Dynamic hydrogels with thermosensitive
cross-links are highly promising
platforms for “on-demand” drug delivery
systems. However, there is a problem with triggering a response in
their whole volume, which reduces their efficiency. To achieve better
thermoresponsiveness, a graphene oxide-filled composite hydrogel based
on boronic ester cross-links, composed of hyperbranched polyglycidol,
HbPGL, and poly(acrylamide-ran-2-acrylamidephenylboronic acid), poly(AM-ran-2-AAPBA),
has been constructed. The homogeneous embedment of graphene oxide
(GO) in the network assured near-infrared (NIR)-photothermal response
in its bulk due to the rapid light-to-heat conversion. The rate and
amplitude of materials response increase with graphene oxide concentration.
The temperature of the hydrogel containing graphene oxide at a concentration
of 13.2 mg/mL increased from 36.6 to 41 °C in 29 s upon NIR irradiation.
The network diffusivity and the extent of its change with temperature
can be regulated by the length of the applied boronic acid-based cross-linking
agent. The hydrogel constructed on the shorter copolymer (M
n = 23 000 g/mol) displayed a significant
increase in diffusivity with temperature. A diffusion ordered NMR
study revealed that the diffusion coefficient determined for niacin,
a model drug encapsulated in the hydrogel, increased from 6.09 ×
10–10 at 25 °C to 1.28 × 10–9 m2/s at 41 °C. In the case of the hydrogel constructed
on the longer acrylamide copolymer (M
n = 43 000 g/mol), in which physical entanglements stabilize
the network, the change of encapsulated niacin diffusion coefficient
was significantly smaller, i.e., from 3.83 × 10–10 at 25 °C to 6.63 × 10–10 m2/s at 41 °C. The possibility of on-demand NIR-regulated diffusivity
of the reported boronic ester-based hydrogels makes them promising
candidates for controlled drug delivery platforms.