A colorimetric and SERS dual-readout sensor for sensitive detection of tyrosinase activity based on 4-mercaptophenyl boronic acid modified AuNPs

Tyrosinase (TYR) is as a well-known polyphenol oxidase and important biomarker of melanocytic lesions. Thus, developing powerful methods to determine TYR activity is of great value in the early diagnosis of skin disease. Direct surface-enhanced Raman scattering (SERS) detection of biomolecules is usually affected by non-specific interference and complicate structure of the analytes. It is a challenge to develop Raman-active molecules with specific recognition to analytes in complex media. Here, we report a novel colorimetric and surface-enhanced Raman scattering (SERS) dual-readout assay for the determination of TYR using commercially available and economical 4-mercaptophenyl boronic acid (4-MPBA) as a Raman-active and recognition molecule. 4-MPBA provides a unique interactive boronic acid group to the diol group of TYR substrate and exhibits good SERS signal. Also, the introduction of magnetic beads could promptly improve the anti-interference ability of dual-mode sensor. The TYR-incubated tyramine-modified magnetic beads could obviously change the concentration of 4-MPBA-AuNPs in the presence of O2 and ascorbic acid, where the ultraviolet visible (UV-vis) absorption and SERS intensity were directly related to the concentration of TYR added. The dual-mode sensor had a rapid response to TYR within 1 min under optimized conditions and had high selectivity for TYR with a limit of detection at 0.001 U/mL. In addition, the dual-mode strategy showed promising prospects in the determination of TYR activity in serum samples and could be used to screen TYR inhibitors.