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Tyrosinase (TYR) expression and activity determine the rate and yield of melanin production. Studies have shown that TYR is a potential biomarker for melanoma and highly sensitive detection of TYR benefits early diagnosis of melanoma-related diseases. In this study, we developed a method that combines surface-enhanced Raman scattering (SERS) and sandwich-type immunity for sensitive detection of TYR, in which 4-mercaptobenzonitrile (4 MB) embedded between the Au core and Au shell (Au4MB @ Au) core-shell structure was employed as a SERS probe for quantitative detection of TYR while the magnetic bead serves as a capture substrate. Our results demonstrated that under magnetic separation, the specific SERS signal obtained is highly correlated with TYR concentrations. Furthermore, the combination of magnetic beads and Au4MB @ Au core-shell structure significantly improved the sensitivity of the sensing platform, resulting in detection limits of 0.45 ng mL−1. More importantly, the detection and analysis of TYR concentration in human serum samples showed good accuracy and an excellent recovery rate. Accuracy of the system was investigated from % recovery of spiked TYR standard solutions and found to be in the range of 90–104%, which further verified the feasibility and reliability of our method applied in a complex environment. We anticipate this SERS-based immunoassay method to be applied to TYR detection in the clinical setting and to be extended to other promising related fields. Image 1 • An interference-free SERS-based immunoassay method has been developed for the first time to measure the levels of TYR. • Au4MB@AuNPs as SERS probes significantly amplified the 4-mercaptobenzonitrile SERS signal. • The limit of detection of our proposed detection method is 0.45 ng mL−1 for TYR. • The detection of TYR concentration in human serum samples showed good accuracy and an excellent recovery rate. [ABSTRACT FROM AUTHOR]

Tryptophan plays an important role in the metabolic pathway and tryptophan metabolism is abnormal in tumor tissues. Therefore, Trp and its metabolites in body fluids can be used as tumor markers for cancer monitoring. However, the traditional tryptophan detection method has many shortcomings, such as low sensitivity, time-consuming and so on, which is difficult to meet the clinical needs. Herein, a rapidly, sensitive and reliable method for indirectly detecting Tryptophan (Trp) in serum was proposed by combining diazo-coupling reaction mechanism with surface-enhanced Raman scattering (SERS). The limit of detection (LOD) of Trp can be as low as 20 nM, which is much lower than existing detection methods. In addition, because of obvious change in color in diazo-coupling reaction, a colorimetric detection was applied for convenient determination of Trp in the concentration ranged from 3 × 10−5 - 10−3 M. Furthermore, with the support of good results by SERS assay, the presented method was successfully carried out for the determination of Trp in serum that came from healthy people and colorectal cancer patients. Comparing the difference of Trp content in serum between the two groups, it was found that tryptophan metabolism disorder exists in colorectal cancer patients, which suggested that the accurate detection of tryptophan content may provide important reference for the pathogenesis, prediction and prevention of colorectal cancer. Image 1 • A sensitive method based on SERS and diazo coupling reaction mechanism was developed to detect trace tryptophan in complex biological samples. • A limit of detection of 20 nM with the range of 5∗10-8 to 10-3 M can be achieved by this method. • To compare the difference of Trp content between healthy people and colorectal cancer patients. • The method was not interfered by other amino acids. [ABSTRACT FROM AUTHOR]