Unraveling the structural evolution of silver plasmonic hotspots for the detection of oxidative ONOO− radicals via SERS probe decay

IF 5.3 2区化学 Q1 CHEMISTRY, ANALYTICAL Microchimica Acta Pub Date : 2025-02-24 DOI:10.1007/s00604-025-07045-9

Xiaoying Zhu, Qi Zhang, Xiaohua Qi, Yibo Feng, Mingqiang Zou, Qingbian Ma, Lin Zhang, Qiang Ma, Cong Wang

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Abstract

Peroxynitrite (ONOO⁻) plays a pivotal role in environmental pollution and ecosystem health, necessitating its detection for assessing ecological impacts and risks. Surface-enhanced Raman scattering (SERS) offers high sensitivity but is often limited by narrow Raman cross sections of analytes. Specialized molecules can aid SERS detection, but are complex to design and may cause nonspecific reactions in biological systems. Therefore, developing new SERS strategies is crucial for simpler, more accurate ONOO⁻ detection. Herein, the shape instability of Ag nanomaterials in the hotspots, due to oxidation and dissolution of Ag atoms at the edges and corners, is investigated, and the detection of ONOO⁻ is performed by SERS probes. ONOO⁻ reacts first with the (111) facet, especially at the edges and corners. Consequently, the SERS signal of the adsorbed probe, Rhodamine 6G in hotspots can be used to monitor edge and corner dissolution that positively related to the ONOO⁻ concentration. As a result, ONOO⁻ concentration from 0.1 to 25 μM was detected, achieving a coefficient of determination of R² = 0.9896. The method exhibits good reproducibility (RSD < 3.25%) and stability (> 7 days), and quantitative detection of ONOO⁻ was achieved in bovine serum samples. Ag nanocubes exhibited an eightfold stronger response and higher precision compared to Ag nanoparticles in ONOO⁻ detection. This simple detection technique offers a promising method for the accurate, quantitative detection of ONOO⁻ in wide range of biological systems.

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揭示银等离子体热点的结构演变，通过SERS探针衰变检测氧化ONOO−自由基

过氧亚硝酸盐（ONOO−）在环境污染和生态系统健康中起着关键作用，因此需要对其进行检测以评估生态影响和风险。表面增强拉曼散射（SERS）具有很高的灵敏度，但通常受到分析物拉曼截面狭窄的限制。专门的分子可以帮助SERS检测，但设计复杂，可能导致生物系统中的非特异性反应。因此，开发新的SERS策略对于更简单，更准确的ONOO -检测至关重要。本文研究了银纳米材料在热点区域的形状不稳定性，这是由于银原子在边缘和角落的氧化和溶解，并通过SERS探针进行ONOO -的检测。ONOO -首先作用于（111）面，尤其是在边角处。因此，热点区域吸附探针罗丹明6G的SERS信号可用于监测与ONOO−浓度正相关的边缘和角落溶解。结果表明，ONOO−浓度范围为0.1 ~ 25 μM，检测系数R2 = 0.9896。该方法重现性好（RSD < 3.25%），稳定性好（>； 7天），可在牛血清样品中实现ONOO−的定量检测。在ONOO−检测中，银纳米立方体表现出比银纳米颗粒强8倍的响应和更高的精度。这种简单的检测技术为广泛的生物系统中ONOO−的准确、定量检测提供了一种有前途的方法。图形抽象

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来源期刊

Microchimica Acta 化学-分析化学

CiteScore

9.80

自引率

5.30%

发文量

410

审稿时长

2.7 months

期刊介绍： As a peer-reviewed journal for analytical sciences and technologies on the micro- and nanoscale, Microchimica Acta has established itself as a premier forum for truly novel approaches in chemical and biochemical analysis. Coverage includes methods and devices that provide expedient solutions to the most contemporary demands in this area. Examples are point-of-care technologies, wearable (bio)sensors, in-vivo-monitoring, micro/nanomotors and materials based on synthetic biology as well as biomedical imaging and targeting.