| In this paper, some medicine such as granisetron hydrochloride, tropisetron hydrochloride, ciprofloxacin, pipemidic acid, lomefloxacin, norfloxacin, lysozyme and papain were studied by absorption, fluorescence and resonance Rayleigh scattering spectra. The actions between these medicines and [PW12O40]3-、MoO42-and Pd (Ⅱ), the mechanisms of interactions, the binding modes, the binding sites and the forces were investigated and new methods for determination of granisetron hydrochloride, ciprofloxacin, lysozyme and so on were established. The main work of this thesis is as follows:1. Study on the interactions of antiemetic drugs and12-tungstophosphoric acid and its analytical applicationIn0.1mol·L-1HCl medium, some antiemetic drugs (ATM) such as granisetron hydrochloride (GS) and tropisetron hydrochloride (TS) could react with H3PW12O40·nH2O to form3:1ion-association complex of [(ATM)3PW12O40], which would self-aggregate to form nanoparticles-[(ATM)3PW12O40]n with an average size of100nm. This resulted in the enhancement of resonance Rayleigh scattering (RRS) and UV-vis absorption (UV). The increments of scattering intensity (A/RRS) and absorbance (△A) were both directly proportional to the concentrations of ATM in certain ranges. Accordingly, new RRS and UV methods were proposed for ATM detection. The detection limits (3δ) of GS and TS were3.2ng·mL-1and4.0ng·mL-1(RRS method),112.5ng·mL-1and100.0ng·mL-1(UV 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)3PW12O40]n was characterized by atomic force microscopy (AFM). Take the RRS method which was more sensitive as an example, the reaction mechanism and the reasons for enhancement of scattering were discussed.2. Study on Methyl Orange-Quinolones-Pd (II) Systems by Resonance Rayleigh Scattering Spectra and Their Analytical ApplicationsA new method based on the resonance Rayleigh scattering (RRS) was proposed for the determination of quinolones (QNS) at the nanogram level. In pH3.3-4.4BR buffer medium, QNS such as ciprofloxacin (CIP), pipemidic acid (PIP), lomefloxacin (LOM), norfloxacin (NOR) and sarafloxacin (SAR) were protonated and reacted with methyl orange (MO) to form ion-pair complex, then formed6-membered ring chelate with Pd(Ⅱ). As a result, new spectra of resonance Rayleigh scattering appeared and their intensities were enhanced greatly. The RRS spectral characteristics of the MO-QNS-Pd (Ⅱ) systems, the optimum conditions of the reaction, and the influencing factors have been investigated. Under the optimum conditions, the increments of scattering intensity (AT) were directly proportional to the concentration of QNS in certain ranges. The method had high sensitivity, and the detection limits (3δ) ranged from6.8ng·mL-1to12.6ng·mL-1. The proposed method has been successfully applied for the determination of QNS in pharmaceutical formulation and human urine sample. In addition, the mechanism of the reaction system was discussed by the IR spectra, absorption spectra and fluorescence spectra. The reasons for the enhancement of scattering spectra were discussed in some ways, such as fluorescence-scattering resonance energy transfer, hydrophobicity and molecular size.3. Study on the ternary system of MoO42--Enzyme-PdCl2by resonance Rayleigh scattering, second order scattering and frequency doubling scattering spectra and its analytical applicationIn pH4.0BR buffer medium, PdCl2could react with enzyme (EZ) such as lysozyme (Lyso) and papain (Pa) to form coordination complex (EZ-PdCl2), which further react with MoO42-to form ternary complex (MoO42--EZ-PdCl2). As a result, not only the absorption spectra and fluorescence spectra changed, but also the new spectra of resonance Rayleigh scattering (RRS), second order scattering (SOS) and frequency doubling scattering (FDS) appeared and their intensities were enhanced greatly. The maximum RRS, SOS and FDS wavelengths of two ternary complexes were located at310nm,560nm and350nm, respectively. The increments of scattering intensity (A/RRS, A/SOS and A/FDS) were directly proportional to the concentrations of Lyao (or Pa) in certain ranges. The detection limits (3δ) of Lyso and Pa were4.5ng·mL-1and14.0 ng·mL-1(RRS method),9.6ng·mL-1and57.8ng·mL-1(SOS method),5.2ng·mL-1and106.0ng·mL-1(FDS method), respectively. Take the MoO42-Lyso-PdCl2:system which was more sensitive as an example, the effects of coexisting substances were evaluated. The methods showed excellent selectivity. Accordingly, new rapid, convenient, sensitive and selective scattering methods for determination of Lyso and Pa were proposed and applied to determine Lyso in egg white with satisfactory results. The reaction mechanism and the reasons for enhancement of scattering were discussed. |
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