Surface vs. core N/S/Se-heteroatom doping of carbon nanodots produces divergent yet consistent optical responses to reactive oxygen species

Abstract

Carbon nanodots (CNDs) have attracted substantial scientific curiosity because of their intriguing stimuli-responsive optical properties. However, one obstacle to the more widespread use of CNDs as transducers for e.g., biodetection systems is incomplete knowledge regarding the underlying chemical changes responsible for this responsiveness, and how these chemical features can be engineered via the precursors chosen for CND synthesis. This study demonstrates that the precursor's functional groups play a key role in directing N/S/Se heteroatom dopants either towards the surface of the CNDs, towards the aromatic core, or towards small organic fluorophores in the core. Divergent optical properties, which were consistent amongst groups of CNDs prepared with similar precursors, were obtained including either a decrease or increase of fluorescence intensity in the presence of hydrogen peroxide. Moreover, CNDs were identified with orthogonal responsiveness to radical (hydroxyl radicals, ˙OH; down to 2.5 μM) vs. non-radical oxidants (H₂O₂; down to 50 μM), which suggests that control of the chemistry of CNDs via the choice of precursor could yield probes that are specific to certain sub-species of reactive oxygen species or entirely different molecules altogether, based on the way they chemically-modify the surface (respond faster) and core functional groups (respond slower) associated with chromophores/fluorophores of which the CNDs are composed.