In situ-engineered NU-1000@graphene with kinetics-efficiency dual-boosted ECL for ultrasensitive detection of PD-L1+ extracellular vesicles in NSCLC

In situ -engineered NU-1000@Gra gives 2.20-fold ECL enhancement via dual paths, surmounting single-component trade-off. • First Zr-MOF/graphene synergistically boosts ECL, lifting quantum yield from 11.89% to 15.69% via excited-state optimization. • TDN strategy enhances stability and anti-interference, enabling PD-L1 + tEV detection with LOD 899.35 particles/mL. • NGTA platform detects NSCLC with 100% sensitivity, 90.91% accuracy, 32.09-fold lower LOD than ELISA for tEV biopsy. Tumor-derived PD-L1 + extracellular vesicles (PD-L1 + tEVs) represent valuable liquid-biopsy biomarkers for non-small-cell lung cancer, whereas their reliable quantification is largely restricted by low abundance and complex matrix interference. Herein, we fabricated an in-situ engineered NU-1000@Graphene (Gra) nanohybrid as a kinetics-efficiency dual-boosted electrochemiluminescence (ECL) emitter to build the N U-1000@ G ra t etrahedral a ptasensor (NGTA). Benefiting from intimate interfacial coupling, Gra acted as a bifunctional accelerator in the NU-1000/S 2 O 8 2− system, accelerating interfacial electron transfer and sulfate radical production to realize a 1.58-fold improvement in ECL kinetics and a 1.39-fold enhancement in luminescence efficiency. Assisted by the tetrahedral DNA nanostructure scaffold that suppressed non-specific adsorption, the NGTA achieved an ultralow detection limit of 899.35 particles/mL for PD-L1 + tEVs. Preliminary clinical results demonstrated its diagnostic potential. This work underscores the significance of metal-organic framework (MOF)-Gra interfacial engineering for synergistic ECL amplification, providing a rational material design paradigm for high-performance liquid-biopsy biosensors.