Fabrication of CuInZnS/ZnS Quantum Dot Microbeads by a Two-Step Approach of Emulsification-Solvent Evaporation and Surfactant Substitution and Its Application for Quantitative Detection.

CuInS2 quantum dots (CIS QDs) are considered to be promising alternatives for Cd-based QDs in the fields of biology and medicine. However, high-quality hydrophobic CIS QDs are difficult to be transferred to water due to their 1-dodecylmercaptan (DDT) ligands. Therefore, the fluorescence and stability of the prepared aqueous CIS QDs is not enough to meet the requirement for sensitive detection. Here, as large as 13 nm CuInZnS/ZnS QDs with DDT ligands were first synthesized, and then, CuInZnS/ZnS microbeads (QBs) containing thousands of QDs were successfully fabricated by a two-step approach of emulsion-solvent evaporation and surfactant substitution. Through emulsion-solvent evaporation, the CuInZnS/ZnS QDs formed microbeads in the microemulsion with dodecyl trimethylammonium bromide (DTAB), and the Förster resonance energy transfer (FRET) has been effectively overcome. Then, CO-520 was introduced to substitute DTAB to improve the stability and water solubility. Lastly, the microbeads were coated with a SiO2 shell and carboxylated. Subsequently, the constructed QBs (∼210 nm) were used as labels in a fluorescence immunosorbent assay (FLISA) for quantitative detection of heart type fatty acid binding protein (H-FABP), and the limit of detection was 0.48 ng mL-1, which indicated a greatly improved detection sensitivity compared to that of the Cd-free QDs. The highly fluorescent and stable CuInZnS/ZnS QBs will have great application prospects in many biological fields.