Unique Electron-Transfer-Mediated Electrochemiluminescence of AuPt Bimetallic Nanoclusters and the Application in Cancer Immunoassay

Noble Metal nanoclusters (NCs) are promising electrochemiluminescence (ECL) emitters due to their amazing optical properties and excellent biocompatibility. They have been widely used in the detection of ions, pollutant molecules, biomolecules, etc. Herein, we found that glutathionecapped AuPt bimetallic NCs (GSH-AuPt NCs) emitted strong anodic ECL signals with triethylamine as co-reactants which had no fluorescence (FL) response. Due to the synergistic effect of bimetallic structures, the ECL signals of AuPt NCs were 6.8 and 94 times higher than those of monometallic Au and Pt NCs, respectively. The electric and optical properties of GSH-AuPt NCs differed from those of Au and Pt NCs completely. An electron-transfer mediated ECL mechanism was proposed. The excited electrons may be neutralized by Pt(II) in GSH-Pt and GSH-AuPt NCs, resulting in the vanished FL. Furthermore, abundant TEA radicals formed on the anode contributed electrons to the highest unoccupied molecular orbital of GSH-Au2.5Pt NCs and Pt(II), booming intense ECL signals. Because of the ligand effect and ensemble effect, bimetallic AuPt NCs exhibited much stronger ECL than GSH-Au NCs. A sandwich-type immunoassay for alpha fetoprotein (AFP) cancer biomarkers was fabricated with GSH-AuPt NCs as signal tags, which displayed a wide linear range from 0.01 to 1000 ng center dot mL(-1) and a limit of detection (LOD) down to 1.0 pg center dot mL(-1) at 3S/N. Compared to previous ECL AFP immunoassays, this method not only had a wider linear range but also a lower LOD. The recoveries of AFP in human serum were around 108%, providing a wonderful strategy for fast, sensitive, and accurate cancer diagnosis.

Automated summary

Noble Metal nanoclusters (NCs) exhibit strong electrochemiluminescence (ECL) signals and excellent biocompatibility. Glutathione-capped AuPt bimetallic NCs (GSH-AuPt NCs) show enhanced ECL signals compared to monometallic Au and Pt NCs, thanks to the synergistic effect of the bimetallic structure. The unique electric and optical properties of GSH-AuPt NCs contribute to their strong ECL emission. A sandwich-type immunoassay using GSH-AuPt NCs as signal tags achieves sensitive and accurate cancer diagnosis with a wide linear range and a lower limit of detection.