Development of a selective electrochemical microsensor based on molecularly imprinted polydopamine/ZIF-67/laser-induced graphene for point-of-care determination of 3-nitrotyrosine

Abstract

3-nitrotyrosine (3-NT) is a biomarker closely associated with the early diagnosis of oxidative stress-related disorders. The development of an accurate, cost-effective, point-of-care 3-NT sensor holds significant importance for self-monitoring and clinical treatment. In this study, a selective, sensitive, and portable molecularly imprinted electrochemical sensor was developed. ZIF-67 with strong adsorption capacity was facilely modified on an electrochemically active laser-induced graphene (LIG) substrate (formed ZIF-67/LIG). Subsequently, biocompatible dopamine was chosen as the functional monomer, and interference-free ʟ-tyrosine was used as the dummy template to create molecularly imprinted polydopamine (MIPDA) on the ZIF-67/LIG, endowing the sensor with selectivity. The morphologies, electrochemical properties, and detection performance of the sensor were comprehensively investigated using scanning electron microscopy, cyclic voltammetry, electrochemical impedance spectroscopy, and differential pulse voltammetry. To achieve the best performance, several parameters were optimized, including the number of polymerization cycles (15), elution time (60 min), incubation time (7 min), and pH of the buffer solution (6). The turnaround time for this sensor is 10 min. Benefiting from the alliance of MIPDA, ZIF-67, and LIG, the sensor exhibited excellent sensitivity with a detection limit of 6.71 nM, and distinguished selectivity against 11 interfering substances. To enable convenient clinical diagnosis, a customized electrochemical microsensor with MIPDA/ZIF-67/LIG was designed, showcasing excellent reliability and convenience in detecting biological samples without pretreatment. The proposed microsensor will not only facilitate clinical diagnosis and improve patient care, but also provide inspiration for the development of other portable and accurate electrochemical biosensors.

Keywords: 3-nitrotyrosine; Electrochemical biosensor; Laser-induced graphene; Molecularly imprinted polydopamine; Oxidative stress; Point-of-care testing.