The biomolecular interaction of ligand-presenting switchable
microgels
is studied with respect to the polymer type, composition, and structure
of the microgels. Monodisperse microgels are prepared through precipitation
polymerization of N-isopropylacrylamide (PNIPAM microgels)
or oligo(ethylene glycol methacrylamide)s (POEGMA microgels) in the
presence of crosslinkers or in their absence (self-crosslinked). Functionalization
with mannose or biotin as model ligands and affinity measurements
upon heating/cooling are conducted to obtain mechanistic insights
into how the microgel phase transition affects the specific interactions.
In particular, we are interested in adjusting the crosslinking, swelling
degree, and ligand density of mannose-functionalized microgels to
reversibly catch and release mannose binding Escherichia
coli by setting the temperature below or above the
microgels’ volume phase transition temperature (VPTT). The
increased mannose density for collapsed microgels above the VPTT results
in stronger E. coli binding. Detachment
of E. coli by reswelling the microgels
below the VPTT is achieved only for self-crosslinked microgels showing
a stronger decrease in ligand density compared to microgels with dedicated
crosslinkers. Owing to a reduced mannose density in the shell of POEGMA
microgels, their E. coli binding was
lower compared to PNIPAM microgels, as supported by ultraresolution
microscopy. Importantly, an inverse temperature-controlled binding
of microgels decorated with hydrophilic mannose and hydrophobic biotin
ligands is observed. This indicates that hydrophobic ligands are inaccessible
in the collapsed hydrophobic network above the VPTT, whereas hydrophilic
mannose units are then enriched at the microgel–water interface
and thus are more accessible.