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“二合一”硫氮共掺杂荧光硅纳米粒子:同时作为荧光探针和光催化剂用于四环素类抗生素的原位实时可视化监测与降解。

"Two-in-one" sulfur and nitrogen co-doped fluorescent silicon nanoparticles: Simultaneous as the fluorescent probe and photocatalyst for in-situ real time visual monitoring and degradation of tetracycline antibiotics.

机构信息

Tongji School of Pharmacy, Huazhong University of Science and Technology, Wuhan 430030, PR China.

Tongji School of Pharmacy, Huazhong University of Science and Technology, Wuhan 430030, PR China.

出版信息

Sci Total Environ. 2022 Nov 10;846:157470. doi: 10.1016/j.scitotenv.2022.157470. Epub 2022 Jul 19.

Abstract

Detection and removal of contaminants are significant for environmental monitoring and remediation. In the present study, "two-in-one" silicon nanoparticles (SiNPs) were designed and prepared to simultaneously act as the fluorescent probe and degradation catalyst to detect and remove tetracycline (TCs) antibiotics. Thiourea and 3-aminopropyltrimethoxysilane were dopant and silicon source to generate fluorescent sulfur and nitrogen co-doped SiNPs (SN-SiNPs). The blue fluorescence of SN-SiNPs was selectively quenched by TCs due to the inner filter effect, whilst accompanied by the newly appeared yellow-green fluorescence resulting from aggregation induced fluorescence emission effect. Based on this phenomenon, SN-SiNPs can be used as fluorescent colorimetric probes for detection of doxycycline, oxytetracycline and tetracycline with limits of detection of 1.8 μg/L, 3.0 μg/L and 4.2 μg/L, respectively; the semi-quantitation can even be visually achieved by naked eyes. Particularly, SN-SiNPs were capable to catalyze the degradation of the three TCs effectively, achieving the removal rates of doxycycline, oxytetracycline and tetracycline of >90 %, >80 % and > 70 % after 240 min exposure to UV light. The catalytic ability of SN-SiNPs was derived from hydroxyl radical (•OH), superoxide radical (•O) and singlet oxygen (O) produced by SN-SiNPs under UV irradiation. Moreover, integrating the fluorescent probe and photocatalyst together, the proposed SN-SiNPs simultaneously realized catalyzing the degradation of the three TCs and in-situ visually monitoring of the degradation process in real time. This study innovatively proposed an integrated probe for the detection and catalytic degradation of TCs, providing a new "two-in-one" strategy for rapid and simple detection and removal of drug pollutants.

摘要

污染物的检测和去除对于环境监测和修复至关重要。在本研究中,设计并制备了“二合一”硅纳米粒子(SiNPs),以同时充当荧光探针和降解催化剂,用于检测和去除四环素(TCs)抗生素。硫脲和 3-氨丙基三甲氧基硅烷作为掺杂剂和硅源,生成荧光硫氮共掺杂 SiNPs(SN-SiNPs)。由于内滤效应,SN-SiNPs 的蓝色荧光被 TCs 选择性猝灭,同时伴随着由于聚集诱导荧光发射效应而新出现的黄绿光。基于这一现象,SN-SiNPs 可用作检测强力霉素、土霉素和四环素的荧光比色探针,检测限分别为 1.8 μg/L、3.0 μg/L 和 4.2 μg/L;甚至可以通过肉眼进行半定量检测。特别地,SN-SiNPs 能够有效地催化三种 TCs 的降解,在暴露于紫外光 240 分钟后,强力霉素、土霉素和四环素的去除率分别达到>90%、>80%和>70%。SN-SiNPs 的催化能力源自 SN-SiNPs 在紫外光照射下产生的羟基自由基(•OH)、超氧自由基(•O)和单线态氧(O)。此外,将荧光探针和光催化剂集成在一起,所提出的 SN-SiNPs 同时实现了对三种 TCs 的催化降解和降解过程的实时原位可视化监测。本研究创新性地提出了一种用于 TCs 检测和催化降解的集成探针,为快速、简单地检测和去除药物污染物提供了一种新的“二合一”策略。

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