We report the use of acid-diffusion to assemble core–shell
supramolecular gel beads with different low-molecular-weight gelators
(LMWGs) in the core and shell. These gel beads grow a shell of dibenzylidenesorbitol-based
DBS-COOH onto a core comprising DBS-CONHNH2 and agarose
that has been loaded with acetic acid. Diffusion of the acid from
the core triggers shell assembly. The presence of DBS-CONHNH2 enables the gel core to be loaded with metal nanoparticles (NPs)
as acyl hydrazide reduces metal salts in situ. The
pH-responsiveness of DBS-COOH allows responsive assembly of the shell
with both temporal and spatial control. By fixing multiple gel beads
in a Petri dish, the cores become linked to one another by the assembled
DBS-COOH gel shella process we describe as diffusion-adhesion
assembly. By controlling the geometry of the beads with respect to
one another, it is possible to pattern the structures, and using a
layer-by-layer approach, 3D objects can be fabricated. If some of
the beads are loaded with basic DBS-carboxylate instead of CH3COOH, they act as a “sink” for diffusing protons,
preventing DBS-COOH shell assembly in the close proximity. Those beads
do not adhere to the remainder of the growing gel object and can be
simply removed once diffusion-assembly is complete, acting as templates,
and enabling the fabrication of 3D “imprinted” multigel
architectures. Preloading the gel beads with AuNPs or AgNPs suspends
these functional units within the cores at precisely defined locations
within a wider gel object. In summary, this approach enables the dynamic
fabrication of shaped and patterned gels with embedded metal NPssuch
objects have potential next-generation applications in areas including
soft nanoelectronics and regenerative medicine.