A novel electrochemical sensor based on process-formed laccase-like catalyst to degrade polyhydroquinone for tumor marker

Abstract

Methods to improve the sensitivity of electrochemical sensors based on catalytic reactions generally require adscititious or pre-modified catalysts, which make the sensitive detection of sensors extremely challenging. This is because the activity of the catalyst is susceptible to the storage and modification process, such as aggregation during storage or loss of active sites during multi-step modification, which impairs the performance of the sensor. To solve this thorny issue, a novel electrochemical sensor based on a process-formed laccase-like catalyst was constructed for sensitive detection of tumor markers. Cu²⁺-polydopamine (CuPDA) combined with antibody (Ab₂) were employed as copper-containing immunoprobe, which released Cu(Ⅱ) ions under acidic stimulation. Cu(Ⅱ) ions coordinate with the self-assembly cationic diphenylalanine-glutaraldehyde nanospheres (CDPGA) to form a laccase-like catalyst, which had stronger catalytic activity than laccase. The freshly formed catalyst was immediately used to degrade the polyhydroquinone-reduced graphene oxide (PHQ-rGO) composite, resulting in a significant reduction in the current signal. The PHQ-rGO composite plays dual roles of signal substance and substrate on the sensing interface. The proposed electrochemical sensor demonstrated wide linearity for the determination of a model analyte, human epididymis protein 4 (HE4), from 1 pg mL^-1 to 100 ng mL^-1, and the detection limit was as low as 0.302 pg mL^-1 (S/N = 3), which had good consistency with that of electrochemiluminescence method. This process-formed catalyst approach will have potential reference significance for the construction of other sensors.

Keywords: Cationic diphenylalanine-glutaraldehyde nanospheres; Electrochemical sensor; Human epididymis protein 4; Hydroquinone degradation; Laccase-like catalyst.