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基于绿色Ag/CuO(CuO)纳米复合材料的表面增强拉曼散射(SERS)传感器用于茶叶中多菌灵农药的超灵敏检测:金属/半导体转变在传感性能中的作用

Ultrasensitive detection of carbendazim pesticide in tea leaves using a green Ag/CuO(CuO) nanocomposite-based SERS sensor: role of metal/semiconductor transition in sensing performance.

作者信息

Thi Linh Dong, Mai Quan-Doan, Thi Hanh Trang Dang, Anh Nguyen Tuan, Vu Xuan Hoa, Le Anh-Tuan

机构信息

Phenikaa University Nano Institute (PHENA), Phenikaa University Hanoi 12116 Vietnam

Faculty of Fundamental Sciences, Thai Nguyen University of Technology 666 3/2 Road Thai Nguyen City 24000 Vietnam.

出版信息

RSC Adv. 2025 May 27;15(22):17635-17647. doi: 10.1039/d5ra00846h. eCollection 2025 May 21.

Abstract

Surface-enhanced Raman spectroscopy (SERS) is increasingly recognized as a powerful tool for analytical applications, especially in food safety, due to its ability to detect molecular fingerprints even at the single-molecule level. Developing SERS substrates that offer not only high sensitivity but also reliability and practicability is critical for transitioning SERS from a laboratory-based technique to practical field applications. In this study, we present an outstandingly sensitive, reliable, and practical Ag/CuO nanocomposite SERS substrate, fabricated through a simple green electrochemical method. The Ag/CuO substrate demonstrates remarkable sensitivity, detecting carbendazim (CBZ), a hazardous pesticide widely used in tea leaves, at an ultra-low limit of 8.85 × 10 M, outperforming bare Ag substrate, which only reaches 10 M. The high reliability of the Ag/CuO substrate is confirmed by excellent repeatability and reproducibility, with a relative standard deviation (RSD) of less than 10%. Practicability was validated through the direct detection of CBZ in fresh tea leaves, yielding sharp recovery values of 85% to 106%. Additionally, the SERS enhancement mechanism was explored by comparing the performance of Ag, Ag/CuO, and Ag/CuO substrates, revealing the critical role of metal (Ag) and semiconductor (CuO, CuO) transitions in overall sensing performance. These findings underscore the potential of Ag/CuO nanocomposites for ultrasensitive pesticide detection in real-world agricultural environments and highlight the importance of metal/semiconductor transitions in designing more efficient SERS substrates. This paves the way for the development of versatile, field-ready SERS platforms applicable to a wide range of analytical and environmental monitoring needs.

摘要

表面增强拉曼光谱(SERS)作为一种强大的分析工具正日益受到认可,尤其是在食品安全领域,因为它即使在单分子水平也能检测分子指纹。开发不仅具有高灵敏度而且具有可靠性和实用性的SERS基底对于将SERS从基于实验室的技术转变为实际现场应用至关重要。在本研究中,我们展示了一种通过简单的绿色电化学方法制备的极其灵敏、可靠且实用的Ag/CuO纳米复合SERS基底。Ag/CuO基底表现出卓越的灵敏度,能以8.85×10⁻⁸ M的超低检测限检测多菌灵(CBZ),这是一种广泛用于茶叶中的有害农药,性能优于仅能达到10⁻⁷ M的裸银基底。Ag/CuO基底的高可靠性通过出色的重复性和再现性得到证实,相对标准偏差(RSD)小于10%。通过对新鲜茶叶中CBZ的直接检测验证了其实用性,回收率在85%至106%之间,结果良好。此外,通过比较Ag、Ag/CuO和CuO基底的性能探索了SERS增强机制,揭示了金属(Ag)和半导体(CuO、Cu₂O)转变在整体传感性能中的关键作用。这些发现强调了Ag/CuO纳米复合材料在实际农业环境中超灵敏农药检测方面的潜力,并突出了金属/半导体转变在设计更高效SERS基底中的重要性。这为开发适用于广泛分析和环境监测需求的通用、现场可用的SERS平台铺平了道路。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ce46/12108759/ba0e81bf0aa4/d5ra00846h-f1.jpg

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