Highly Sensitive Amperometric Sensor Based on Laccase-Mimicking Metal-Based Hybrid Nanozymes for Adrenaline Analysis in Pharmaceuticals

Abstract

Nanozymes are nanomaterials which exhibit artificial enzymatic activities and are considered as alternatives to natural enzymes. They are characterized by good catalytic activity and high stability, as well as ease and low cost of preparation. In this study, the mimetics of laccase or “nanolaccases” (NLacs) were synthesized by a simple method of chemical reduction of transition metal salts. The NLacs were tested for their catalytic activity in solution and on the electrode surface. The most effective NLacs, namely nAuCePt and nPtFe, were found to possess excellent laccase-like activities capable of oxidizing the endocrine hormone adrenaline (AD). These NLacs were characterized in detail and used for the development of amperometric sensors for AD determination. The amperometric sensors containing the best NLacs, as well as a natural fungal laccase, were constructed. The most effective nAuCePt-containing sensor had good specificity in relation to AD and improved analytical characteristics. It possessed a 384-fold higher sensitivity than adrenaline (230,137 A·M−1·m−2), a 64-fold lower limit of detection (0.025 µM), and a broader linear range (0.085–45 µM) in comparison with the sensor based on natural laccase. The constructed nAuCePt-containing sensor was successfully used for AD analysis in pharmaceutical formulation.