A Dual Quantum Dot Fluorescent Probe for Time-Resolved Chemometric Detection of Chloramphenicolin Pharmaceuticals

Dual-emission photoluminescence (PL) nanoprobes provide improved analytical performance to develop a reliable and sensitive sensing platform for quantifying chloramphenicol in pharmaceutical samples, thereby ensuring therapeutic efficacy and patient safety. In this work, a dual-emission PL sensing platform combining carbon dots (CDs) and AgInS₂ quantum dots (QDs) capped with mercaptopropionic acid (MPA) was developed for the quantitative determination of chloramphenicol, resorting to chemometric methods for data analysis. CDs, CdTe QDs, and AgInS₂ QDs were synthesized and individually evaluated considering their photostability, PL response and kinetics of their interaction with the antibiotic. After this, two dual-emission probes, CDs/MPA-CdTe and CDs/MPA-AgInS₂, were prepared and assessed based on the complementarity of their individual emission features. The obtained kinetic PL dataset was processed using unfolded partial least squares (U-PLS) in order to explore the multidimensional information of the dual-emission systems and to evaluate the performance of both sensing platforms. CDs/MPA-AgInS₂ probe was demonstrated to be the most efficient sensing platform due to its better compromise between sensitivity and photostability, as well as its cadmium-free composition, allowing the implementation of a more environmentally friendly analytical methodology. The optimization of the U-PLS models involved the assessment of the kinetic acquisition time and different spectral regions. The results showed that reliable, sensitive and efficient quantification could be achieved within the first 5 min of interaction and using the full emission spectrum of the sensing probe. Additionally, different interaction mechanisms were observed for each nanomaterial in the combined probe, being static for the CDs/chloramphenicol interaction and dynamic for MPA-AgInS₂/chloramphenicol interaction, which supports the synergetic behavior of the combined probe. The proposed methodology was effectively applied to commercial pharmaceutical formulations, yielding accurate results with good figures of merit. Therefore, this approach can be used as a relevant alternative to existing methodologies for a rapid, robust, and environmentally friendly method for chloramphenicol quantification.