The Maritime Silk Road was the major trade route between eastern and western civilizations in the Middle Ages. However, hardly any silk products have been found along the transoceanic trade route. Thus, the extrasensitive detection of silk relic traces has tremendous importance in research regarding the Maritime Silk Road. In this study, an electrochemical immunosensor based on a tailored monoclonal antibody and gold nanoparticles using the layer-by-layer self-assembly method was devised. The fabricated immunosensor demonstrated preeminent performance in the analysis of silk fibroin, with a linear detection range of 0.01−100 ng mL −1 and a detection limit of 3.8 pg mL −1 . In particular, the performance of the immunosensor was excellent in the analysis of ancient silk samples, especially in the qualitative and quantitative detection of soil samples extracted from Nanhai No. 1 shipwreck archeological sites. The proposed electrochemical immunosensor proves the existence of silk products on the Maritime Silk Road and demonstrates enormous potential for studying the formation and development of the ancient transoceanic trading route.

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