Chlorine-functionalized black phosphorus quantum dots induced superoxide anion generation and depletion for efficient chemiluminescence detection

Abstract

Background

Due to their unique optoelectronic properties, environmental friendliness, and excellent biocompatibility, metal-free quantum dots have been a new star in exploring novel chemiluminescence (CL) systems for analytical applications in recent years. However, unknown CL property, relatively weak emission and instability of some of them in water (eg. black phosphorus) often seriously hindered their further applications. Hence, developing a novel QDs-assist CL signal amplification to achieve efficient analyst detection is significant and currently hot topic for researchers.

Results

In this work, we purposely synthesized chlorine-functionalized black phosphorus quantum dots (Cl-BPQDs) with improved stability and rich-hole property, which were demonstrated to exhibit the excellent capability for the activation of ferrate (VI) with large reactive oxygen species generation and leading to enhanced CL signal. The detail mechanism was demonstrated, the unique CL response to the presence of active sites (P–Cl) in Cl-BPQDs, which accelerated ferrate (VI) decomposition and produced a large amount of superoxide anion (^•O₂⁻). And then, the radiative recombination of the exogenous electron-donated and existing holes Cl-BPQDs accounting for the strong CL emission. Furthermore, based on the consumption capacity of ascorbic acid (AA) and glutathione (GSH) for ^•O₂⁻, a direct CL sensing platform of Cl-BPQDs/ferrate (VI) quenching was fabricated to AA and GSH detection. This fabricated assay has broad detection linear ranges (2–200 μM) and low detection limit (GSH: 1.3 μM; AA: 1.7 μM). Compared with the reported CL technique, this new method displayed superior sensitivity and anti-interference capabilities toward transition-metal ions and inorganic anions. The potential analytical application of the new CL system was further demonstrated by the evaluation of total antioxidant capacity (TAC) in diabetic patients.

Significance

This study proposes a new strategy for enhancing CL signal via Cl-BPQDs triggering ^•O₂⁻ generation and depletion, which provides an innovative tool for ascorbic acid and glutathione detection. This method not only enriches our understanding of the optical characteristics of BP, but also provides a new charge transfer-based path for CL amplification.