Shape‐Shifting 3D Protein Microstructures with Programmable Directionality via Quantitative Nanoscale Stiffness Modulation

The ability to shape‐shift in response to a stimulus increases an organism's survivability in nature. Similarly, man‐made dynamic and responsive “smart” microtechnology is crucial for the advancement of human technology. Here, 10–30 μm shape‐changing 3D BSA protein hydrogel microstructures are fabricated with dynamic, quantitative, directional, and angle‐resolved bending via two‐photon photolithography. The controlled directional responsiveness is achieved by spatially controlling the cross‐linking density of BSA at a nanometer lengthscale. Atomic force microscopy measurements of Young's moduli of structures indicate that increasing the laser writing distance at the z‐axis from 100–500 nm decreases the modulus of the structure. Hence, through nanoscale modulation of the laser writing z‐layer distance at the nanoscale, control over the cross‐linking density is possible, allowing for the swelling extent of the microstructures to be quantified and controlled with high precision. This method of segmented moduli is applied within a single microstructure for the design of shape‐shifting microstructures that exhibit stimulus‐induced chirality, as well as for the fabrication of a free‐standing 3D microtrap which is able to open and close in response to a pH change.