Ultrasensitive “signal-on” sandwich electrochemiluminescence immunosensor based on Pd@Au-L-cysteine enabled multiple-amplification strategy for Apolipoprotein-A1 detection

Abstract

In this work, a “signal on” electrochemiluminescence (ECL) strategy was proposed to detect Apolipoprotein-A1 (Apo-A1), a common tumor biomarker for bladder cancer. The tris(2,2′-bipyridyl)-ruthenium(II) [Ru(bpy)32+] was used as luminophor captured by three-dimensional (3D) zinc oxalate metal–organic frameworks (MOFs), which constructed as the ECL nanoprobe (Ru-MOF) for detecting Apo-A1. Meanwhile, L-cysteine (L-Cys) as the co-reactant was connected to the Pd@Au core–shell nanostructure through Au-S bond, which was directly modified on the glassy carbon electrode (GCE) to significantly reduce the electron transfer distance between the luminophor and co-reactant. The ECL intensity was “signal on” when the ECL probe of Ru-MOF was linked to the electrode by the immunoreaction of antigen–antibody. Based on these principles, the quantitative relationship between the concentration of Apo-A1 and the ECL intensity was obtained in the range of 1.00 fg·mL−1 to 1.00 ng·mL−1 with a linear coefficient of 0.9968. The proposed ECL immunosensor showed some great advantages, such as simplification, rapidity, stability and selectivity. It was also successfully applied for the determination of Apo-A1 in real serum and urine samples with the recovery of 98.0% ∼ 115.0% (RSD < 5.2%). To sum up, a “signal on” ECL immunosensor was successfully constructed for Apo-A1 detection, and it may facilitate the diagnosis of bladder cancer in clinic.