【作者】 宋彦琪；

【导师】 胡小莉；

【作者基本信息】 西南大学 ， 无机化学， 2010， 硕士

【摘要】 生物碱和磺胺类药物无论是在数量上还是在药用性质方面,都具有其独特的地位。本文主要以苦参碱(Mat)、氧化苦参碱(Oxy)、硫酸阿托品(AS)、丁溴东莨菪碱(HBB)和磺胺二甲嘧啶(SM2)为研究对象,研究、发展和建立简便快速的测定生物碱类和磺胺类药物的共振瑞利散射(Resonance Rayleigh Scattering,RRS)、二级散射(Second-Order Scattering, SOS)和倍频散射(Frequency Doubling Scattering, FDS)方法,并将这些方法运用于生物制剂和天然药物的检测中。研究体系如下：1.共振瑞利散射和共振非线性散射光谱法测定苦参中的苦参碱和氧化苦参碱在0.1 mol／L(pH 1.0)的HCl介质中,12-钨磷酸(TP)和苦参碱(Mat)、氧化苦参碱(Oxy)结合形成离子缔合物,引起共振瑞利散射(RRS)、二级散射(SOS)和倍频散射(FDS)显著增强,并产生新的RRS, SOS和FDS光谱。最大RRS,SOS和FDS峰分别位于370 nm,670 nm和393 nm,散射强度在一定范围内与Mat和Oxy的浓度成正比,据此建立测定Mat和Oxy的新方法。本方法具有较高的灵敏度,检出限在3.3～40.8 ng／mL范围内。考察了体系的RRS、SOS、FDS和吸收光谱特征,优化了适宜的测定条件,实验了常见共存物质的影响,表明该方法具有良好的选择性,可用于苦参中Mat和Oxy的测定,结果满意。对离子缔合反应机理和RRS增强的原因进行了讨论。2.共振瑞利散射法测定硫酸阿托品眼膏中的硫酸阿托品在pH范围为3.0～4.5的HAc-NaAc缓冲溶液中,建立了简便快速的测定硫酸阿托品眼膏中硫酸阿托品(AS)含量的共振瑞利散射(RRS)方法。I3-与AS反应形成离子缔合物,导致共振瑞利散射强度的增强。最大散射峰634 nm处,AS浓度在一定范围内与散射增强程度成良好线性关系,据此提出测定AS的新方法。检出限(3σ)为6.5 ng/mL。考察了体系的光谱特征、适宜的反应条件和共存物质的影响。方法具有良好的选择性,可用于硫酸阿托品眼膏中AS的测定。3.共振瑞利散射法测定丁溴东莨菪碱胶囊中丁溴东莨菪碱的含量在pH 5.0的条件下,建立了简便快速的测定丁溴东莨菪碱(HBB)的共振瑞利散射(RRS)方法。I3-与HBB反应形成离子缔合物,导致共振瑞利散射强度的增强,最大散射峰位于623 nm处,HBB浓度在一定范围内与散射增强程度成良好线性关系,据此提出测定HBB的新方法。本法具有较高灵敏度,其检出限为5.7 ng／mL,可用于胶囊中HBB含量的测定。4.二卤代荧光素-Ag+共振瑞利散射法测定丁溴东莨菪碱在pH 4.2～5.6 HAc-NaAc缓冲溶液的条件下,丁溴东莨菪碱(HBB)与Ag+和二卤代荧光素染料(二氯荧光素DCF,二溴荧光素DBF和二碘荧光素DIF)反应形成离子缔合物,导致共振瑞利散射强度的增强,最大散射峰分别位于322 nm(DCF)、320 nm(DBF)、335 nm(DIF)处。HBB浓度在一定范围内与散射增强程度成良好线性关系,据此提出测定HBB的新方法。考察了体系的光谱特征、适宜的反应条件和共存物质的影响。方法用于胶囊中HBB的测定,结果与文献一致。文中对离子缔合反应机理和RRS增强的原因进行了讨论。5.高锰酸钾共振瑞利散射法测定磺胺二甲嘧啶在0.2 mol／L H2SO4介质中,磺胺二甲嘧啶(SM2)和KMnO4在加热条件下发生氧化还原反应生成MnO2微粒,导致共振瑞利散射增强,并产生新的散射峰。其最大散射波长位于595 nm附近,散射强度在一定范围内与SM2的浓度成正比,据此建立了测定SM2的RRS新方法。本方法具有较高的灵敏度,检出限为8.6 ng／mL。实验优化了测定条件,考察了共存物质的影响,表明方法具有良好的选择性,用于片剂中SM2的测定,结果满意。更多还原

【Abstract】 Alkaloids and sulfonamides, whether in quantity or in the medicinal properties, have unique position. New RRS, SOS and FDS methods for the determination of matrine, oxymatrine, atropine sulphate, hyoscine butylbromide and sulfadimidine have been established and developed. It can be used in the determination of trace drugs in the natural medicine and the pharmaceutical preparation. Main investigated systems are listed as follow:1. Determination of Matrine and Oxymatrine in Radix Sophorae Flavescentis by Resonance Rayleigh Scattering and Resonance Nonlinear Scattering SpectraIn 0.1 mol/L （pH 1.0） HCl medium,12-tungstophosphoric acid （TP） reacted with matrine （Mat） and oxymatrine （Oxy） to form an ion-association complex. As a result, 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 wavelengths of RRS, SOS and FDS were located at 370 nm,670 nm and 393 nm, and the scattering intensities were proportional to the concentration of Mat and Oxy in certain ranges. Based on this, new methods for the determination of Mat and Oxy have been established. The detection limits （3σ） of these methods were in the range of 3.6～28.2 ng/mL. The RRS, SOS, and FDS characteristics, absorption spectrum characteristics and optimum reaction conditions of these systems were discussed. Effects of coexistent substances were tested, and the results demonstrated that the methods had good selectivity. It has been applied to the determination of Mat and Oxy in samples of radix sophorae flavescentis with satisfactory result. The reaction mechanism and reasons of RRS enhancement were discussed.2. Determination of Atropine Sulphate in Atropine Sulphate Eye Ointment by Resonance Rayleigh Scattering TechniqueIn pH 3.0-4.5 HAc-NaAc buffer medium, a resonance Rayleigh scattering method was developed for the determination of atropine sulphate （AS）. I₃^- reacted with AS to form an ion-association complex. As a result, the new spectra of resonance Rayleigh scattering （RRS） appeared and the intensities were enhanced greatly. The maximum wavelength of RRS was located at 634 nm. The scattering intensities were proportional to the concentration of AS. The detection limit （3a） was 6.5 ng/mL. The spectra characteristics, the optimum reaction conditions and influencing factors have been discussed. The method was selective. It has been applied to the determination of AS in atropine sulphate eye ointment with satisfying results.3. Determination of Hyoscine Butylbromide in Hyoscine Butylbromide Capsules by Resonance Rayleigh Scattering TechniqueIn pH 5.0 medium, a resonance Rayleigh scattering method was developed for the determination of hyoscine butylbromide （HBB）. I₃^- reacted with HBB to form an ion-association complex. As a result, the new spectra of resonance Rayleigh scattering （RRS） appeared and the intensities were enhanced greatly. The maximum wavelength of RRS was located at 623 nm. The scattering intensities were proportional to the concentration of HBB. The detection limit （3a） was 5.7 ng/mL. The spectra characteristics, the optimum reaction conditions and influencing factors had been discussed. The method is selective. It has been applied to the determination of HBB in capsules with satisfying results.4. Determination of Hyoscine Butylbromide with Ag⁺and Dihalogenated Fluorescein Dyes in Capsules by Resonance Rayleigh Scattering TechniqueIn pH 4.2～5.6 HAc-NaA buffer solution, hyoscine butylbromide （HBB） reacts with Ag⁺ and dihalogenated fluorescein dyes such as dichlorofluorescein （DCF）, dibromofluorescein （DBF） and diiodofluorescein （DIF） to form a ion-association complex. This resulted in the significant enhancement of RRS intensity. The maximum wavelengths of RRS were located at 322 nm （DCF）,320 nm （DBF） and 335 nm （DIF）, respectively. The scattering intensities were proportional to the concentration of HBB. Based on these, new methods for the determination of HBB have been established. The spectra characteristics, the optimum reaction conditions and influencing factors have been discussed. It has been applied to the determination of HBB in capsules and the results were in good agreement with those obtained by the literature methods.5. Determination of Sulfadimidine with Potassium Permanganate by Resonance Rayleigh Scattering TechniqueIn 0.20 mol/L H2SO4 medium, a redox reaction took place between sulfadimidine （SM2） and potassium permanganate to form MnO₂ particles by heating. As a result, the new spectra of resonance Rayleigh scattering appeared and their intensities were enhanced greatly. The maximum peak of RRS was located at 595 nm, and the scattering intensities were proportional to the concentration of SM2. Based on it, a new method for the determination of SM2 has been established. The detection limit （3σ） was 8.6 ng/mL. Effects of coexistent substances were tested, and the results demonstrated that this method had good selectivity. It has been applied to the determination of SM2 in tablet with satisfactory results.更多还原