MD and DFT Calculations to Analyze Raman and SERS Spectra of Paraquat—From Computer Aided Spectra Interpretation to Pesticide Identification

Andrea Hermsen, Florian Hertel, Dominik Wilbert, Christian Mayer, Martin Jaeger
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Abstract

The use of pesticides is an important practice in today's agricultural and nutritional supply chain worldwide. Their potentially harmful effects require rapid and reliable monitoring. As an emerging technology, surface-enhanced Raman spectroscopy (SERS) is paving its way through established methodologies. The Raman enhancing effect is based on the interaction of the analyte and nanoparticles prepared from noble metals. To better support and exploit analytical applications, the interaction between gold nanoparticles and the pesticide paraquat were studied. To this purpose, molecular dynamic calculations were performed with paraquat on single-crystal structures of gold at a distance of 3.4 Å and an intramolecular dihedral angle of 18.8° between the two paraquat ring systems. The molecular dynamic calculations showed that the two noble metal surface models exhibited only slight differences in their effects on paraquat. Experimental SERS spectra with gold nanoparticles were recorded and compared to the experimental Raman spectrum. The observed differences were further investigated using density functional theory calculations and reducing the gold cell to a gold cluster of 20 atoms. A co-planar orientation of paraquat to the gold cluster surface was thereby deduced. Based on an optimized paraquat geometry including a dihedral angle of 36.77° at a distance of 3.85 Å to the gold cluster, an excellent agreement between computed and experimental spectra was obtained. A head-on geometry was discarded due to spectral mismatch. This computational approach may help to analyze SERS spectra and make SERS further suitable for pesticide analysis.

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农药的使用是当今世界农业和营养供应链中的一项重要实践。需要对其潜在的有害影响进行快速可靠的监测。作为一项新兴技术,表面增强拉曼光谱(SERS)正在通过成熟的方法铺平道路。拉曼增强效应基于分析物与贵金属制备的纳米颗粒之间的相互作用。为了更好地支持和利用分析应用,我们研究了金纳米粒子与农药百草枯之间的相互作用。为此,研究人员在金的单晶结构上对百草枯进行了分子动力学计算,两个百草枯环系统之间的距离为 3.4 Å,分子内二面角为 18.8°。分子动力学计算表明,两种贵金属表面模型对百草枯的影响仅有微小差异。记录了金纳米粒子的实验 SERS 光谱,并与实验拉曼光谱进行了比较。利用密度泛函理论计算并将金单元缩小为 20 个原子的金簇,进一步研究了观察到的差异。由此推断出百草枯在金簇表面的共面取向。基于优化的百草枯几何形状,包括与金簇的距离为 3.85 Å、二面角为 36.77°,计算光谱与实验光谱之间获得了极好的一致性。由于光谱不匹配,我们放弃了正面几何图形。这种计算方法可能有助于分析 SERS 光谱,并使 SERS 进一步适用于农药分析。
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