Conspectus
The concept of colloids encompasses
a wide range of isotropic and
anisotropic particles with diverse sizes, shapes, and functions from
synthetic nanoparticles, nanorods, and nanosheets to functional biological
units. They are addressed in materials science for various functions,
while they are ubiquitous in the biological world for multiple functions.
A large variety of synthetic colloids have been researched due to
their scientific and technological importance; still they characteristically
suffer from finite size distributions, imperfect shapes and interactions,
and not fully engineered functions. This contrasts with biological
colloids that offer precision in their size, shape, and functionality.
Materials science has searched for inspiration from the biological
world to allow structural control by self-assembly and hierarchy and
to identify novel routes for combinations of functions in bio-inspiration.
Herein, we first discuss different approaches for highly defined
structural control of technically relevant synthetic colloids based
on guided assemblies of biological motifs. First, we describe how
polydisperse nanoparticles can be assembled within hollow protein
cages to allow well-defined assemblies and hierarchical packings.
Another approach relies on DNA nanotechnology-based assemblies, where
engineered DNA structures allow programmed assembly. Then we will
discuss synthetic colloids that have either particularly narrow size
dispersity or even atomically precise structures for new assemblies
and potential functions. Such colloids can have well-defined packings
for membranes allowing high modulus. They can be switchable using
light-responsive moieties, and they can initiate packing of larger
assemblies of different geometrical shapes. The emphasis is on atomically
defined nanoclusters that allow well-defined assemblies by supramolecular
interactions, such as directional hydrogen bonding. Finally, we will
discuss stimulus-responsive colloids for new functions, even toward
complex responsive functions inspired by life. Therein, stimulus-responsive
materials inspired by biological learning could allow the next generation
of such materials. Classical conditioning is among the simplest biological
learning concepts, requiring two stimuli and triggerable memory. Therein
we use thermoresponsive hydrogels with plasmonic gold nanoparticles
and a spiropyran photoacid as a model. Heating is the unconditioned
stimulus leading to melting of the thermoresponsive gel, whereas light
(at a specified wavelength) originally leads to reduced pH without
plasmonic or structural changes because of steric gel stabilization.
Under heat-induced gel melting, light results in pH-decrease and chain-like
aggregation of the gold nanoparticles, allowing a new plasmonic response.
Thus, simultaneous heating and light irradiation allow conditioning
for a newly derived stimulus, where the logic diagram is analogous
to Pavlovian conditioning. The shown assemblies demonstrate the different
functionalitie...