Lanthanide-Assisted Function Tailoring of the HOF-Based Logic Gate Sensor Array for Biothiol Detection and Disease Discrimination

The advancement of lanthanide fingerprint sensors characterized by targeted emission responses and low self-fluorescence interference for the detection of biothiols is of considerable importance for the early diagnosis and treatment of cancer. Herein, the lanthanide “personality function tailoring” HOF composite sensor array is designed for the specific discrimination of biothiols (GSH, Cys, and Hcy) based on the activation of various luminescent molecules, such as r-AuNCs/luminol via HOF surface proximity. Lumi-HOF@Ce serves as a versatile platform for catalyzing the oxidation of o-phenylenediamine (OPD) to generate yellow fluorescent oligomers, accompanied by the fluorescence attenuation of luminol. HOF@Tb functions as a confinement interface that gathers gold nanoclusters (r-AuNCs) with red fluorescence, facilitating an aggregation-induced emission enhancement (AIEE). The fluorescence properties of AuNCs are subsequently impacted to varying degrees by the Au(I)-thiolate motifs from biothiol rooted in an enhanced ligand–metal charge transfer (LMCT) process. Additionally, the catalytic activity of Lumi-HOF@Ce, which exhibits oxidase-like properties, can be inhibited by different biothiols to varying extents. The five-channel fluorescent array demonstrates exceptional discrimination of biothiol fingerprints, aided by machine learning algorithms. Feature-tailored lanthanide HOF sensor arrays achieve sensitive identification with nearly 100% accuracy in classifying clinical liver cancer samples versus normal samples, using a logic gate strategy. The current strategy of lanthanide function tailoring boosts the suitability of biosensing applications.