Programmable Construction of Asymmetric Polymeric Semiconductor Nanorobots for Active Antibacterial and Synergistic Therapy.

Light-driven micro/nanorobots require semiconductor materials with efficient light harvesting and well-defined structural asymmetry to achieve high-performance propulsion. However, most reported systems rely on inorganic semiconductors with rigid band structures and limited stability, while polymeric semiconductors have been restricted by the lack of controllable asymmetric architectures. Here, we report a kinetically programmed one-pot strategy for constructing asymmetric polymeric semiconductor nanorobots with tunable island architectures. By regulating interfacial free energy and competitive nucleation kinetics, mesoporous aminophenol-formaldehyde resin/silica Janus nanoparticles with single-, dual-, and multi-island configurations are precisely synthesized. The resulting asymmetric nanostructures support synergistic light- and fuel-driven self-diffusiophoretic propulsion, allowing programmable motion behaviors. Benefiting from the autonomous motion and photocatalytic activity, the polymeric semiconductor nanorobots exhibit enhanced interaction with bacteria, deep biofilm penetration, and efficient diffusion of reactive oxygen species. This work establishes a general strategy for asymmetric polymeric semiconductor construction and highlights its potential in active antimicrobial and wound-healing nanomedicine.