Molecularly imprinted electrochemical sensor for the ultrasensitive detection of cytochrome c

Cytochrome c (Cyt c) is an important biomarker for the early stage of apoptosis that plays a role in the diagnosis and therapy of several diseases including cancer. Here, an electrochemical sensor based on molecularly imprinted polymer (MIP) for the ultrasensitive detection of Cyt c is studied. It is prepared by electropolymerization of o-phenylenediamine in the presence of Cyt c as template, followed by solvent extraction, resulting in the formation of Cyt c recognition sites. The MIP is characterised by cyclic voltammetry and differential pulse voltammetry, using ferrocenecarboxylic acid as redox probe. Voltammetric data indicates that the MIP-sensor behaves as an electrode with partially blocked surface. The partition isotherm obtained fits the Langmuir model, indicating a high affinity for Cyt c, with an association constant Ka = 5 × 10^11 M^−1. DPV measurements allow to achieve extremely high analytical sensitivity and low detection limit, in the femtomolar range, with negligible unspecific adsorption. Satisfactory analytical recovery tests performed in the presence of possible interfering proteins and in diluted human serum confirmed the selectivity of the MIP-sensor as well as its potential applicability for real samples analysis.