The Preparation Of Novel Potentiometric Chemical Sensors With Porphyrinoid Derivatives As Recognition Carriers

The design and synthesis of molecular recognition carriers are main research subjects in the ion-selective electrode studies. Porphyrins and metalloporphyrins are recognized as perfect host for molecular recognition owing to their diversity, their rigid molecular structures, the position and direction of the substituents on the porphyrin ring being controllable, as well as the variety of metal ligands of the metalloporphyrins. Corrole, an old member of the porphyrinoid family, has attracted a great deal of interest in recent years owning to the synthetic breakthroughs. Due to the structural similarity to porphyrins, corrole can be selected as the carrier for potentiometric chemical sensors. The study of the chemical sensing characteristics of porphyrins and metalloporphyrins is an active area all the while. Searching for novel porphyrin derivatives, including corrole, with high selectivity as the molecular recognition ionophores for chemical sensors, therefore, remains task of theoretical and practical significance.The contents of the thesis are presented as follows:1. The syntheses of series of porphyrin derivatives were presented in the second charpter. 1) The synthesis and structural characterization of 5,10,15- Tris(penta- fluorophenyl)corrole and its corresponding [5,10,15- Tris(pentafluorophenyl) corrolato] manganese(III);2) The synthesis and structural characterization of series of porphyrin and metalloporphyrins as follows: chloro[5,10,15,20-tetra(p-methyl- phenyl)- porphinato]manganese (III), chloro[5,10,15,20-tetra (p-methyl- phenyl)- porphinato] iron(III), [5,10,15,20-tetra (p-methyl- phenyl)- porphinato]copper (Ⅱ) andμ-oxo- bis[5,10,15,20-tetra (p-methyl-phenyl)-porphinatomanganese(III)].2. In the third charpter, a highly selected silver electrode based on 5,10,15-tris (pentafluorophenyl)corrole has been prepared, and its response was compared with that of metallo corrole counterpart and 5,10,15,20-tetra(phenyl) porphyrin. The composition of the electrode membrane has been optimized. The response mechanism of the electrode was investigated using UV-Vis spectrophotometry and lipophilic ion additive experiment. Experimental results indicated that the electrode response to Ag(I) is more likely via a neutral carrier mechanism. The electrode was applied to the determination of silver ions in real ore samples.3. In the forth charpter, anμ-oxo-bismetalloporphyrin based on molybdate-...