Severe bone defects pose a formidable clinical challenge in orthopedics, urgently demanding the development of advanced biomaterials to restore structural and functional integrity. While current regenerative materials, such as collagen-containing products, demonstrate a certain degree of biocompatibility, they are still hampered by limitations that include poor mechanical performance, restricted barrier effects, and arduous preparation methods. Here, we report a rapid-curing methodology to engineer recombinant resilin bioshield with tunable modulus, superior bioactivity, and rapid assembly kinetics. The resilin bioshield is rapidly formed within minutes via a tyrosine-mediated photo-crosslinking strategy, achieving spatially programmable assembly. Enzymatic integration of alkaline phosphatase into the resilin matrix drives in situ mineralization, yielding densely packed hydroxyapatite (HAP) nanocrystals. Remarkably, this process enables controlled modulus tuning of the bioshield across three orders of magnitude, achieving an exceptional maximum modulus of 145 MPa while retaining excellent flexibility, thus surpassing conventional guided bone regeneration materials. Beyond its mechanical superiority, the mineralized resilin bioshield not only directs cellular behavior by enhancing adhesion and spreading but also robustly drives the osteogenic differentiation of mesenchymal stem cells, thereby accelerating functional bone regeneration. As a result, our work provides an alternative approach for creating high-performance barrier membranes for guided bone regeneration.

Defects in acceptor-doped perovskite piezoelectric materials have a significant impact on their electrical properties. Herein, the defect mediated evolution of piezoelectric and ferroelectric properties of Fe-doped (Pb,Sr)(Zr,Ti)O₃ (PSZT–Fe) piezoceramics with different treatments, including quenching, aging, de-aging, and poling, was investigated systematically. Oxygen vacancies with a cubic symmetry are preserved in the quenched PSZT–Fe ceramics, rendering them robust ferroelectric behaviors. In the aged PSZT–Fe polycrystals, defect dipole between Fe dopant and oxygen vacancy has the same orientation with spontaneous polarization P_S, which enables the reversible domain switching and hence leads to the emergence of pinched polarization hysteresis and recoverable strain effect. And the defect dipoles can be gradually disrupted by bipolar electric field cycling, once again endowing the aged materials with representative ferroelectric properties. For the poled PSZT–Fe polycrystals, the defect dipoles are reoriented to be parallel to the applied poling field, and an internal bias field aligning along the same direction emerges simultaneously, being responsible for asymmetric hysteresis loops.