Stimuli-responsive multilayer hydrogels
have opened new opportunities
to design hierarchically organized networks with properties controlled
at the nanoscale. These multilayer materials integrate structural,
morphological, and compositional versatility provided by alternating
layer-by-layer polymer deposition with the capability for dramatic
and reversible changes in volumes upon environmental triggers, a characteristic
of chemically cross-linked responsive networks. Despite their intriguing
potential, there has been limited knowledge about the structure–property
relationships of multilayer hydrogels, partly because of the challenges
in regulating network structural organization and the limited set
of the instrumental pool to resolve structure and properties at nanometer
spatial resolution. This Feature Article highlights our recent studies
on advancing assembly technologies, fundamentals, and applications
of multilayer hydrogels. The fundamental relationships among synthetic
strategies, chemical compositions, and hydrogel architectures are
discussed, and their impacts on stimuli-induced volume changes, morphology,
and mechanical responses are presented. We present an overview of
our studies on thin multilayer hydrogel coatings, focusing on controlling
and quantifying the degree of layer intermixing, which are crucial
issues in the design of hydrogels with predictable properties. We
also uncover the behavior of stratified “multicompartment”
hydrogels in response to changes in pH and temperature. We summarize
the mechanical responses of free-standing multilayer hydrogels, including
planar thin coatings and films with closed geometries such as hollow
microcapsules and nonhollow hydrogel microparticles with spherical
and nonspherical shapes. Finally, we will showcase potential applications
of pH- and temperature-sensitive multilayer hydrogels in sensing and
drug delivery. The knowledge about multilayer hydrogels can advance
the rational design of polymer networks with predictable and well-tunable
properties, contributing to modern polymer science and broadening
hydrogel applications.