Probing DNA-stabilized fluorescent silver nanocluster spectral heterogeneity by time-correlated single photon counting

Abstract

DNA-stabilized silver nanoclusters (DNA-AgNCs) are promising fluorophores whose photophysical properties and synthesis procedures have received increased attention in the literature. However, depending on the preparation conditions and the DNA sequence, the DNA-AgNC samples can host a range of different emitters, which can influence the reproducibility of the optical response and the evolution over time of the populations of these emitters. We have developed a simple method to characterize the spectral heterogeneity and time evolution of these emissive species at any given point in time after preparation, by plotting the average decay time as a function of emission wavelength. These so-called average decay time spectra were acquired for different excitation wavelengths of AgNCs stabilized by an oligonucleotide containing 24 cytosines (C24-AgNCs). The average decay time spectra allowed the comparison of sample preparation and the judgment of reproducibility. Therefore, we propose the use of the average decay time spectra as a robust and easy tool to characterize and compare different as-synthesized DNA-AgNC samples. The average decay time spectra can in general also be used to characterize the spectral heterogeneity of other fluorophores, such as luminescent colloidal nanoparticles, and to assess the reproducibility of a synthetic procedure containing an unknown distribution of emissive species.