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

Olha Demkiv,Mykhailo Gonchar,Galina Gayda,Nataliya Stasyuk

doi:10.3390/catal11121510

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.

Highlights

The detection of biologically active toxic pharmaceutical compounds and their metabolites in surface waters cause great concern for humanity [1,2]
Several chemicals have already been found in raw urban wastewaters at concentrations up to μg·L−1, which are dangerous for health [3]
We report the synthesis of NLacs, their characterization, and their application in the development of amperometric sensors for the direct measurement of AD

Summary

Introduction

The detection of biologically active toxic pharmaceutical compounds and their metabolites in surface waters cause great concern for humanity [1,2]. Several chemicals have already been found in raw urban wastewaters at concentrations up to μg·L−1 , which are dangerous for health [3]. Pharmaceutical manufacturing has become a significant source of harmful chemicals as pollutants of the environment. Households and hospitals make a significant contribution to the excretion of pharmaceuticals into urban wastewaters [4]. Among the chemicals detected in terrestrial and aquatic environments, some antiinflammatories and analgesics, catecholamines and psychiatric drugs are the most dangerous for humans and wildlife [5]. As the influence of these contaminants in the environment is clearly recognized, early detection and quantification of the mentioned pharmaceuticals is necessary, for controlling the quality of water, especially drinking water, and for the diagnosis and monitoring of various health conditions [4,6]

Methods

Results

Conclusion