Green Synthesis of Carboxymethyl Chitosan-Based CuInS2 QDs with Luminescent Response toward Pb2+ Ion and Its Application in Bioimaging

Polysaccharide-based QDs have attracted great attention in the field of biological imaging and diagnostics. How to get rid of the high heavy metal toxicity resulting from conventional Cd- and Pb-based QDs is now the main challenge. Herein, we offer a simple and environmentally friendly approach for the "direct" interaction of thiol-ending carboxymethyl chitosan (CMC-SH) with metal salt precursors, resulting in CuInS2 QDs based on polysaccharides. A nucleation–growth mechanism based on the LaMer model can explain how CMC-CuInS2 QDs are formed. As-prepared water-soluble CMC-CuInS2 QDs exhibit monodisperse particles with sizes of 5.5–6.5 nm. CMC-CuInS2 QDs emit the bright-green fluorescence at 530 nm when excited at 466 nm with the highest quantum yield of ∼18.0%. Meanwhile, the fluorescence intensity of CMC-CuInS2 QD aqueous solution is quenched with the addition of Pb2+ and the minimal limit of detection is as little as 0.4 nM. Furthermore, due to its noncytotoxicity, great biocompatibility, and strong biorecognition ability, CMC-CuInS2 QDs can be exploited as a possible cell membrane imaging reagent. The imaging studies also demonstrate that CMC-CuInS2 QDs are suitable for Pb2+ detection in live cells and living organisms (zebrafish). Thus, this work offers such an efficient, green, and practical method for creating low-toxicity and water-soluble QD nanosensors for a sensitive and selective detection of toxic metal ion in live cells and organisms.