【作者】 王齐；

【导师】 刘绍璞；

【作者基本信息】 西南大学 ， 分析化学， 2007， 硕士

【摘要】 共振瑞利散射（RRS）和非线性散射（RNLS）技术作为新兴的、简便的、高灵敏的分析技术受到人们的广泛关注，国内外已用于痕量无机金属离子、非金属离子、药物及生物化学分析研究，获得了较好的效果。本文以CdS、ZnS和Cu纳米微粒为新型无机纳米探针，研究了研究了它们与某些药物和生物大分子之间相互作用的RRS光谱其分析应用。本文主要的研究内容如下：1硫化镉纳米微粒与某些药物相互作用的共振瑞利散射光谱研究及其分析应用1．1硫化镉纳米微粒作探针共振瑞利散射测定某些蒽环类抗癌药物在pH5．0～9．0的水溶液中，硫化镉纳米微粒[（CdS）_n]与蒽环类抗生素米托蒽醌（MXT）、表柔比星（DNR）和柔红霉素（EPI）借静电引力、疏水作用力结合，形成粒径更大的聚集体，导致共振瑞利散射（RRS）的增强并产生新的RRS光谱，最大RRS峰位于292nm（MXT体系）、285nm（DNR体系）和315nm（EPI体系）。与此同时也观察到二级散射（SOS）和倍频散射（FDS）强度明显提高。其最大SOS峰位于540nm（MXT体系）和560nm（EPI、DNR体系），而最大FDS峰分别位于335nm（MXT体系）、320nm（EPI体系）和330nm（DNR体系）。在一定条件下，三种散射强度（△I）均与药物的浓度成正比，反应具有高灵敏度，对于三种药物的检出限在3.6～9.1ng／mL之间。其中（CdS）_n-MXT体系灵敏度最高，对MXT的检出限分别为4.1 ng／mL（RRS）、3.8 ng／mL（SOS）和3.6 ng／mL（FDS）。据此发展了一种用纳米硫化镉作探针，灵敏、简便、快速测定蒽环类抗癌药物的共振瑞利散射新方法。1．2某些氨基糖苷类抗生素与硫化镉纳米微粒相互作用的共振瑞利散射光谱研究在pH2.0～7.0的溶液中，硫化镉纳米微粒[（CdS）_n]与氨基糖苷类抗生素阿米卡星（AMK）、卡那霉素（KANA）、妥布霉素（TOB）和庆大霉素（GEN）借静电引力、疏水作用力结合，形成粒径更大的聚集体，导致共振瑞利散射（RRS）的增强并产生新的RRS光谱，最大RRS峰位于289nm（AMK体系）、291nm（KANA体系）、291nm（TOB体系）和287nm（GEN体系）。在一定条件下，RRS散射强度（△I）均与药物的浓度成正比，反应具有高灵敏度，对于四种药物的检出限在7.7～8.8ng／mL之间。其中（CdS）_n-AMK体系灵敏度最高，对AMK的检出限为7.7 ng／mL。据此发展了一种用纳米硫化镉作探针，灵敏、简便、快速测定氨基糖苷类抗生素药物的共振瑞利散射新方法。2．硫化镉纳米微粒与蛋白质的相互作用的共振瑞利散射光谱研究及其分析应用在pH3.3～3.8的BR缓冲溶液中，硫化镉纳米微粒[（CdS）_n]能与牛血清白蛋白（BSA）、人血清白蛋白（HSA）、溶菌酶（Lys）、血红蛋白（HGB）和卵白蛋白（OVA），形成粒径更大的聚集体，导致共振瑞利散射（RRS）的增强并产生新的RRS光谱，五种蛋白质与（CdS）_n的反应产物具有相似的光谱特征，最大RRS峰位于280nm左右。反应产物的散射强度（△I）与蛋白质的浓度成正比，反应具有高的灵敏度。本文考察了适宜的反应条件和影响因素，研究了共存物质的影响，并将此方法应用于合成样及血清和尿样中蛋白质含量的测定，得到了满意的结果。3．硫化锌纳米微粒与氨基糖苷抗生素相互作用的共振瑞利散射光谱研究及其分析应用在pH4.2～5.6的水溶液中，硫化锌纳米微粒[（ZnS）_n]与氨基糖苷类抗生素阿米卡星（AMK）、卡那霉素（KANA）和妥布霉素（TOB）借静电引力、疏水作用力结合，形成粒径更大的聚集体，导致共振瑞利散射（RRS）的增强并产生新的RRS光谱，最大RRS峰位于290 nm（TOB）、285 nm（AMK）和280 nm（KANA），同时也观察到二级散射（SOS）和倍频散射（FDS）强度明显提高，其最大SOS峰均位于540nm，而它们的最大FDS峰则分别均位于300 nm。在一定条件下，三种散射强度均与药物的浓度成正比，其中（ZnS）_n-TOB体系灵敏度最高，对TOB的检出限为6.1ng／mL（RRS）、3.8 ng／mL（SOS）、3.1 ng／mL（FDS）。据此发展了一种用纳米硫化锌作探针，灵敏、简便、快速测定氨基糖苷类抗生素药物的共振瑞利散射新方法4．铜纳米微粒与维生素B₁相互作用的吸收光谱和共振瑞利散射光谱研究在过量碘离子（I^-）的存在下，用硼氢化钠还原硫酸铜溶液，得到铜纳米微粒。铜纳米微粒因表面吸附I^-而带负电荷。在弱碱性介质中，它能与正电荷的维生素B₁（VB₁）反应，此时不仅引起吸收光谱的变化，而且导致共振瑞利散射的显著增强，其最大RRS波长位于369 nm处。VB₁浓度在0.02～0.40μg／mL范围内与散射强度（△I）强度成正比，方法具有较高灵敏度，对VB₁检出限为6.4 ng／mL；可用于复合维生素中维生素B₁含量的测定。据此发展了一种用铜纳米微粒探针用RRS技术灵敏、简便、快捷测定VB₁的新方法。更多还原

【Abstract】 Resonance Rayleigh scattering （RRS） and resonance non-linear scattering （RNLS） is a new analytical technique developed in recent ten years. Because of their merits of high sensitivity, cheapness instrument, simple operation and rapid analysis speed, these methods catch people’s more attention and have been widely used to determine trace of metal ions, nonmetal ions, biologic molecule and some pharmaceuticals. In this dissertation, the reactions between three new kinds of inorganic nanoparticles （CdS, ZnS and Cu） and some Pharmaceuticals or protein were investigated. The reaction mechanisms, affecting factors and their analytical application have been studied.1. A study on the Resonance Rayleigh scattering spectra of the interactions of CdS Nanoparticle with some Pharmaceuticals and their analytical application1.1 Resonance Rayleigh scattering spectra method for the determination of anthracycline anticancer drugs with CdS nanoparticles as probeIn pH5.0～9.0 water solution, the CdS nanoparticles [（CdS）_n] can react with a kind of anthracycline anticancer drugs such as MXT, DNR and EPI to form the bigger aggregates by virtue of electrostatic attraction and hydrophobic force. The aggregates arouse Resonance Rayleigh scttaring（RRS） instancing greatly, and the new RRS spectra appeared. The maximum RRS peaks are at 292nm for MXT system, 285nm for DNR system and 315 nm for EPI system. At the same time, the Second-order Scattering （SOS） and Frequency-double Scattering （FDS） are also enhanced obviously. The maximum SOS peaks are at 540 run for MXT system, 560 nm for EPI system and DNR system, but their maximum FDS peak are at 320 nm for EPI system, 330 nm for DNR system and 330 nm for MXT system. The enhancements of three scattering （ΔI） are directly proportional to the concentration of anthracycline drugs in a certain ranges. The reactions have high sensitivities, the detection limits for different drugs are 3.6～9.1 ng/mL. Among them, （CdS）_n-MXT system is the most sensitive, its limits for MXT are4.1 ng/mL for RRS method, 3.8 ng/mLfor SOS method and 3.6 ng/mL for FDS method, respectively. So a new method for the determination of the anthracycline anticancer drugs with CdS nanoparticles as probe has been developed, the method is highly sensitive, very simple and fast.1.2 Resonance Rayleigh scattering spectra of aminoglycoside antibiotics with CdS nanoparticles and their analytical applicationsIn pH2.0～7.0 water solution, the CdS nanoparticles [（CdS）_n] can react with a kind of aminoglycoside antibiotics such as AMK,KANA, TOB and GEN to form the bigger aggregates by virtue of electrostatic attraction and hydrophobic force. The aggregates arouse Resonance Rayleigh scttaring（RRS） greatly, and the new RRS spectra appeared. The maximum RRS peaks locate at 289 nm for AMK system, 291 nm for KANA system, 291 nm for TOB system and 287 nm for GEN system. The enhancements of four scattering （ΔI） are directly proportional to the concentration of aminoglycoside antibiotics. The reactions have high sensitivities, the detection limits for different drugs are 7.7～8.8 ng/mL. Among them, （CdS）_n-AMK system is the most sensitive, its limits for AMK are 7.7 ng/mL. So a new method for the determination of the aminoglycoside antibiotics with CdS nanoparticles as probe has been developed. The method is highly sensitive, and it is very simple and fast.2 Resonance Rayleigh scattering spectra of proteins with CdS nanoparticles and their analytical applicationsIn pH3.29 BR buffer solution, some water-soluble proteins such as human serum albumin（HSA）, bovine serum albumin（BSA） , lysozyme（Lys）, hemoglobin （HGB） and ovalbumin （Ova） can react with the CdS nanoparticles [（CdS）_n] form the bigger aggregates .The aggregates arouse Resonance Rayleigh scttaring（RRS） intensities greatly, and the new RRS spectra appeared. The maximum RRS peaks locate near 280 nm. The enhancements of three scattering （ΔI） are directly proportional to the concentration of proteins. The reactions have high sensitivities. Base on the research results, the RRS method for the determination of water-soluble protein with CdS nanoparticles was established. This method is applied to the direct determination of proteins in synthetic, urine and serum samples.3 Resonance Rayleigh scattering spectra of aminoglycoside antibiotics with ZnS nanoparticles and their analytical applicationsIn pH4.2～5.6 water solution, the ZnS nanoparticles [（ZnS）_n] can react with a kind of aminoglycoside antibiotics such as AMK,KANA and TOB to form the bigger aggregates by virtue of electrostatic attraction and hydrophobic force. The aggregates arouse Resonance Rayleigh scttaring（RRS） greatly, and the new RRS spectra appeared. The maximum RRS peaks locate at 285 nm for AMK system, 280nm for KANA system and 290 nm for TOB system 287 nm for GEN system respectively. At the same time, the Second-order Scattering （SOS） and Frequency-double Scattering （FDS） are also enhanced obviously. The maximum SOS peaks are at 540 nm, and but their maximum FDS peak are all at 300nm. The enhancements of three scattering （AT） are directly proportional to the concentration of anthracycline drugs aminoglycoside antibiotics in a certain ranges. The reactions have high sensitivities. （ZnS）_n-TOB system is the most sensitive. The Detection limits for TOB are 6.1 ng/mL （RRS） , 3.8 ng/mL （SOS） and 3.1 ng/mL （FDS） . So a new method for the determination of the aminoglycoside antibiotics with ZnS nanoparticles as probe has been developed. The method is highly sensitive, very simple and fast.4 Study on the absorption and resonance Rayleigh scattering spectra of the interaction for copper nanoparticles with vitamin B₁In the presence of excess I^-, copper nanoparticles are prepared by using NaBH₄ to reduce copper sulphate. In the solution, I^- anions self-assemble on the surface of Cu nanoparticles which become large anionic complexes [Cu_nI_m]^x-. It can react further with VB₁ cations to form binging products, resulting in the change of the absorption spectrum and great enhancement of resonance Rayleigh scattering （RRS） .The maximum scatting wavelength is at 369nm. There was a linear relationship between the RRS intensity（ΔI） and the VB₁ concentration in the range of 0.02～0.40μg/mL. The detection limit for Vitamin B₁ was 6.4 ng/ mL. A sensitive, simple, fast and new method for the determination of Vitamin B₁ with nanoparticles as probe by RRS technique has been developed.更多还原