| Resonance Rayleigh Scattering (RRS) is a new analytical technique developed in 1990s. For its excellence of high sensitivity (detection limit of ng·mL-1 level), cheap instrument, simple operation and rapid analysis speed, the method has attracted to much attention and interest. At present, as the aggregation of dye chromophore on biological macromolecule leading to enhancement of RRS intensity, the method is mainly used to study biological macromolecules such as nucleic acids, proteins and heparin ect. Furthemrore, when two ions of different charges form ion association complexes by electrostatic force, hydrophobic force or charge transferring effect, RRS can be enhanced and the spectra charaeteristic can be changed. This method has been widely applied to the detemrination of trace metal ions, nonmetal ions, ogranic compounds, nanoparticles and pharmaceutical analysis.The present thesis consisted of two parts:overview and research reports.The overview involves the history, the basic principles, characteristics and the main systems of RRS, and the applications of RRS systems in pharmaceutical analysis in last five years are intensively reviewed.The searcher part of the reports mainly involves three aspects:Terbium-fluoroquinolones-alizarin red (AR) systems; Europium--fluoroquinolones--chromeazurol S (CAS) systems; Cobalt-fluoroquinolone--congo red (CR) systems. Their absorption (A), fluorescence and RRS spectral characteristies, optimum reaction conditions, influening factors and analytical applications have been studied. Furthermore, the reaction mechanism, the reason of A or RRS enhanced, and the relationships between RRS spectra and absorption spectra and the structures of the ion-association complexes are discussed. The main research contents are as follows:1. Study on Terbium--fluoroquinolones antibiotics--alizarin red systems by Resonance Rayleigh Scattering Spectra and their applicationIn the weak acid of HAc-NaAc buffer solution, fluoroquinolone antibiotics (FLQs) such as: fleroxacin (FLE), pefloxacin (PEFX), ciprofloxacin (CIP), lomefloxacin (LOM) and pazufloxacin (PAZ) can react with Tb (Ⅲ) to form chelated cations, which further bound with alizarin red (AR) to form the 2:1:1 (FLQs:Tb3+:AR) ternary ion-association complexes, resulting in the great enhancement of resonance Rayleigh scattering (RRS). The five reaction products have similar spectral characteristics and the maximum scattering wavelengths are located near 373 nm respectively. The linear ranges and the detection limits (3σ) of the FLQs are 0.04～3.69μg·mL-1, 22.7 ng·mL-1 for FLE at 373 nm; 0.03～3.33μg·mL-1,13.3 ng·mL-1 for PEFX at 373 nm; 0.03～ 3.31μg·mL-1,22.6 ng·mL-1 for CIP at 373 nm; 0.004～3.52μg·mL-1,14.3 ng·mL-1 for LOM at 370 nm; 0.16～3.18μg·mL-1,28.6ng·mL-1 for PAZ at 373 nm, respectively. The method, which is simple, rapid and selective, has been successfully applied to the determination of FLQs in tablet, injection, urine and human serum with satisfactory results. The mechanism of reaction has also been investeinged.2. Study on Europium--fluoroquinolones--chromeazurol S systems by Resonance Rayleigh Scattering Spectrum and their ApplicationIn the weak acid of HAc-NaAc buffer solution, fleroxacin (FLE), lomefloxacin (LOM) and ciprofloxacin (CIP) can react with Eu (Ⅲ) to form chelated cations, which further bound with chromeazurol S (CAS) by virtue of electrostatic attraction and hydrophobic force to form ternary ion-association complexes, resulting in the great enhancement of resonance Rayleigh scattering (RRS). A new method for the determination of FLQs based on RRS has been developed. The FLQs reaction products have similar spectral characteristics and the maximum scattering wavelengths are located at 361 nm and 560 nm respectively. The linear ranges and the detection limits (3a) of the FLQs are 0.037-3.69μg·mL-1,55.8 ng·mL-1 for FLE; 0.035～3.52μg·mL-1,14.5 ng·mL-1 for LOM; 0.033～3.31μg·mL-1,12.4 ng·mL-1 for CIP at 361 nm, respectively. The method, which is simple, rapid and selective, has been successfully applied to the determination of FLQs in tablet, injection, urine and human serum with satisfactory results.3. Study on Cobalt--fluoroquinolone antibiotics--congo red systems by Resonance Rayleigh Scattering Spectrum and their ApplicationIn the weak acid of Britton-Robinson buffer solution,fleroxacin (FLE), gatifloxacin (GTFX), and pefloxacin (PEFX) can react with Co(Ⅱ)to form a chelated cation, but its resonance Rayleigh scattering(RRS) was very weak. Significant enhancement of RRS intensity and new RRS spectrum was observed when the chelated cation further reacts with congo red to form an ion association complexe showing two scattering peaks near 372 nm and 560 nm respectively. The linear ranges and the detection limits (3σ) of the FLQs are 0.03～3.69μg·mL-1,6.0 ng·mL-1 for FLE at 372 nm; 0.03～5.26μg·mL-1,7.5 ng·mL-1 for GTFX at 382 nm; 0.033～3.31μg·mL-1,26.4 ng·mL-1 for PEFX at 380 nm, respectively. The proposed method has been applied to the determination of fluoroquinolone antibiotics in tablet, human urine and plasma with satisfactory results. |
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