【作者】 韩颜颜；

【导师】 魏琴；

【作者基本信息】 济南大学 ， 分析化学， 2010， 硕士

【摘要】 卟啉及金属卟啉化合物广泛存在于自然界和生命体,在生命活动中起着非常重要的作用。卟啉作为显色剂已经广泛应用于单一金属离子的测定;卟啉化合物还可作为过氧化物模拟酶催化化学发光反应用于生物大分子的检测。本文首先详细叙述了卟啉化合物基本的合成方法及卟啉化合物在金属离子和生物大分子分析中的应用。论文主要包括以下几个方面:一、采用4-甲氧基苯甲醛、苯甲醛、吡咯为原料,通过经典的Alder-Longo合成法,得到了不对称甲氧基卟啉化合物及其金属配合物,并合成了Meso-四-（3-甲氧基-4-羟基苯基）卟啉及其锌、锰、铽金属配合物。产物经过红外、紫外、核磁等表征,确定其结构并将部分化合物应用到分析测定中。二、5,10-二苯基^-15,20-二（4-甲氧基苯基）卟啉作为显色剂,结合光谱拟合软件对吸收光谱进行二阶求导,利用导数分光光度法同时测定了铜、镉、铅三种金属离子,考察了同时测定的最佳条件;铜、镉、铅三种金属离子分别在0.05 - 0.80、0.01 - 0.56、0.12 - 1.66μg·mL^-1线性范围内符合朗伯-比尔定律,摩尔吸光系数分别为2.10×10⁵、3.95×10⁵、3.36×10⁵ L·mol^-1·cm^-1,并将该方法用于实际样品中多种金属离子的同时测定。三、建立了Meso-四（3-甲氧基-4-羟基苯基）卟啉（[T-（3-MO-4-HP）P]）作为显色剂分光光度法同时测定铜、锌、镉、汞、铅的方法,考察了各个条件对测定的影响,铜、锌、镉、汞、铅五种金属离子分别在0 - 0.60、0 - 0.60、0 - 0.40、0 - 0.80、0 - 0.48μg·mL^-1线性范围内符合朗伯-比尔定律,显色体系的摩尔吸光系数分别为1.38×10⁵、1.01×10⁵、3.24×10⁵、1.0⁷×10⁵、1.29×10⁵ L·mol^-1·cm^-1;并将其应用于多种实际样品中金属离子的同时测定。四、采用流动注射化学发光法以5-（4-甲氧基苯基）^-10,15,20-三苯基锌卟啉为过氧化物模拟酶测定牛血清白蛋白,在最佳条件下,绘制牛血清白蛋白的工作曲线,线性范围为0.05 - 25.0μg·mL^-1,检测限为2.73 ng·mL^-1。初步从理论上探讨了其作用机理,并采用荧光光谱研究了该锌卟啉与牛血清白蛋白之间的相互作用力、猝灭机理及其卟啉化合物对蛋白质构型变化的影响等。五、采用流动注射化学发光法以Meso-四（3-甲氧基-4-羟基苯基）锰卟啉为过氧化物模拟酶测定转铁蛋白,探讨该发光反应的最佳实验条件,在最佳条件下,绘制转铁蛋白的工作曲线,线性范围为0.04 - 20.0μg·mL^-1,检测限为1.62 ng·mL^-1。并成功地将所建立的方法应用于血清样品中转铁蛋白含量的测定。更多还原

【Abstract】 Porphyrin and metalloporphyrin existed in nature and life body widely, playing an important role in life activities. It has been used as chromogenic reagent for the determination of single metal ion in analytical chemistry. It also can be used as peroxidase mimic enzyme for the determination of biomacromolecule using the flow injection-chemiluminescence method.In this paper, the synthesis methods for porphyrin were discussed. Then the application of porphyrin in determination of metal ion and biomacromolecule were also mentioned. The main content of the study are provided as follows:1. Using 4-Methoxybenzaldehyde, benzaldehyde and pyrrole as raw materials, asymmetry methoxylporphyrin compounds and metal complexes were synthesized by classical Alder-longo method. The Meso-tetra （3-methoxyl-4-hydroxylphenyl）porphyrin and its metal complex was also obtained. All the products were characterized using infrared spectrum（IR）, nuclear magnetic resonance （NMR）, ultraviolet-visible absorption spectrum（UV-Vis）.2. With the help of software on the second-order derivation of original absorption spectrum, Cu²⁺, Cd²⁺, Pb²⁺ could be determinated simultaneously by spectrophotometry method. 5,10-diphenyl^-15,20-dimethoxylphenyl porphyrin was used as chromomeric reagent. The optimal conditions of this system have been investigated. The results showed that: measurements were available in the ranges of 0.05 - 0.80, 0.01 - 0.56, 0.12 - 1.66μg·mL^-1 for Pb²⁺, Cd²⁺ and Cu²⁺, respectively. The molar absorptivity of these color systems were 2.10×10⁵, 3.95×10⁵ and 3.36×10⁵ L·mol^-1·cm^-1. Then this method was applied to simultaneous determination of real samples with satisfactory results.3. With the help of software on the second-order derivation of original absorption spectrum, Cu²⁺, Zn²⁺, Cd²⁺, Hg²⁺ and Pb²⁺ could be determinated simultaneously by spectrophotometry method. Meso-tetra （3-methoxyl-4-hydroxylphenyl）porphyrin was used as chromomeric reagent. The results showed that: measurements were available in the ranges of 0 - 0.60, 0 - 0.60, 0 - 0.40, 0 - 0.80 and 0 - 0.48μg·mL^-1 for Cu²⁺, Zn²⁺, Cd²⁺, Hg²⁺ and Pb²⁺, respectively. The molar absorptivity of these color systems were 1.38×10⁵, 1.01×10⁵, 3.24×10⁵, 1.0⁷×10⁵ and 1.29×10⁵ L·mol^-1·cm^-1. Then this method was applied to simultaneous determination of real samples with satisfactory results.4. The ability of bovine serum albumin（BSA） to reduce the chemiluminescence reaction of luminol-hydrogen peroxide（H2O2）, catalyzed by 5-（4-methoxyl）phenyl^-10,15,20-triphenyl zinc Porphyrin（ZnP） as mimetic enzyme of Peroxidase, has been exploited to develop a new flow injection chemiluminescence method for the determination of BSA. Under the optimum conditions, the linearity of the calibration curve for the determination of BSA was in the range of 0.05 - 25.0μg·mL^-1. This method has been successfully applied to the determination metal ions in the real sample. The interaction of porphyrin and BSA were studied by fluorescence spectrum.5. The ability of transferrin（Tf） to reduce the chemiluminescence reaction of luminol-H₂O₂, catalyzed by Meso-tetra（3-methoxyl-4-hydroxyl）phenyl Manganese Porphyrin（MnP） as Mimetic Enzyme of Peroxidase, has been exploited to develop a new flow injection chemiluminescence method for the determination of transferrin. The linearity of the calibration curve for the determination of transferrin was in the range from 0.04 to 20.0μg·mL^-1. The method has been successfully applied to the determination of transferrin in the serum samples.更多还原