Selenium-Decorated Graphene for Peroxynitrite Detection

Peroxynitrite (PON, ONOO−) is a member of the reactive oxygen-nitrogen species family. PON is generated in vivo by the diffusion-limited reaction (~2×1010 M−1S−1) of nitric oxide (·NO) and superoxide (O2·−) radicals. Elevated peroxynitrite levels are associated with several human pathologies, such as arthritis, inflammation, and carcinogenesis, as well as ageing-associated diseases. Thus, the precise detection of this species in biological systems is crucial, not only to understand the genesis and causes of ailments at the tissue/cellular level, but also to suggest and design potential therapies. The essential trace element selenium (Se) is the catalytic cofactor of important endogenous antioxidative systems of the human body. In the past decade, selenium attracted the attention of many research groups for the understanding of fundamental biological functions and biomimetic applications. Selenium is found in several human proteins (selenoproteins), many of them involved in anti-oxidant defense systems. Therefore, selenium plays a key role in redox regulation as a modulator of reactive oxygen species (ROS). Recently, a number of novel synthetic organoselenium compounds has been prepared and used as antioxidants in medicinal chemistry such as ebselen. In this work, we prepare and investigate interfaces based on the electrochemical deposition of selenium nanoparticles. We prepared surfaces of electrodeposited elemental selenium (Se) and selenium-decorated graphene-based nanostructures on glassy carbon electrodes and carbon fiber microelectrodes. We have used several physicochemical methods to characterize these PON-sensitive interfaces, including Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Analysis (EDX), X-ray Photoelectron Spectroscopy (XPS), Raman spectroscopy, and UV-vis on ITO transparent electrodes. We tested these interfaces for electrocatalytic sensing of peroxynitrite. We found that selenium-modified graphene platform is sensitive to peroxynitrite in solution, and it provides a viable interface for electrochemical sensing of this analyte. We observed that there is a synergistic effect of the presence of graphene as a substrate for selenium nanoparticles in the electrocatalytic detection of PON. In this paper, we will present our findings using this new PON-sensitive interface. We will compare and contrast the performance of the various modified carbon electrodes in terms of PON sensitivity using cyclic voltammetry and dose-response chronoamperometry