Boron-enriched rice-like homologous carbon nanoclusters with a 51.5% photoluminescent quantum yield for highly sensitive determination of endogenous hydroxyl radicals in living cells

Abstract

Exploring the ultrahigh quantum efficiency of a carbon-based probe via a green and simple technique, and utilisation of its sensing ability for highly bioactive molecule detection is still highly challenging. Herein, we prepared a novel boron-enriched rice-like homologous carbon nanoclusters (BRCNs) with an ultrahigh quantum efficiency of ∼51.5% by introduction of a conjugated structure attached to the CN bond and an electron-withdrawing boron active centre. Unexpectedly, the BRCNs obtained showed a stable dispersion of rice-like carbon nanograins, composed of small carbon dot assembled nanoclusters with an average diameter size of ∼30 nm, and containing boron units of ∼24.68 at%. What's exciting is that the BRCNs obtained exhibited an “on–off–on” three-state emission with the addition of an hydroxyl radical (OH˙) and its antioxidants. Thus, two distinctive fluorescent responses for OH˙ and antioxidants based on the BRCN probe had been developed, and the mechanism has been determined using TEM, XPS, FT-IR, FL, UV-vis spectrophotometry, UPS and fluorescent lifetimes. The OH˙, generated from the Fenton's reagent, preferentially attack the electron-deficient vacancy p orbit of the boron atom in the surface of the BRCNs, which results in the boron atom being easily substituted/attacked by OH˙, and leading to spontaneous aggregation induced quenching (AIQ) due to the existence of a strong intermolecular hydrogen bond between denatured BRCNs. Furthermore, the proposed method was also successfully applied to monitor endogenous OH˙ generation in HeLa cells by confocal imaging, which could be used for elucidating OH˙-induced oxidative damage to biological tissues and proteins.