 3–4 glucose residues bordering to each side of a cellulose nanocrystal are actually reorganizing to a quasi-crystalline state, which are corroborating recent analytical investigations reporting an increase in crystallinity after acid vapor hydrolysis of CMFs. Combining our molecular dynamics simulation results with these analytical data we can estimate the length of the dislocated cellulose segments in CMFs. We propose that, for the investigated sources of biomass (cotton and ramie), the dislocation lengths are between 3.1–5.8 nm equaling to 6–11 glucose residues in the cellulose crystallites. Graphic abstract: [Figure not available: see fulltext.]