Nanochannel array device operating through Prussian blue nanoparticles for sensitive label-free immunodetection of a cancer biomarker

Abstract

A novel nanochannel array (NC) device that operates through Prussian blue nanoparticles (PBNPs) as redox indicator for sensitive label free immunodetection of a cancer biomarker is presented. Stable and narrow-sized (around 4 nm) PBNPs, protected by polyvinylpyrrolidone, exhibited a well-defined and reproducible redox behavior and were successfully applied for the voltammetric evaluation of the nanochannels (20 nm pore sized) blockage due to the immunocomplex formation. The bigger size of the PBNPs compared with ionic indicators such as the [Fe(CN)6]4−/3− system leads to an increase in the steric effects hindering their diffusion toward the signaling electrode which in turn is transduced to an improvement of the detection limit from 200 µg mL−1 to 34 pg human IgG mL−1. This novel and effective PBNPs-NC technology for the detection of small proteins captured inside the nanochannels is successfully applied for the quantification of a cancer biomarker (parathyroid hormone-related protein, PTHrP) in a real clinical scenario such as cell culture medium. The achieved label-free detection of PTHrP at levels of 50 ng mL−1 is with great interest to study relevant functions that this protein exerts in normal tissues and cancer.