Array-Based Rapid Identification of Herbal Medicines via a Bifunctional Color-BiLink Strategy

Ensuring the authenticity and quality of herbal medicines, particularly licorice, a pivotal component in nearly 60% of traditional Chinese medicine formulations, remains a significant global challenge. However, conventional approaches lack the capacity for direct, rapid, and high-throughput differentiation of licorice mixtures and structurally analogous ingredients. Herein, we present a multisite-binding Color-BiLink (CB) strategy for constructing the dual-mode responsive sensor array, formed by a quantifiable-recognized bifunctional m-nitrophenylboronic acid-modified PEI (PEI-QR) and four CB dyes through dynamic, reversible covalent, and electrostatic interactions. The 6-element array enabled the direct (without pretreatment), rapid (<30 s), simultaneous identification 15 licorice samples─across diverse sources, cultivation methods, and manufacturing processes─with 100% accuracy, concurrently detecting six key ingredients. Notably, coupling the array with high-performance liquid chromatography confers enhanced discriminatory power for complex sample profiling and facilitates reliable detection across varying batches, concentrations, and quality grades. Finally, the array achieved an AUROC of 0.984 in distinguishing pass/fail samples, underscoring its robust analytical capability for large-scale rapid identification of herbal medicine quality and demonstrating its significant application potential in clinical and industrial settings.