Chemical etching of pH-sensitive aggregation-induced emission-active gold nanoclusters for ultra-sensitive detection of cysteine

Abstract

This study reports the utilization of thiol-induced chemical etching of aggregation-induced emission (AIE)-active Au nanoclusters (NCs) for the facile, sensitive, and selective detection of cysteine. The AIE-active Au NCs were formed in an acidic solution containing excess Au(I)–thiolate complexes. At an acidic pH (2.0), the emission of these Au NCs was enhanced by cysteine at a concentratioin below 1 mM. However, the emission was quenched by cysteine at a high concentration, e.g., 500 mM, via the thiol-induced etching of gold, although the process occurred very slowly. Interestingly, in the absence of cysteine, increasing the solution pH enhanced the emission, while the presence of cysteine remarkably accelerated the etching-induced quenching process. The complete quenching of the emission by excess cysteine at pH 2.0 and the enhancement of the emission by the increasing pH in the absence of cysteine indicated that aurophilicity might not be involved in the AIE of the Au NCs prepared using glutathione (GSH) both as the reducing and protecting reagent. On the other hand, the etching process involved the penetration of cysteine molecules through the Au(I)–thiolate complexes, which could assemble or disassemble around the embedded Au NCs in response to the solution pH to get access to the innermost Au(0) cores. Therefore, a facile, sensitive, and selective method for the detection of cysteine was established. This method exhibited an extremely wide linear range as wide as nine orders of magnitude above the cysteine concentration, including two linear regions of the relative emission intensity of the Au NCs versus the logarithm of cysteine concentration, from 10 pM to 150 μM (correlation coefficient, 0.99851) and from 150 μM to 2 mM (correlation coefficient, 0.99866). An ultra-low limit of detection of 6.3 pM (S/N = 3) was also achieved. The developed method showed superior selectivity for cysteine relative to the 19 other natural amino acids and GSH. The method was applied for the analysis of human serum samples spiked with cysteine with satisfactory results. This study demonstrates the potential of the thiol-induced chemical etching approach as a powerful tool for studying luminescent metal NCs.