An electrochemical biosensor based on hemin/G-quadruplex DNAzyme and PdRu/Pt heterostructures as signal amplifier for circulating tumor cells detection

Abstract

Metastasis due to circulating tumor cells (CTCs) shed from the original tumor accounts for the majority of cancer-related death. Efficient CTCs detection is pivotal to the diagnosis of early cancer metastasis. In this work, Platinum nanoparticles (PtNPs) decorated hyperbranched PdRu nanospines (PdRu/Pt) hierarchical structures were firstly synthesized to detect CTCs with the assistance of DNAzyme. Meanwhile, Super P and gold nanoparticles (AuNPs) acted as sensing medium to improve electrical conductivity and immobilization of anti-EpCAM antibody to specifically capture model CTCs. After immune-conjugation of anti-EpCAM-MCF-7-signal probes on the gold electrode, PtNPs, PdRu nanospines (PdRuNSs) and hemin/G-quadruplex co-catalyzed substrate H₂O₂ to realize multiplexed signal amplification, which significantly improves the analytical performance of the electrochemical biosensor. As-proposed biosensor reached a limit of detection (LOD) down to 2 cells mL^-1 and showed a wide detection range of 2 to 10⁶ cells mL^-1. Application of the biosensor to detect MCF-7 cells spiked human blood samples further demonstrated the feasibility for early cancer evaluation in clinic.

Keywords: Circulating tumor cells; Electrochemical biosensor; Hemin/G-quadruplex; PdRu/Pt heterostructures; Super P/gold nanoparticles.