Modular penetration and controlled release (MP-CR): improving the internal modification of natural hierarchical materials with smart nanoparticles.

The internal modification of natural hierarchical materials can largely improve their inherent properties and afford them new functions. However, conventional methods using small-molecule agents often encounter poor uniformity and low efficiency. By comparing the penetration of small molecules and nanoparticles into hierarchical collagen fibers, we propose a general strategy, namely modular penetration and controlled release (MP-CR), for the internal modification of 3D biomass materials. We demonstrate that nano-sized aluminum-loaded particles can penetrate into collagen networks more effectively and evenly than small-molecule crosslinkers. After the on-demand pH-triggered release of interactive aluminum ions, enhanced internal crosslinking is achieved. Importantly, we elucidate the mechanism in depth and show that the MP-CR strategy can comprehensively improve the overall performance of natural hierarchical materials. The MP-CR strategy represents a significant step forward for the internal modification of hierarchical materials, which will find broad applications in biomedicine, catalysis, water treatment, soft electronics, and energy storage.