Label-free detection of creatinine using nitrogen-passivated fluorescent carbon dots

Abstract

In the field of biochemistry and biosensing, the passivation of carbon dots using nitrogen dopants has attracted great attention, as this can control their photoluminescence (PL) properties and quantum yield. To date, in the fabrication of a sensing probe, the impact of the chemical composition of the passivating molecule remained unexplored. In this work, we chose a series of different nitrogen-rich precursors (such as urea, thiourea, cysteine, and glycine) and ascorbic acid to synthesize nitrogen-doped carbon dots (NCDs). A significant change in their surface states was obtained due to the evolution of variable contents of amino, pyridinic and pyrrolic nitrogen species, which is evident from X-ray photoelectron spectroscopy, and this leads to an increment in their PL quantum yields (PLQY ∼ 58%) and average lifetime values. Spectroscopic analysis revealed that a rise in the ratio of pyrrolic : amino groups on the surface of carbon dots cause a bathochromic shift and generate excitation-dependent properties of NCDs. Besides, these NCDs were used as fluorescence off-on sensing probes, where a PA-infested NCD solution was used to detect creatinine. Chiefly, fluorescence restoration was achieved due to the formation of Jaffe chromogen between creatinine and PA. However, all nitrogen-passivated carbon dot surfaces do not respond similarly towards creatinine and only non-amino-rich NCDs exhibit the maximum (50%) PL turn-on response. The PL turn-off-on methodology showed a satisfactory good linearity range between 0 and 150 μM with a detection limit of 0.021 nM for creatinine. Three input molecular logic gates were also designed based on the turn-off-on response of the NCDs@PA towards creatinine. Additionally, for analytical method validation, real-sample analysis was performed for creatinine, which showed good recoveries (93-102%) and verified that nitrogen passivation tailored the physicochemical properties and enhanced the sensing ability.