Tailoring a novel all-in-one host-guest solid-state electrochemiluminescence platform for selective detection of spermine using cucurbit-[6]-uril modified [Ru(bpy)3]2+ electrode

Abstract

Herein, a novel solid-state electrochemiluminescence (ECL) based on electrochemically incorporated [Ru(bpy)3]2+ on nafion modified glassy carbon electrode ([Ru(bpy)3]2+-Nafion/GCE) followed by chemisorption of cucurbit-[6]-uril (CB-[6]) on Ru(bpy)3]2+-Nafion/GCE (as CB-[6]-[Ru(bpy)3]2+-Nafion/GCE) has been developed for selective sensing of spermine (SPM) which belongs to the class of aliphatic biogenic amines and overexpression of SPM is associated with several cancers, particularly “Prostate Cancer” (PCa). Interestingly, the ECL emission of [Ru(bpy)3]2+ be enhanced significantly in the presence of CB-[6] modified [Ru(bpy)3]2+-Nafion/GCE. This is due to inherent ability of CB- [6] act as a co-reactant accelerator. Upon the addition of SPM, the ECL emission was further enhanced due to electron transfer reaction between SPM and [Ru(bpy)3]3+. Selectivity of the proposed ECL sensor towards SPM arises from the host-guest interaction between the CB-[6] and SPM, follows the anodic co-reactant ECL reaction (oxidative reduction mechanism) by confirmation of electrochemical and spectroscopic results like electron spin resonance (EPR) and ECL spectra. The proposed solid-state ECL sensor platform is selectively detect to SPM for a linear range of 10 nM - 5 mM with detection limit (LoD) of 1.4 nM at physiological pH conditions. In addition, the developed ECL platform of CB-[6]-[Ru(bpy)3]2+-Nafion/GCE has been successfully verified to the sensing of SPM in the urine sample, proving the practicability of the proposed sensor is suitable for clinical analysis.