Mini-review: what nuclear magnetic resonance can tell us about protective tissues.

The epidermis and periderm protect plants from water and solute loss, pathogen invasion, and UV radiation. The cell walls of these protective tissues deposit the insoluble lipid biopolyesters cutin and suberin, respectively. These biopolymers interact in turn with polysaccharides, waxes and aromatic compounds to create complex assemblies that are not yet well defined at the molecular level. Non-destructive approaches must be tailored to the insoluble and noncrystalline character of these assemblies to establish the polymer and inter-component interactions needed to create functional barriers and structural supports. In the present mini-review, we illustrate the contribution of solid-state NMR methodology to compare the architecture of intact fruit cuticular polymers in wild-type and single-gene mutant tomatoes. We also show the potential of NMR-based metabolomics to identify the soluble metabolites that contribute to barrier formation in different varieties of potato tubers. Finally, we outline the challenges of these spectroscopic approaches, which include limited spectral resolution in solid state, differential swelling capabilities in solution, and incomplete dissolution in ionic liquids. Given the many genetically modified plants with altered suberin and cutin polymers that are now available, NMR nonetheless offers a promising tool to gain molecular insight into the complexity of these protective materials.