Molecularly imprinted polymer-decorated signal on-off ratiometric electrochemical sensor for selective and robust dopamine detection

Dopamine (DA), as one of the central neurotransmitters, plays an important role in many physiological and pathological processes. Detection of DA is critical to diagnose and monitor some neurological diseases. In this work, a novel on-off ratiometric electrochemical sensor with molecularly imprinted polymers (MIPs) as target molecule recognizer has been developed for selective and accurate detection of DA. Nanoporous gold (NPG) was electrodeposited on bare gold electrode, which not only benefited the output signal amplification, but also provided enlarged surface for immobilization of polythionine (pThi) and MIPs. Oxidation of DA and pThi served as response signal and internal reference signal, respectively. The oxidation peak currents of DA at +0.12 V increased with increasing the concentration of DA, while the peak currents of pThi at -0.2 V decreased simultaneously. Due to the specificity from MIPs and the built-in correction from pThi, the fabricated sensor showed excellent performance in view of selectivity and reproducibility. It's worth to mention that even if the surface area and morphology of working electrode underwent huge variation deliberately, the assay deviation among these ratiometric sensors was largely reduced around 10 times. The proposed sensor demonstrated a broad dynamic range of 0.3-100 μM, as well as a low detection limit of 0.1 μM (S/N = 3). Moreover, superior anti-interfering ability toward DA detection was obtained despite the presence of interferents at high concentration in artificial cerebrospinal fluid (aCSF). Therefore, this work is expected to provide an alternative pathway for constructing ratiometric electrochemical sensor and offer reliable determination of small molecules with high selectivity and stability.