ABSTRACT
Layer-by-layer peeling of surface molecules of native cellulose microfibrils was performed using a repeated sequential process of 2,2,6,6-tetramethylpiperidine-1-oxyl radical-mediated oxidation followed by hot alkali extraction. Both highly crystalline algal and tunicate celluloses and low-crystalline cotton and wood celluloses were investigated. Initially, the C6-hydroxy groups of the outermost surface molecules of each algal cellulose microfibril facing the exterior had the gauche-gauche (gg) conformation, whereas those facing the interior had the gauche-trans (gt) conformation. All the other C6-hydroxy groups of the cellulose molecules inside the microfibrils contributing to crystalline cellulose I had the trans-gauche (tg) conformation. After surface peeling, the originally second-layer molecules from the microfibril surface became the outermost surface molecules, and the original tg conformation changed to gg and gt conformations. The plant cellulose microfibrils likely had disordered structures for both the outermost surface and second-layer molecules, as demonstrated using the same layer-by-layer peeling technique.
Subject(s)
Cell Wall/chemistry , Cellulose/chemistry , Microfibrils/chemistry , Wood/chemistry , Animals , Cell Wall/enzymology , Cyclic N-Oxides/chemistry , Molecular Conformation , Oxidation-Reduction , Urochordata/enzymology , Wood/enzymologyABSTRACT
We report that the intrinsic viscosity [η] of nanocellulose dispersions can be solely expressed as a function of the aspect ratio p of the nanocellulose. Both short rod-like nanocrystalline and long spaghetti-like nanofibrillated celluloses were prepared as dispersions in water. The influence of the flexibility and dimensions of the nanocelluloses on the flow properties of their dispersions was investigated by experimental and theoretical approaches using seven nanocellulose samples with different widths (2.6-14.4 nm) and aspect ratios (23-376). As the aspect ratio of a nanocellulose increases, it becomes more flexible, and its dispersion has higher viscosity. Irrespective of the flexibility and dimensions of these nanocelluloses, the relationship between [η] and p was ρ[η] = 0.15 × p(1.9), where ρ is the density of the nanocellulose.