Nitrogen-doped graphene quantum dot-based portable fluorescent sensors for the sensitive detection of Fe3+ and ATP with logic gate operation

Abstract

Adenosine triphosphate (ATP) and Fe³⁺ are important “signaling molecules” in living organisms, and their abnormal concentrations can be used for the early diagnosis of degenerative diseases. Therefore, the development of a sensitive and accurate fluorescent sensor is essential for detecting these signaling molecules in biological matrices. Herein, nitrogen-doped graphene quantum dots (N-GQDs) with cyan fluorescence emission were prepared by thermal cleavage of graphene oxide (GO) with N,N-dimethylformamide (DMF) as a solvent. The synergistic effect of static quenching and internal filtration enabled the selective quenching of N-GQD fluorescence by Fe³⁺. With the introduction of ATP, Fe³⁺ in the N-GQDs-Fe³⁺ system formed a more stable complex with ATP via the Fe–O–P bond, thus restoring the fluorescence of the N-GQDs. Fe³⁺ and ATP were detected in the linear ranges of 0–34 μM and 0–10 μM with the limits of detection (LOD) of 2.38 nM and 1.16 nM, respectively. In addition to monitoring Fe³⁺ and ATP in mouse serum and urine, the proposed method was also successfully applied for cytoplasmic imaging of 4T1 cells and in vivo imaging of freshwater shrimps. Moreover, the fluorescence and solution color change-based “AND” logic gate was successfully demonstrated in the biological matrix. Importantly, a complete sensing system was constructed by combining the N-GQDs with hydrogel kits and fluorescent flexible films. Thus, the prepared N-GQDs can be expected to serve as a valuable analytical tool for monitoring Fe³⁺ and ATP concentrations in biological matrices.