Key Laboratory on Luminescence and Real-Time Analysis, Ministry of Education, School of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, China.
Spectrochim Acta A Mol Biomol Spectrosc. 2013 Mar 15;105:612-7. doi: 10.1016/j.saa.2012.12.094. Epub 2013 Jan 10.
In 0.1 mol L(-1) HCl medium, antiemetic drugs (ATM), such as granisetron hydrochloride (GS) and tropisetron hydrochloride (TS), reacted with H(3)PW(12)O(40)·nH(2)O and formed 3:1 ion-association complex of [(ATM)(3)PW(12)O(40)], then self-aggregated into nanoparticles-(ATM)(3)PW(12)O(40) with an average size of 100 nm. The reaction resulted in the enhancement of resonance Rayleigh scattering (RRS) and the absorption spectra. The increments of scattering intensity (ΔI(RRS)) and the change of absorbance (ΔA) were both directly proportional to the concentrations of ATM in certain ranges. Accordingly, two new RRS and spectrophotometric methods were proposed for ATM detection. The detection limits (3σ) of GS and TS were 3.2 ng mL(-1) and 4.0 ng mL(-1)(RRS method), 112.5 ng mL(-1) and 100.0 ng mL(-1)(spectrophotometric method). These two methods were applied to determine GS in orally disintegrating tablets and the results were in good agreement with the official method. The ground-state geometries and electronic structures of GS and TS were optimized by the hybrid density functional theory (DFT) method and the shape of (ATM)(3)PW(12)O(40) was characterized by atomic force microscopy (AFM). Take the RRS method with higher sensitivity as an example, the reaction mechanism and the reasons for enhancement of scattering were discussed.
在 0.1 mol L(-1) HCl 介质中,止吐药物(ATM),如盐酸格拉司琼(GS)和盐酸托烷司琼(TS),与 H(3)PW(12)O(40)·nH(2)O 反应形成 3:1 的离子缔合配合物 [(ATM)(3)PW(12)O(40)],然后自组装成平均粒径为 100nm 的纳米粒子-(ATM)(3)PW(12)O(40)。反应导致共振瑞利散射(RRS)和吸收光谱增强。散射强度(ΔI(RRS))的增量和吸光度(ΔA)的变化都与 ATM 在一定范围内的浓度直接成正比。因此,提出了两种新的用于 ATM 检测的 RRS 和分光光度法。GS 和 TS 的检测限(3σ)分别为 3.2ng mL(-1)和 4.0ng mL(-1)(RRS 法)、112.5ng mL(-1)和 100.0ng mL(-1)(分光光度法)。这两种方法均用于测定口腔崩解片中的 GS,结果与官方方法吻合良好。通过混合密度泛函理论(DFT)方法对 GS 和 TS 的基态几何形状和电子结构进行了优化,并通过原子力显微镜(AFM)对 (ATM)(3)PW(12)O(40) 的形状进行了表征。以灵敏度更高的 RRS 方法为例,讨论了反应机制和散射增强的原因。