Using solid-state NMR to understand the structure of plant cellulose

Abstract The structure of plant cellulose microfibrils remains elusive, despite the abundance of cellulose and its utility in industry. Using 2D solid-state NMR of 13 C labelled never-dried plants, six major glucose environments are resolved which are common to the cellulose of softwood, hardwood and grasses. These environments are maintained in isolated holo-cellulose nanofibrils, allowing more detailed microfibril characterisation. We show there are only two glucose environments that reside within the microfibril interior. These have the same NMR 13 C chemical shifts as tunicate cellulose Iβ centre and origin chains, with no cellulose Iα being detected. The third major glucose site with a carbon 4 chemical shift near 89 ppm, previously assigned to the crystalline microfibril interior, is now shown to be one of four surface glucose environments. The NMR peak widths of all four surface glucose environments are similar to those of the core indicating that their glucose local order is comparable; there is no significant ‘amorphous’ cellulose in the microfibrils. Consequently, the ratio of the carbon 4 peaks at ∼89 and ∼84 ppm, which has often provided a sample cellulose crystallinity index, is not a meaningful measure of crystallinity or the interior to surface ratio. The revised ratio for poplar wood microfibrils is estimated to be 1:2, which is consistent with a cellulose Iβ 18-chain microfibril having 6 core and 12 surface chains, although other microfibril sizes are possible. These advances change substantially both the interpretation of solid-state NMR studies of cellulose and the understanding of cellulose microfibril structure and crystallinity.