de Oliveira Rafael, Sant'Ana Antonio Carlos
Laboratório de Nanoestruturas Plasmônicas, Departamento de Química, Instituto de Ciências Exatas, Universidade Federal de Juiz de Fora, 36036-900 Juiz de Fora, Minas Gerais, Brazil.
Laboratório de Nanoestruturas Plasmônicas, Departamento de Química, Instituto de Ciências Exatas, Universidade Federal de Juiz de Fora, 36036-900 Juiz de Fora, Minas Gerais, Brazil.
Spectrochim Acta A Mol Biomol Spectrosc. 2024 Dec 5;322:124832. doi: 10.1016/j.saa.2024.124832. Epub 2024 Jul 14.
The vibrational assignment of the Raman and surface-enhanced Raman scattering (SERS) spectra of the herbicide tebuthiuron (TBH) was accomplished, which allowed unprecedented propositions for adsorption geometries on the surface of silver nanoparticles (AgNP). Ascribed SERS features allowed suggesting that the adsorption occurred through nitrogen atoms of thiadiazole group, since intense band shift assigned to ring mode was marking of the coordination with the metallic surface. AgNP were treated with different surface modifiers that leaded to substantial changes in TBH adsorption geometries. Spectral changes, as the enhancement of out-of-plane ring modes, were indicative of the presence of tilted thiadiazole geometries in relation to the silver surface. Density Functional Theory (DFT) calculations from TBH molecules, in isolation and in interaction with ten-atom cluster of silver leaded to obtain theoretical spectra that gave support to interpret experimental Raman and SERS spectra.
完成了除草剂特丁硫隆（TBH）的拉曼光谱和表面增强拉曼散射（SERS）光谱的振动归属，这为银纳米颗粒（AgNP）表面的吸附几何结构提供了前所未有的推断。归因于SERS的特征表明吸附是通过噻二唑基团的氮原子发生的，因为分配给环模式的强烈带移是与金属表面配位的标志。用不同的表面改性剂处理AgNP，导致TBH吸附几何结构发生显著变化。光谱变化，如面外环模式的增强，表明相对于银表面存在倾斜的噻二唑几何结构。对孤立的TBH分子以及与十个银原子簇相互作用的TBH分子进行密度泛函理论（DFT）计算，得到了理论光谱，为解释实验拉曼光谱和SERS光谱提供了支持。
