Periderms
present in plant barks are essential protective barriers
to water diffusion, mechanical breakdown, and pathogenic invasion.
They consist of densely packed layers of dead cells with cell walls
that are embedded with suberin. Understanding the interplay of molecular
structure, dynamics, and biomechanics in these cell wall-associated
insoluble amorphous polymeric assemblies presents substantial investigative
challenges. We report solid-state NMR coordinated with FT-IR and tensile
strength measurements for periderms from native and wound-healing
potatoes and from potatoes with genetically modified suberins. The
analyses include the intact suberin aromatic–aliphatic polymer
and cell-wall polysaccharides, previously reported soluble depolymerized
transmethylation products, and undegraded residues including suberan.
Wound-healing suberized potato cell walls, which are 2 orders of magnitude
more permeable to water than native periderms, display a strikingly
enhanced hydrophilic–hydrophobic balance, a degradation-resistant
aromatic domain, and flexibility suggestive of an altered supramolecular
organization in the periderm. Suppression of ferulate ester formation
in suberin and associated wax remodels the periderm with more flexible
aliphatic chains and abundant aromatic constituents that can resist
transesterification, attenuates cooperative hydroxyfatty acid motions,
and produces a mechanically compromised and highly water-permeable
periderm.