Histidine-Triggered GO Hybrid Hydrogels for Microfluidic 3D Printing

Graphene oxide (GO) hydrogels have provided tremendous opportunities in designing and fabricating complex constructs for diverse applications, while their 3D printing without photocuring is still a challenging task due to their low viscosity, uncontrollable gelation, and low interfacial tension. Here, we report a histidine-assisted printing strategy to prepare GO hybrid hydrogels through the microfluidic 3D printing technique. We found that the GO additive could significantly hamper the Knoevenagel condensation (KC) reaction between benzaldehyde and cyanoacetate group-functionalized polymers to form a hydrogel, while these GO mixed solutions were rapidly solidified into a hydrogel when histidine was added. This fascinating phenomenon enabled us to prepare low-viscosity GO mixed polymer solutions as printable inks and generate hydrogel microfibers in histidine solutions. The hydrogel fibers could support cell survival and be further constructed into complex 3D structures through microfluidic 3D printing techniques. Moreover, due to the addition of GO, the microfibers exhibited excellent electrical conductivity and could sense the motion changes and convert these stimuli as electrical resistance signals. This strategy adds an option for the design and application of 3D printable aqueous GO inks in many fields.