Catalytic Network states Govern Programmable Analytical Functions in a Multifunctional Nanozyme.

Although multifunctional nanozymes enable diverse analytical applications, existing activity-based models cannot adequately explain how a single nanozyme is programmably reconfigured to perform distinct analytical functions under different reaction conditions. Here, we show that programmable analytical functions emerge from catalytic network states rather than isolated enzyme-like activities. Using hyaluronic acid-confined platinum nanozymes (HA-Pt) as a model system, we identify an autonomous chromogenic oxidation (ACO) process that proceeds without externally supplied H2O2. Mechanistic studies reveal that ACO emerges from localized coupling between oxygen activation and substrate oxidation within a confined polymeric microenvironment. Microenvironment disruption destabilizes the catalytic network state, whereas pH continuously redistributes catalytic pathway contributions to drive predictable state transitions. The resulting catalytic network states enable the same nanozyme platform to quantify total antioxidant capacity, uric acid, and hyaluronidase, thereby decoding complementary physiological dimensions of redox homeostasis, purine metabolism, and extracellular matrix remodeling. The strategy was validated using 22 clinical urine samples. This work establishes catalytic network state as a conceptual framework for programmable multifunctional analysis, shifting nanozyme design from activity engineering toward network-state engineering.