| Resonance Rayleigh scattering(RRS)and resonance non-linear scattering(RNLS) were a new technology developed in1990s. Due to its remarkable characteristics of simple operation and high sensitivity, this method has received much attention. In this thesis, taking a,-receptor blocker drugs and famciclovir as research objects. we developed some new systems and methods for the determination of them by RRS and RNLS methods. The optimum conditions and the influencing factors were investigated. The reaction mechanisms and the reasons for RRS enhancement of the svstems were discussed. Main investigated systems are listed as follows:1. Resonance Rayleigh Scattering Spectra of a1-receptor blocker drugs and Some Isopoly Acids and Their Analytical ApplicationIn an acid solution, an isopoly-acid anion such as isopoly-molybdic acid or isopoly-tungstic acid could react with prazosin hydrochloride(PRH)and doxazosin mesyllate(Dox) α1-receptor blocker drugs to form ion-association complexes respectively. It resulted in the great enhancement of Resonance Rayleigh Scattering(RRS)intensities and new RRS spectra appear, and the maximum RRS wavelength was located at367nm(isopoly-molybdic acid system)and290nm(isopoly-tungstic acid system). The reaction products of the two drugs had similar spectral characteristics. The optimum pH ranges are2.1～2.3for isopoly-molybdic acid-PRH system and3.1～3.3for isopoly-tungstic acid-PRH system, respectively. In a certain range, the intensities of RRS are directly proportional to the concentration of drugs in the two different reaction systems. The reactions have high sensitivity and the detection limit(3s/s)of PRH is4.76ng/mL(isopoly-molybdic acid-PRH system)and9.88ng/mL(isopoly-tungstic acid-PRH system). The method also has good selectivity. It was applied to the determination of α,-receptor blocker drugs in tablets and human urine samples. In this paper, Gaussview3.07and Gaussian03W softwares at a B3LYP/6-31G(base group)level based on the density functional theory(DFT)were used to calculate the charge distribution of PRH for investigating the reaction mechanism; in addition, the reasons for RRS enhancement of the system were discussed.2. Study on the interaction between a1-receptor blocker drugs and Some Anionic Surfactants by resonance Rayleigh scattering and resonance nonlinear scattering spectra and its analytical applicationsIn an acid solution, anionic surfactants(AS)such as sodium dodecylbenzene sulfonate(SDBS) or sodium dodecylsulphate(SDS)could react with doxazosin mesyllate(Dox) and prazosin hydrochloride(PRH) a,-receptor blocker drugs to form ion-association complexes respectively. It resulted in the great enhancement of resonance Rayleigh Scattering(RRS), second-order scattering(SOS) and frequency doubling scattering(FDS)intensities and new scattering spectra appeared. The maximum RRS, SOS and FDS wavelength was located at288,544and391nm(sodium dodecylbenzene sulfonate system and sodium dodecylsulphate system). The reaction products of the two drugs had similar spectral characteristics. The optimum pH ranges are3.2-3.4for sodium dodecylbenzene sulfonate-Dox system and3.1～3.3for sodium dodecylsulphate-Dox system, respectively. In a certain range, the intensities of RRS, SOS and FDS were directly proportional to the concentration of drugs in the two different reaction systems. The reactions have high sensitivity and the detection limit(3s/s)of Dox were4.49(RRS)、8.28(SOS) and10.4ng/ml (FDS)(sodium dodecylbenzene sulfonate-Dox system)and4.52(RRS、9.63(SOS) and12.2ng/ml (FDS)(sodium dodecylsulphate-Dox system). The method also has good selectivity. It was applied to the determination of a1-receptor blocker drugs in capsuleis and human urine samples. In this paper, Gaussview3.07and Gaussian03W softwares at a B3LYP/6-31G(base group)level based on the density functional theory(DFT)were used to calculate the charge distribution of Dox for investigating the reaction mechanism; in addition, the reasons for RRS enhancement of the system were discussed. 3. Resonance Rayleigh Scattering, Second-order Scattering and Frequency Doubling Scattering Spectra of α,-receptor blocker drugs and Some Heteropoly Acids and Their Analytical ApplicationsIn an acid solution, heteropoly acids such as phosphomolybdic acid (Pma) or phosphowolframic acid (Pwa) could react with prazosin hydrochloride (PRH) and doxazosin mesyllate (Dox) a1-receptor blocker drugs to form ion-association complexes respectively. It resulted in the great enhancement of resonance Rayleigh Scattering (RRS). second-order scattering (SOS) and frequency doubling scattering (FDS) intensities and new scattering spectra appeared. The maximum RRS. SOS and FDS wavelength was located at369.585,390nm (phosphorus-molybdenum heteropoly acid system) and369,624,390nm (phosphowolframic acid system). The reaction products of the two drugs had similar spectral characteristics. In a certain range, the intensities of RRS, SOS and FDS were directly proportional to the concentration of drugs in the two different reaction systems. The reactions have high sensitivity and the detection limit(3s/s) of PRH were3.1(RRS).8.6(SOS) and8.7ng/ml (FDS)(phosphorus-molybdenum heteropoly acid-PRH system) and5.3(RRS).15.2(SOS) and9.6ng/ml (FDS)(phosphowolframic acid-PRH system). The method also has good selectivity. It was applied to the determination of α1-receptor blocker drugs in tablets and human urine samples. In this paper. Gaussview3.07and Gaussian03W softwares at a B3LYP/6-31G (base group) level based on the density functional theory (DFT) were used to calculate the charge distribution of PRH for investigating the reaction mechanism; in addition, the reasons for RRS enhancement of the system were discussed.4. Study on the Interaction between Doxazosin mesyllate Metal Complex and Lissamine green by Resonance Rayleigh Scattering Spectra and Its Analytical ApplicationIn pH3.8HAc-NaAc buffer medium, doxazosin mesyllate (Dox) react with mercury(Ⅱ)(Hg(Ⅱ))、copper(II)(Cu(Ⅱ)、cobalt(II)(Co(Ⅱ))to forml:1cationic chelates, which further react with Lissamine green (LG)to form1:1ternary ion-association complexes. As a result, the reactions result in the great enhancement of Resonance Rayleigh Scattering(RRS) intensities. Their spectral characteristics of RRS are similar and the maximum RRS wavelengths are all located at365nm. But the increments of RRS intensity are different in the series of Hg(II)> Cu(II)> Co(Ⅱ). The enhanced RRS intensities are proportional to the concentration of Dox during a certain range. The detection limits(3s) are7.93ng/mL (Hg2+system),9.94ng/mL(Cu2+system) and15.1ng/mL (Co2+system). In this paper, the optimum conditions of the reactions and the effects of foreign substances are investigated. Based on the ion-association reaction, a highly sensitive, simple and rapid method has been proposed to the determination of Dox.5. Study on the Interaction of Pd (Ⅱ)-Famciclovir with Chrome Azurol S by Resonance Rayleigh Scattering Spectra and Their Analytical ApplicationObjiective:To develop resonance rayleigh scattering(RRS) method for the determination of Famciclovir (FCV). Method:In Britton-Robinson buffer of pH2.95, FCV, palladium (II) and Chrome Azurol S (CAS) with proper properation were mixed. After a while, it was put in Hitachi F-2500and determined the RRS spectra. Result:FCV reacts with palladium (II) to form1:1anionic chelates. Which react further with CAS to form the ion-association complexes. The reactions result in the great enhancement of RRS intensities and new RRS spectra appear. The maximum RRS wavelength locates at367nm. Under the optimum conditions, the intensities of RRS are proportional to the concentration of FCV. The linear range is0.02-2.4μg-mL"1for the system. Conclusion:A method can be used to determine FCV based on our experiments. The method has high sensitivity and the detection limit of FCV is3.6ng-mL-1. The reaction conditions of the system and the effect of coexisting substances were investigated. In addition, the reaction mechanism and the reasons for RRS enhancement of the system were investigated. A simple quick and high sensitive method is developed for the determination of FCV. The method can be applied satisfactorily to determination of FCV in capsule and urine samples. |
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