Excitation-emission fluorescence matrix acquired from glutathione capped CdSeS/ZnS quantum dots in combination with chemometric tools for pattern-based sensing of neurotransmitters.

The presented work concerns pattern-based sensing with quantum dots for the identification and quantification of neurotransmitters by means of excitation-emission fluorescence spectroscopy (2D fluorescence). In the framework of this study, glutathione capped CdSeS/ZnS nanocrystals were used as non-specific nanoreceptors capable of differentiated interaction with neurotransmitters. The pattern-based sensing with QDs was realized by using excitation-emission fluorescence spectroscopy to provide analyte-specific multidimensional optical information. These characteristic fluorescent response patterns were processed by unfolded partial least squares-discriminant analysis, showing that satisfactory identification of all investigated neurotransmitters: dopamine, norepinephrine, epinephrine, serotonin, GABA, and acetylcholine, can be achieved through the proposed sensing strategy. The impact of the considered fluorescence signal (datum, i.e. zeroth-order data acquired per sample; spectrum, i.e. first-order data acquired per sample; excitation-emission matrix, i.e. second-order data acquired per sample) on the sensing capability of glutathione capped QDs was also verified. The best performance parameters such as accuracy, precision, sensitivity, and specificity were obtained using excitation-emission matrices (88.9-93.3%, 0.93-0.95, 0.89-0.93, and 0.99-1.00, respectively). Thus, it was revealed that excitation-emission fluorescence spectroscopy may improve the recognition of neurotransmitters while using only one type of nanoreceptor. Furthermore, is was demonstrated that the proposed excitation-emission fluorescence spectroscopy assisted QD assay coupled with unfolded partial least squares regression can be successfully utilized for quantitative determination of catecholamine neurotransmitters at the micromolar concentration range with R2 in the range 0.916-0.987. Consequently, the proposed sensing strategy has the potential to significantly simplify the sensing element and to expand the pool of bioanalytes so far detectable with the use of QDs.