School of Chemistry, Sun Yat-Sen University, Guangzhou, 510006, China.
Faculty of Food Science and Engineering, Kunming University of Science and Technology, Kunming, 650500, China.
Anal Bioanal Chem. 2022 Mar;414(7):2385-2395. doi: 10.1007/s00216-022-03876-0. Epub 2022 Jan 10.
In this work, a simple, high-throughput, and sensitive analytical method based on surface-enhanced Raman spectroscopy (SERS) and principal component analysis (PCA) was fabricated for simultaneous and rapid determination of three polychlorinated phenols (PCPs) including 2,4-dichlorophenol (2,4-DCP), 2,4,5-trichlorophenol (2,4,5-TCP), and 2,3,4,6-tetrachlorophenol (2,3,4,6-TeCP). The aggregated Ag nanoparticles (AgNPs) induced by inorganic salt ions were used as sensitive SERS substrate, and the electromagnetic field distribution of AgNPs with different distances was simulated by finite difference time domain (FDTD) to verify the theory feasibility. The high throughput and rapid detection can be achieved by commercial 96-pore plate. Under the optimum conditions, the linear relationship between the Raman intensity and the concentrations of PCPs was established with satisfied correlation coefficient. The limits of detection (LOD) for 2,4-DCP, 2,4,5-TCP, and 2,3,4,6-TeCP are 0.27 mg L, 0.09 mg L, and 0.10 mg L by rules of 3σ, respectively. The simultaneous quantitative analysis can be achieved thanks to the independent Raman characteristic peaks of three PCPs. Afterwards, the PCA method was used to eliminate the limitations of overlapping of characteristic Raman peaks in structural analogues of 2,4-DCP, 2,4,5-TCP, and 2,3,4,6-TeCP. The recovery experiments including single PCPs and mixed PCP samples show satisfied recoveries ranging from 85.0 to 113.9% and 80.4 to 114.0% with RSDs in range of 0.4-9.5% and 1.1-10.7%, respectively. The proposed method shows great potentials in rapid, high-throughput, and sensitive monitoring of the contaminants in water and pesticide samples with similar structure. Here, we introduced aggregated Ag nanoparticles (AgNPs) induced by inorganic salt ion for simultaneous, rapid, and sensitive determination of polychlorinated phenols (PCPs) including 2,4-dichlorophenol (2,4-DCP), 2,4,5-trichlorophenol (2,4,5-TCP), and 2,3,4,6-tetrachlorophenol (2,3,4,6-TeCP) by surface-enhanced Raman spectroscopy (SERS) combined with principal component analysis (PCA). The AgNPs induced by inorganic salt ions were used as sensitive SERS substrate, and the electromagnetic field distribution of AgNPs with different distances was simulated by finite difference time domain (FDTD) to verify the theory feasibility. The PCA method was used to eliminate the limitations of overlapping of characteristic Raman peaks in structural analogues of 2,4-DCP, 2,4,5-TCP, and 2,3,4,6-TeCP. The proposed method shows great potentials in rapid, high-throughput, and sensitive monitoring of the contaminants in water and pesticide samples with similar structure.
在这项工作中，我们构建了一种简单、高通量且灵敏的基于表面增强拉曼光谱（SERS）和主成分分析（PCA）的分析方法，用于同时快速测定三种多氯酚（PCPs），包括 2,4-二氯苯酚（2,4-DCP）、2,4,5-三氯苯酚（2,4,5-TCP）和 2,3,4,6-四氯苯酚（2,3,4,6-TeCP）。利用无机盐离子诱导的聚集态 Ag 纳米颗粒（AgNPs）作为灵敏的 SERS 基底，并通过有限差分时域（FDTD）模拟不同距离的 AgNPs 的电磁场分布，以验证理论的可行性。通过商用的 96 孔板可实现高通量和快速检测。在最佳条件下，PCPs 的浓度与拉曼强度之间建立了线性关系，相关系数令人满意。通过 3σ 规则，2,4-DCP、2,4,5-TCP 和 2,3,4,6-TeCP 的检测限（LOD）分别为 0.27 mg/L、0.09 mg/L 和 0.10 mg/L。由于三种 PCPs 具有独立的拉曼特征峰，因此可以实现同时定量分析。随后，利用 PCA 方法消除了 2,4-DCP、2,4,5-TCP 和 2,3,4,6-TeCP 结构类似物中特征拉曼峰重叠的限制。包括单 PCP 和混合 PCP 样品的回收实验表明，回收率在 85.0%至 113.9%之间，相对标准偏差（RSD）在 0.4%至 9.5%之间；回收率在 80.4%至 114.0%之间，RSD 在 1.1%至 10.7%之间。该方法在快速、高通量和灵敏监测具有类似结构的水中和农药样品中的污染物方面具有很大的潜力。在这里，我们引入了由无机盐离子诱导的聚集态 Ag 纳米颗粒（AgNPs），用于同时、快速和灵敏地测定 2,4-二氯苯酚（2,4-DCP）、2,4,5-三氯苯酚（2,4,5-TCP）和 2,3,4,6-四氯苯酚（2,3,4,6-TeCP）等多氯酚（PCPs），该方法结合表面增强拉曼光谱（SERS）和主成分分析（PCA）。利用无机盐离子诱导的 AgNPs 作为灵敏的 SERS 基底，并通过有限差分时域（FDTD）模拟不同距离的 AgNPs 的电磁场分布，以验证理论的可行性。利用 PCA 方法消除了 2,4-DCP、2,4,5-TCP 和 2,3,4,6-TeCP 结构类似物中特征拉曼峰重叠的限制。该方法在快速、高通量和灵敏监测具有类似结构的水中和农药样品中的污染物方面具有很大的潜力。
