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用于灵敏且可重复的表面增强拉曼光谱分析的同质热点等离子体微胶囊集成富集-检测一体化技术

Homogeneous Hot Spots Plasmonic Microcapsules Integrated Enrichment-Detection All-in-One for Sensitive and Repeatable Surface-Enhanced Raman Spectroscopy Analysis.

作者信息

Li Dan, Xia Ling, Li Gongke

机构信息

School of Chemistry, Sun Yat-sen University, Guangzhou 510006, China.

出版信息

Anal Chem. 2025 Jul 22;97(28):15482-15491. doi: 10.1021/acs.analchem.5c02796. Epub 2025 Jul 11.

Abstract

Rapid and accurate analysis of complex samples by surface-enhanced Raman spectroscopy (SERS) still faces challenges. Herein, an enrichment-detection all-in-one strategy within plasmonic microcapsules (PMCs) was proposed for sensitive and repeatable SERS analysis. The PMC had silver nanoparticles (AgNPs) as shells, which were prepared using any immiscible solvents in 1 min. It could not only serve as microreaction chambers for phase separation and rapid enrichment of analytes but also offer homogeneous hot spots and powerful signal enhancement for SERS detection. The PMC showed good SERS performance with a relative standard deviation (RSD) of less than 5.0% for uniformity and less than 7.0% for intrabatch and interbatch stability. Moreover, PMC showed high SERS enhancement for methylene blue (MB), malachite green (MG), and rhodamine 6G (R6G), with enhancement factors () of 3.4 × 10, 2.1 × 10 and 1.1 × 10, respectively, corresponding to 2 orders of magnitude higher than that of Ag sol method. Subsequently, the selectivity and enhancement mechanisms were studied. MB and T-2 toxin were chosen as model analytes to present two application scenarios. The detection limits of MB and T-2 toxin were 0.03 nmol/L and 1.6 ng/L, respectively. It was applied to the detection of MB in animal-source samples and T-2 toxin in plant-source samples, with recovery rates of 91.5-104% and RSD of 1.0-7.2%. Validation using the high-performance liquid chromatography method with a relative error of -7.1-0.5%. The proposed method shows great potential for the sensitive and repeatable SERS detection of trace analytes.

摘要

通过表面增强拉曼光谱(SERS)对复杂样品进行快速准确的分析仍然面临挑战。在此,提出了一种在等离子体微胶囊(PMC)内的富集-检测一体化策略,用于灵敏且可重复的SERS分析。该PMC以银纳米颗粒(AgNP)为壳层,可在1分钟内使用任何不混溶的溶剂制备而成。它不仅可以作为微反应室用于分析物的相分离和快速富集,还能为SERS检测提供均匀的热点和强大的信号增强。该PMC显示出良好的SERS性能,均匀性的相对标准偏差(RSD)小于5.0%,批内和批间稳定性的RSD小于7.0%。此外,PMC对亚甲基蓝(MB)、孔雀石绿(MG)和罗丹明6G(R6G)表现出高SERS增强,增强因子()分别为3.4×10、2.1×10和1.1×10,比Ag溶胶法高出2个数量级。随后,研究了选择性和增强机制。选择MB和T-2毒素作为模型分析物以展示两种应用场景。MB和T-2毒素的检测限分别为0.03 nmol/L和1.6 ng/L。它被应用于动物源样品中MB的检测以及植物源样品中T-2毒素的检测,回收率为91.5 - 104%,RSD为1.0 - 7.2%。使用高效液相色谱法进行验证,相对误差为 -7.1 - 0.5%。所提出的方法在痕量分析物的灵敏且可重复的SERS检测方面显示出巨大潜力。

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