Solid-state nmr and dnp investigations of carbohydrates and cell-wall biomaterials

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© 2020 John Wiley & Sons, Ltd. The cell walls in plants and microbes serve as a central source for biorenewable energy and biomaterials, as well as the target for novel antibiotics and antifungals. They are biocomposites abundant in complex carbohydrates, a class of biologically important but underinvestigated molecules. Solid-state nuclear magnetic resonance (ssNMR) of carbohydrate materials and cell walls has made significant progress over the past 10 years. This article summarizes the recent ssNMR studies that have elucidated the polymorphic structure and heterogeneous dynamics of polysaccharides and other biomolecules, such as proteins, lignin, and pigment, in the intact cell walls or biofilms of 11 species across plants, fungi, bacteria, and algae. We also highlight the assistance of magic-angle spinning dynamic nuclear polarization (MAS-DNP) in the enhanced detection of the interaction interface involving lowly populated biopolymers and summarize the recent applications of natural-abundance MAS-DNP in cell-wall research, which could substantially broaden the scope of biomolecular NMR by skipping isotope labeling.

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