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

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.

Design of a versatile and selective electrochemical sensor based on dummy molecularly imprinted PEDOT/laser-induced graphene for nitroaromatic explosives detection.

Considering the formidable explosive power and human carcinogenicity of nitroaromatic explosives, the implementation of an accurate and sensitive detection technology is imperative for ensuring public safety and monitoring post-blast environmental contamination. In the present work, a versatile and selective electrochemical sensor based on dummy molecularly imprinted poly (3,4-ethylenedioxythiophene)/laser-induced graphene (MIPEDOT/LIG) was successfully developed and the specific detection of multiple nitroaromatic explosives was realized in the single sensor. The accessible and nontoxic trimesic acid (TMA) and superior 3, 4-ethylenedioxythiophene (EDOT) were selected as the dummy-template and the functional monomer, respectively. The interaction between the functional monomer and the template, and the morphology, electrochemical properties and detection performance of the sensor were comprehensively investigated by ultraviolet-visible spectroscopy, Fourier-transform infrared spectroscopy, scanning electron microscopy, cyclic voltammetry, and differential pulse voltammetry. Benefiting from the alliance of TMA and EDOT, the MIPEDOT/LIG sensor manifested outstanding selectivity and sensitivity for 2,4,6-trinitrotolueen (TNT), 2,4,6-trinitrophenol (TNP), 2,4-dinitrotoluene (DNT), 1,3,5-trinitrobenzene (TNB), 2,4-dinitrophenol (DNP), and 1,3-dinitrobenzene (DNB) (representative nitroaromatic explosives) with limits of determination of 1.95 ppb, 3.06 ppb, 2.49 ppb, 1.67 ppb, 1.94 ppb, and 4.56 ppb, respectively. The sensor also exhibited extraordinary reliability and convenience for environmental sample detection. Therefore, a perfect combination of versatility and selectivity in the MIPEDOT/LIG sensor was achieved. The findings of this work provide a new direction for the development of multi-target electrochemical sensors using a versatile dummy template for explosives detection.