Study On The Applications Of Resonance Rayleigh Scattering Spectra In Natural Medicine Analysis

Resonance Rayleigh scattering (RRS) is a new analytical technology developed in recent ten years. For its remarkable characteristics of high sensitivity, simple operation and good selectivity, this method brings to more attention and interesting and has been studied and applied more and more. At present, as the aggregation of dye chromophore on biological macromolecule leading to enhancement of RRS intensity, these methods are mainly used to study biological macromolecules such as nucleic acids, proteins and heparin ect. Furthermore, when two ions of different charges form ion association complexes by electrostatic force, hydrophobic force or charge transferring effect, RRS and RNLS (resonance nonlinear scattering)(including double frequency (FDS) or second order scattering (SOS)) can be enhanced and the spectra characteristic can be changed. These methods have been used to determination of trace metal ions, nonmetal ions, organic compounds and pharmaceutical analysis.Pharmaceutical analysis is an important part of analytical chemistry. As natural medicine becomes more and more important, the research is necessary and it needs to develop more and more new analytical technology and analytical methods. Up to now, these are few reports about the applications of RRS and RNLS in natural medicines. This dissertation indicates when some effective compositions react with small molecular or biological macromolecule, RRS can be enhanced and new RRS spectrum appears. The researches have important application prospects and worth to further studies.In this dissertation berberine hydrochloride, tanshinone IIA and their modificatial product sodium tanshinon IIA silate, morin, glycyrrhizinic acid and their modificatial product glycyrrhizinic acid monoammonium are as examples to study the interaction ofalkaloids, quinones, flavone and saponins with metal ions, metal complex anions or some natural medicines. Their RRS spectral characteristics, optimum reaction conditions, influencing factors and analytical applications have been studied. Furthermore, the reaction mechanism, the reasons of RRS enhanced the relationships between RRS spectra and absorption spectra and the structures of the ion-association complexes and coordination complexes are discussed.In addition, this dissertation expatiate the category, pharmacologic effects and the analytical methods of traditional Chinese medicines; introduces the elementary properties of resonance Rayleigh scattering and their applications in scientific research, reviews the developing course of this technique and discusses mainly the theoretical basement, the present situation of application and the development of RRS as analytical technique.Under the supports of the National Natural Science Foundation of China (Grant No.20175018 and 20175019), we studied the follow research systems:1 Resonance Rayleigh scattering spectrum of the interaction between chloroauric acid and berberine hydrochloride and its analytical applicationsIn a pH 2.0 HCl-NaAc buffer solution, when berberine cation reacts with chloroauric acid anion by electrostatic force and hydrophobic force to form an ion association complex, the RRS intensity can be enhanced greatly and a new RRS spectrum appears. The maximum RRS peak is at 370nm and another RRS peak locates at 277nm. There is a linear relationship between the RRS intensity and the berberine concentration in the range of 0~5.0><10" mol/L. The method is very sensitive and the detection limit (3o7K) for berberine hydrochloride is 1.83><10"8mol/L (7.5ng/mL). The optimum condition and the effect of coexisting substances had been discussed and the results show the method also has good selectivity. Base on RRS spectrum of the ion association complex, a method of high sensitive, simple and rapid for the determination of trace amounts of berberine has been developed. It has been applied to the determination of berberine in pharmaceuticals and goldthread extracts with satisfactory results. Furthermore, the reasons of enhancement of RRS are discussed.2 A Study on the interaction of [HgX4]2' with berberine by absorption and resonance Rayleigh scattering spectra and their analytical applicationsIn a diluted H2SO4 solution, Hg(II) react with halide anions X" (including Cl", Br" and I") to form the anionic complexes [HgX4]2", which can further react with berberine to the formation of ion-association complexes [Ber]2[HgX4]. As the result, the absorption spectra changes and their maximum absorption wavelength are at 230nm for [Ber]2[HgCl4], 278nm for [Ber]2[HgBr4] and 300nm for [Ber]2[HgI4]. However, among the three complexes, only [Ber]2[Hgl4] can lead a distinctly enhanced Resonance Rayleigh scattering (RRS) and a new RRS spectrum appeared. The maximum RRS wavelength is located at 397nm and the RRS intensity is proportional to the concentration of berberine in the range of 0~2.5jig/mL. The optimum conditions, the influence factors for the reaction and the effects of coexisting substances have been investigated. A new, simple and fast RRS method for the determination of berberine based on the ion-association reaction of [Hgl4]2" with Ber+ was developed. The method has high sensitivity and good selectivity, and the detection limit for berberine (3a/K) is 7.22ng/mL. The method can be applied to the determination of berberine in some Chinese patent drug and the extracts of Coptis Chinensis. Furthermore, the mechanism of the reaction and the reasons of RRS enhancement have been discussed.3 Synthesis of sodium tanshinon IIA silate and its characterization, spectral characteristics and analytical applicationBy the way of UV-vis absorption spectrum, fluorescent spectrum, infrared absorption spectrum and nuclear magnetic resonance spectroscopy, sodium tanshinon IIA silate was characterized and identified. The characteristics of its UV-vis absorption spectrum and fluorescent spectrum have been discussed. At first, a HPLC method for the determination of sodium tanshinon IIA silate was developed. Furthermore, in a pH3.3 HAc-NaAc buffer solution, sodium tanshinon IIA silate was determined by fluorometric method in the linear range of 0~40ug/mL and the detection limit for sodium tanshinon IIA silate (3a/K) is 11.67ng/mL. A new, simple and sensitive fluorometric method for the determination of sodium tanshinon IIA silate was developed. It can be applied to the determination oftanshinon IIA silate in the synthesis processes and Nuoxinkang injection and the results were compared to HPLC method with satisfactory results.4 Resonance Rayleigh scattering of the chelate for lanthanum (III) with sodium tanshinon IIA silate and its analytical applicationIn a pH3.6-5.0 HAc-NaAc buffer solution, when sodium tanshinon IIA silate reacted with La (III) to form a chelate, the resonance Rayleigh scattering (RRS) intensity could be enhanced greatly and a new RRS spectrum appeared. The maximum RRS peak was located at 306nm and the RRS intensity was proportional to the concentration of sodium tanshinon IIA silate. The method is very sensitive and the detection limit for sodium tanshinon IIA silate (3o7K) is 82.12ng/mL. The optimum conditions and the effect of coexisting substances had been investigated. A new, simple and fast method for the determination of sodium tanshinon IIA silate base on RRS method was developed. It can be applied to the determination of tanshinon IIA silate in the synthesis processes and Nuoxinkang injection. Combined with infrared absorption spectrum and NMR spectrum, the structure of the chelate and the reasons of RRS enhancement were investigated also.5 A Study on the interaction of morin and berberine by resonance Rayleigh scattering spectra and its analytical applicationIn a pH 5.5 BR buffer solution, when morin reacts with berberine by electrostatic force and hydrophobic force to form an ion association complex, the RRS intensity can be enhanced greatly and a new RRS spectrum appears. The maximum RRS peak is at 467nm. There is a linear relationship between the RRS intensity and the berberine concentration in the range of 0-4.0xlO"5mol/L. The method is very sensitive and the detection limit (3a/K) for morin is 4.18><10"8 mol/L (14.14ng/mL) . The optimum condition and the effect of coexisting substances had been discussed and the results show the method also has good selectivity. Base on RRS spectra of the ion association complex, a method of high sensitive, simple and rapid for the determination of trace amounts of morin has been developed. It has been applied to the determination of morin in mulberry...