【作者】 刘海燕；

【导师】 胡刚；

【作者基本信息】 安徽大学 ， 分析化学， 2010， 硕士

【摘要】 化学振荡表现出来的一些特征引起化学家、物理学家、生物学家、药物学家的热切关注。近年来化学振荡在分析化学和生命科学等领域的应用日益广泛。但是这些应用都局限于被测物对化学振荡体系的直接干扰作用。本文首次提出了根据被测物对振荡体系的间接扰动作用,实现对被测物的定量分析。被测物抗坏血酸磷酸酯和磷酸苯酯二钠二水本身对振荡体系没有扰动作用,但是在一定的实验条件下可以水解生成抗坏血酸和苯酚,而抗坏血酸和苯酚对振荡体系能产生扰动,使振幅发生改变,而振幅的改变量和抗坏血酸磷酸酯和磷酸苯酯二钠二水的浓度对数在一定范围内都呈线性关系,依此实现对这两种被测物的分析检测。参照文献合成催化剂大环铜配合物,利用元素分析和红外谱图对其进行结构和性质表征,然后以大环铜配合物[CuL](ClO4)2+硫酸+溴酸钠+苹果酸建立稳定的振荡体系,得到规则的振荡图形。以碱性磷酸酶作为催化剂,在一定的实验条件下将被测物抗坏血酸磷酸酯钠水解为抗坏血酸,加入振荡体系,引起了振幅的迅速增大,之后恢复到原态。结果表明在1.0×10-5-5.0×10-4 mol／L浓度范围内时,抗坏血酸磷酸酯钠浓度对数与振荡振幅的改变量△A呈良好的线性关系(R=0.9952,n=10)。同时分析了对体系可能存在干扰的常见离子的干扰情况,最后对可能的反应机理进行了推测。同样建立稳定的振荡体系以后,以碱性磷酸酶作催化剂,在37℃下反应30分钟,把磷酸苯酯二钠二水水解为苯酚。经实验研究发现,苯酚对该振荡体系有干扰作用。水解之后的产物加入振荡体系后,引起振幅的改变,结果发现在2.0×10-6-6.0×10-4mol／L范围内时,磷酸苯酯二钠二水的浓度对数与振幅的改变量△A呈良好的线性关系。同时做了干扰离子实验,并利用循环伏安方法对可能的机理进行了探究。更多还原

【Abstract】 The special behaviors of oscillating chemical reaction have attracted great interest of some chemists, physicists biologists, and medical scientists. Chemical oscillation reactions have been applied in analytical chemistry and life system in recent years. But the applications are all based on the direct perturbation effect of the analyte on the oscillating system. A new method for quantitative analytical determination by Analyte Indirect Perturbation (AIP) on an oscillating system is proposed in this paper for the first time. The analytes 2-phospho-L-ascorbic acid trisodium salt and Disodium phenyl phosphate dihydrate could not cause perturbation effects on the oscillating reaction, but they can be hydrolyzed to ascorbic acid and phenyl in certain conditions, and ascorbic acid and phenyl cause the perturbation on the oscillating reaction. So we can accomplish the indirect determination of the analytes.The catalyst tetraazamacrocyclic complex [CuL](ClO4)2 was synthesized according to literature and was identified by I.R. spectrum and elemental analyses.Then a stable oscillating system involves [CuL](ClO4)2), sulfuric acid, sodium bromate and malic acid was established. The 2-phospho-L-ascorbic acid trisodium salt was hydrolyzed into ascorbic acid catalyzed by alkaline phosphatase. Then different volumes of the mixture solution involves ascorbic acid were injected to the oscillating system, and the amplitude increased shaply and then came back the normal state. The result shows that the changes of the amplitude (△A) were linearly proportional to the logarithm of the PATS concentration over the range of 1.0×10-5 to 5.0×10-4 M. We also studied the effect of some potential interference from foreign species and the possible mechanism.The stable system was established firstly. Then the analyte phenyl phosphate was hydrolyzed into phenol which cause perturbation effect on the oscillating system. Different volumes of phenol was injected to the oscillating system and induced the change of the oscillation amplitude. The result shows that the changes of the oscillation amplitude were linearly proportional to the concentration of logarithm of the DPPD very well in the range 2.0×10-6 to 6.0×10-4 M, with a correlation coefficient of 0.9930. The influence of some foreign species was investigated, and we also studied the possible mechanism by cyclic voltammetry.更多还原