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

IF 5.7 2区化学 Q1 CHEMISTRY, ANALYTICAL

Analytica Chimica Acta Pub Date : 2025-04-01 DOI:10.1016/j.aca.2025.343991

Hui Gong, Dayang Zhao, Houjing Liu

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引用次数: 0

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.

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氯功能化黑磷量子点诱导超氧阴离子产生和耗尽，用于高效化学发光检测

无金属量子点由于其独特的光电特性、环境友好性和良好的生物相容性，近年来成为探索新型化学发光（CL）系统的新星。但CL性质未知，有的在水中发射较弱且不稳定(如：黑磷)往往严重阻碍了它们的进一步应用。因此，开发一种新的qds辅助CL信号放大来实现高效的分析物检测是目前研究人员的一个重要课题。结果在本研究中，我们有目的地合成了具有稳定性和富空穴特性的氯功能化黑磷量子点（CL - bpqds），该量子点具有高铁酸盐（VI）的激活能力，产生大量活性氧，并导致CL信号增强。结果表明：高铁酸盐（VI）分解速度加快，产生大量超氧阴离子（•O2-）；然后，外源给电子与现有空穴CL - bpqds的辐射重组，产生强CL发射。此外，基于抗坏血酸（AA）和谷胱甘肽（GSH）对•O2-的消耗能力，构建了CL - bpqds /高铁酸盐（VI）淬灭的直接CL传感平台，用于检测AA和GSH。该方法检测线性范围宽（2 ~ 200 μM），检出限低(GSH: 1.3 μM；Aa: 1.7 μm)。与已有的CL技术相比，该方法对过渡金属离子和无机阴离子具有更高的灵敏度和抗干扰能力。通过评估糖尿病患者的总抗氧化能力（TAC），进一步证明了新CL系统的潜在分析应用。本研究提出了一种通过CL - bpqds触发O2生成和消耗来增强CL信号的新策略，为抗坏血酸和谷胱甘肽的检测提供了一种创新的工具。该方法不仅丰富了我们对BP光学特性的认识，而且为CL放大提供了一种基于电荷转移的新途径。

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来源期刊

Analytica Chimica Acta 化学-分析化学

CiteScore

10.40

自引率

6.50%

发文量

1081

审稿时长

38 days

期刊介绍： Analytica Chimica Acta has an open access mirror journal Analytica Chimica Acta: X, sharing the same aims and scope, editorial team, submission system and rigorous peer review. Analytica Chimica Acta provides a forum for the rapid publication of original research, and critical, comprehensive reviews dealing with all aspects of fundamental and applied modern analytical chemistry. The journal welcomes the submission of research papers which report studies concerning the development of new and significant analytical methodologies. In determining the suitability of submitted articles for publication, particular scrutiny will be placed on the degree of novelty and impact of the research and the extent to which it adds to the existing body of knowledge in analytical chemistry.