Sensitive Detection of Hg2+ and l-Cysteine through Optical Asymmetry-Tuned Fluorescence Switch Off-On Behavior in N-Doped Chiral Carbon Dot.

Abstract

Blue-emissive nitrogen-doped chiral carbon dots (d-NCD230 and l-NCD230) exhibiting antipodal chiroptical activity, synthesized from the thermal pyrolysis of citric acid and d/l-aspartic acid in 1:2 molar ratios, have been explored as chirality-based fluorescent turn-off/on probes for the detection of Hg²⁺ and l-cysteine (l-Cys). Circular dichroism (CD) spectroscopy revealed that the chiroptical activity originates from a synergy among intrinsic chirality, chiral precursors on the NCD surface, and hybridization of lower energy levels within the embedded chiral chromophore. Quantitative analysis of optical asymmetry using the Kuhn asymmetry factor (g) at the CD signal of 312 nm showed a higher value for d-NCD230 (1.03 × 10^-4) compared to l-NCD230 (1.13 × 10^-5). Moreover, we have demonstrated chirality transfer and chiral inversion phenomena in d/l-NCDs by preparing carbon dots with different precursor ratios at different temperatures and probing them through CD spectroscopy. The NCDs exhibited selective fluorescence quenching in the presence of Hg²⁺, demonstrating linearity in the Stern-Volmer plot. Limits of detection (LODs) for Hg²⁺ were calculated to be 129 and 192 nM for d-NCD230 and l-NCD230, respectively, in the 0-150 μM concentration range. The quenching mechanism involves nonradiative electron transfer due to Hg²⁺ binding to oxygen-rich functional groups on the d/l-NCD230 surface. The slight variation in LOD values between d-NCD230 and l-NCD230 indicates the negligible effect of the chirality on Hg²⁺ sensing. Notably, the fluorescence intensity of d/l-NCD230 could be restored upon adding l-cysteine, with d-NCD230 showing a more pronounced enhancement than l-NCD230. This differential response is attributed to a preferential stereoselective interaction arising from the homochirality of d-NCD230/Hg²⁺ and l-cysteine. These findings demonstrate the potential of chiral nitrogen-doped carbon dots as sensitive and selective probes for Hg²⁺ and l-cysteine, with implications for environmental monitoring and biological sensing applications.