The rapid and sensitive detection of trace copper ions by L-cysteine capped ZnS nanoparticle fluorescent probe and the insight into micro-mechanism: Experiments and DFT study.

[Display omitted] • Fluorescent quantitative detection of Cu2+ realized by L-cysteine modified ZnS. • The formation of ground state complexes is verified by experiments and simulations. • Fluorescence quenching mechanism of the probe by Cu2+ revealed by simulation. L-cysteine (L-Cys) capped ZnS fluorescent probe (L-ZnS) were synthesized by binding ZnS nanoparticles in situ with L-Cys, the fluorescence intensity of L-ZnS increased more than 3.5 times than that of ZnS due to the cleavage of S–H bonds and the formation of Zn–S bonds between the thiol group of L-Cys and ZnS. The addition of copper ions (Cu2+) can effectively quench the fluorescence of L-ZnS to realize the rapid detection of trace Cu2+. The L-ZnS showed high sensitivity and selectivity to Cu2+. The LOD (limit of detection) of Cu2+ was as low as 7.28 nM and linearity in the concentration range of 3.5–25.5 μM. Meanwhile, for the first time, electron localization function (ELF), bond order density (BOD), and natural adaptive orbital (NAdO) analysis in the Multiwfn wavefunction program based on density functional theory were carried out to probe the binding sites and binding mode of L-Cys with Cu2+, it indicated that the deprotonated carboxyl oxygen atoms of L-Cys had the lowest electrostatic potential (ESP) and provided lone pair electrons to coordinate with Cu2+ to form non-luminescent ground state complexes, which led to fluorescence quenching of L-ZnS. From the microscopic point of view of atoms, the mechanism of fluorescence enhancement of L-Cys capped ZnS and the mechanism of fluorescence quenching after adding Cu2+ were revealed in depth, the theoretical analysis results were accordance with the experiments. [ABSTRACT FROM AUTHOR]