In
contrast to synthetic
gels, their biological counterparts such
as cells and tissues have synergistic biphasic components containing
both hydrophilic and lyophilic phases, providing them some special
abilities including adaptive biomechanics and freezing tolerance.
Hydrogels containing both hydrophilic and lyophilic phases, referred
to as organohydrogels (OHGs), are capable of mimicking the biological
systems, and they might have great potential in various applications.
Here, we present a facile strategy to obtain adaptive OHGs with tunable
and programmable mechanics and viscoelasticity. We utilize a hydrophilic
cryogel scaffold as the continuous phase of OHGs, while the pores
of the scaffold act as the reaction loci for the formation of organogel
microinclusions. Thus, we first prepared mechanically robust cryogels
based on silk fibroin (SF) via cryogelation reactions at −18
°C. The cryogels with 94% porosity containing interconnected
μm-sized pores were then immersed in an ethanolic solution of
acrylic acid (AAc), n-octadecyl acrylate (C18A), N,N′-methylenebis(acrylamide), and
a free-radical initiator. Polymerization reactions conducted within
the pores of the cryogels lead to mechanically strong adaptive OHGs
consisting of a SF scaffold containing semi-crystalline poly(AAc-co-C18A) organogel microinclusions. The mechanical strength
of OHGs is much higher than that of their components due to the significant
energy dissipation in the OHG networks. Depending on the amount of
the crystallizable C18A monomer units, the melting temperature T
m and the degree of crystallinity of OHGs could
be varied between 49 and 54 °C and 1.3 and13%, respectively.
The crystallinity created in OHGs provided them switchable mechanics
and viscoelasticity in response to a temperature change between below
and above T
m. All OHGs exhibited shape-memory
function with a shape-recovery ratio of more than 92%. The strategy
developed here to obtain high-strength smart OHGs is suitable for
a wide variety of combinations of hydrophilic scaffolds and organogels.