Nowadays, multiplex analysis is very popular, since it allows to detect a large number of biomarkers simultaneously. Traditional multiplex analysis is usually based on changes of photoluminescence (PL) intensity and/or PL band spectral positions in the presence of analytes. Using PL lifetime as an additional parameter might increase the efficiency of multiplex methods. Quantum dots (QDs) can be used as luminescent markers for multiplex analysis. Ternary in-based QDs are a great alternative to the traditional Cd-based one. Ternary QDs possess all advantages of traditional QDs, including tunable photoluminescence in visible range. At the same time ternary QDs do not have Cd-toxicity, and moreover they possess long spectral dependent lifetimes. This allows the use of ternary QDs as a donor for time-resolved multiplex sensing based on Förster resonance energy transfer (FRET). In the present work, we implemented FRET from AgInS2/ZnS ternary QDs to cyanine dyes absorbing in different spectral regions of QD luminescence with different lifetimes. As the result, FRET-induced luminescence of dyes differed not only in wavelengths but also in lifetimes of luminescence, which can be used for time-resolved multiplex analysis in biology and medicine.

Ternary quantum dots (QDs) are very promising nanomaterials with a range of potential applications in photovoltaics, light-emitting devices, and biomedicine. Despite quite intensive studies of ternary QDs over the last years, the specific relaxation channels involved in their emission mechanisms are still poorly understood, particularly in the corresponding core-shell nanostructures. In the present work, we have studied the recombination pathways of AgInS2 QDs stabilized with the ZnAgInS alloy layer and the ZnS shell (AIS/ZAIS/ZnS QDs) using time-resolved fluorescence spectroscopy. We have also investigated FRET in complexes of AIS/ZAIS/ZnS QDs and cyanine dyes with the absorption bands overlapping in the different regions of the QD emission spectrum, which allowed us to selectively quench the radiative transitions of the QDs. Our studies have demonstrated that FRET from QDs to dyes results in decreasing of all QD PL decay components with the shortest lifetime decreasing the most and the longest one decreasing the least. This research presents important approaches for the investigation of ternary QD luminescence mechanisms by the selective quenching of recombination pathways. These studies are also essential for potential applications of ternary QDs in photodynamic therapy, multiplex analysis, and time-resolved FRET sensing.

Here we report on the development and investigation of a novel multiplex assay model based on polymer microspheres (PMS) encoded with ternary AIS/ZnS quantum dots (QDs). The system was prepared via layer-by-layer deposition technique. Our studies of Förster resonance energy transfer (FRET) between the QD-encoded microspheres and two different cyanine dyes have demonstrated that the QD photoluminescence (PL) quenching steadily increases with a decrease in the QD-dye distance. We have found that the sensitized dye PL intensity demonstrates a clear maximum at two double layers of polyelectrolytes between QDs and Dye molecules on the polymer microspheres. Time resolved PL measurements have shown that the PL lifetime decreases for the QDs and increases for the dyes due to FRET. The designed system makes it possible to record spectrally different bands of FRET-induced dye luminescence with different decay times and thereby allows for the multiplexing by wavelength and photoluminescence lifetimes of the dyes. We believe that PMS encoded with AIS/ZnS QDs have great potential for the development of new highly selective and sensitive sensor systems for multiplex analysis to detect cell lysates and body fluids’ representative biomarkers.

No abstract