Revealing the nature of optical activity in carbon dots produced from different chiral precursor molecules

• Main Authors: Baranov, A.V (Author), Cherevkov, S.A (Author), Danilov, D.V (Author), Das, A. (Author), Fedorov, A.V (Author), Koroleva, A.V (Author), Kundelev, E.V (Author), Litvin, A.P (Author), Rogach, A.L (Author), Tsypkin, A.N (Author), Ushakova, E.V (Author), Vedernikova, A.A (Author), Zhizhin, E.V (Author)
• Format: Article
• Language: English
• Published: Springer Nature 2022
• Subjects: Amides; Amino acids; Biocompatibility; Biology and medicine; Carbon; Carbon dots; Chiral precursors; Chirality; Chromophores; Dichroism; Doping (additives); Ethylene diamine; Hydrothermal synthesis; Intrinsic features; Isomers; Optical activity; Optical chirality; Precursor molecules; Recognition site; Site-specific; Stereochemistry; Two photon processes
• Online Access: View Fulltext in Publisher

 Carbon dots (CDs) are light-emitting nanoparticles that show great promise for applications in biology and medicine due to the ease of fabrication, biocompatibility, and attractive optical properties. Optical chirality, on the other hand, is an intrinsic feature inherent in many objects in nature, and it can play an important role in the formation of artificial complexes based on CDs that are implemented for enantiomer recognition, site-specific bonding, etc. We employed a one-step hydrothermal synthesis to produce chiral CDs from the commonly used precursors citric acid and ethylenediamine together with a set of different chiral precursors, namely, L-isomers of cysteine, glutathione, phenylglycine, and tryptophan. The resulting CDs consisted of O,N-doped (and also S-doped, in some cases) carbonized cores with surfaces rich in amide and hydroxyl groups; they exhibited high photoluminescence quantum yields reaching 57%, chiral optical signals in the UV and visible spectral regions, and two-photon absorption. Chiral signals of CDs were rather complex and originated from a combination of the chiral precursors attached to the CD surface, hybridization of lower-energy levels of chiral chromophores formed within CDs, and intrinsic chirality of the CD cores. Using DFT analysis, we showed how incorporation of the chiral precursors at the optical centers induced a strong response in their circular dichroism spectra. The optical characteristics of these CDs, which can easily be dispersed in solvents of different polarities, remained stable during pH changes in the environment and after UV exposure for more than 400 min, which opens a wide range of bio-applications. © 2022, The Author(s).