Noncovalent interactions, which usually feature tunable
strength,
reversibility, and environmental adaptability, have been recognized
as driving forces in a variety of biological and chemical processes,
contributing to the recognition between molecules, the formation of
molecule clusters, and the establishment of complex structures of
macromolecules. The marriage of noncovalent interactions and conventional
covalent polymers offers the systems novel mechanical, physicochemical,
and biological properties, which are highly dependent on the binding
mechanisms of the noncovalent interactions that can be illuminated
via quantification. This review systematically discusses the nanomechanical
characterization of typical noncovalent interactions in polymeric
systems, mainly through direct force measurements at microscopic,
nanoscopic, and molecular levels, which provide quantitative information
(e.g., ranges, strengths, and dynamics) on the binding behaviors.
The fundamental understandings of intermolecular and interfacial interactions
are then correlated to the macroscopic performances of a series of
noncovalently bonded polymers, whose functions (e.g., stimuli-responsiveness,
self-healing capacity, universal adhesiveness) can be customized through
the manipulation of the noncovalent interactions, providing insights
into the rational design of advanced materials with applications in
biomedical, energy, environmental, and other engineering fields.