Bioinspired molecular recognition via pore confinement and interfacial electric-field regulation in g-C₃N₅@Zn-TCPP...

Ammonia (NH₃) in exhaled breath is a promising biomarker for non-invasive monitoring of metabolic disorders, but achieving selective and sensitive detection under complex breath environments remains challenging. Here, we report a bioinspired g-C₃N₅@Zn-TCPP heterojunction formed through π-π stacking that enables molecular-recognition-driven breath NH₃ sensing. Inspired by the synergistic functions of ammonium transporter (AmtB) and ammonia monooxygenase (AMO), this heterostructure integrates pore-confined molecular enrichment with interfacial electric-field regulation. The intrinsic aperture of Zn-TCPP (∼2.8 Å), closely matching the kinetic diameter of NH₃ (2.6 Å), enables size-selective molecular sieving, while the g-C₃N₅-induced interfacial electric field modulates the electronic environment of Zn²⁺ active sites and strengthens Lewis acid-base interactions with NH₃ molecules. Benefiting from this synergistic molecular recognition mechanism, the optimized 0.08@g-;C₃N₅@Zn-TCPP sensor achieves a remarkable response (R₀/R_g = 223 toward 5 ppm NH₃), a low detection limit of 232 ppb, and excellent durability over 1000 bending cycles at room temperature. Machine-learning-assisted analysis further enables accurate discrimination of NH₃ from interfering gases (R² = 0.91). The sensor also distinguishes breath NH₃ variations between healthy individuals and disease-related samples, highlighting its potential for intelligent non-invasive breath analysis. This work establishes a bioinspired molecular recognition strategy by coupling pore confinement with interfacial electric-field regulation, providing a new paradigm for selective gas sensing and wearable health-monitoring platforms.