Designing an “Off–On” Fluorescence Sensor Based on Cluster-Based Ca^II-Metal–Organic Frameworks for Detection of l‑Cysteine in Biological Fluids

Recently, luminescent metal–organic framework (MOF) materials have attracted considerable attention in fluorescence sensing. In this essay, we prepared a new cluster-based Ca^II-MOFs {[Ca_1.5(μ₈-HL₁)­(DMF)₂]·DMF}_n (1) with good water dispersibility, excellent photoluminescence properties (FL quantum yield of 20.37%) and great fluorescence stability. Further, it was employed to design as an “off–on” fluorescence sensor for sensitive detection of l-cysteine. This proposed strategy was that fluorescence of Ca^II-MOFs 1 was quenched for providing a low fluorescence background by the introduction of Pb²⁺ forming the Ca^II-MOFs 1/Pb²⁺ hybrid system. The quenching effect could be ascribed to the static quenching mechanism because of the formation of ground-state complexes and coordination interactions between the free carboxyl of H₄L₁ ligands of Ca^II-MOFs 1 and Pb²⁺. Then, with the addition of l-cysteine into the Ca^II-MOFs 1/Pb²⁺ hybrid system, the fluorescence signal was immediately restored. This result was because the Pb²⁺ was gradually released from the hybrid system by chelation interactions between the −SH groups of l-cysteine and Pb²⁺. This method received a relative wide linear range varying from 0.05 to 40 μM and a low detection limit of 15 nM for detection of l-cysteine. This proposed strategy was also successfully applied to detect l-cysteine in human serum samples with satisfactory recoveries from 95.9 to 101.5%.