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Multidimensional high-resolution magic-angle-spinning solid-state NMR (SSNMR) spectroscopy has recently been shown to have the unique capability of revealing the molecular structure and dynamics of insoluble macromolecules in intact plant cell walls. This chapter summarizes the 2D and 3D SSNMR techniques used so far to study cell walls and key findings about cellulose interactions with matrix polysaccharides, cellulose microfibril structure, polysaccharide–protein interactions that are responsible for wall loosening, and polysaccharide–water interactions in the hydrated primary walls. These results provide detailed molecular insights into the structure of near-native plant cell walls, and revise the conventional tethered-network model by suggesting a single-network model for the primary cell wall, which has found increasing support from recent biochemical and biomechanical data.

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