Study Of Spectra Properties About Aggregation Behaviors And Metal Complexes Of Water-solube Porphyrin

The H atoms of 8 positions and 4 meso-positions(R positions) in four pyrrole rings could be replaced by other groups to generate a variety of porphine derivatives, which is porphyrin. The greater rigidity spatial structure leads to porphyrin’s poor water solubility, which limited the research and application of them. In recent years, people attempts by modifying and adjusting the substituents, increasing its water solubility, and then develop revalence academic research become hot. Three water-soluble porphyrin meso-tetrakis (4-carboxyphenyl) porphyrin (TCPP), meso-tetra (4-sulfophenyl) porphyrin (TSPP) and meso-tetra (4-trimethylanilinium-phenyl) porphyrin (TTAP) were selected in this paper. The spectra properties of aggregation behavior and metal complexes were investigated, specific contents as follows:Chapter I:Summary of the properties and applications of porphyrins, especially the structure, aggregation behavior, research status of water-soluble porphyrin and significance of the subject, the research content and innovation points were summarized.Chapter Ⅱ:Self-aggregates conditions of anion porphyrin TCPP were discussed. We found self-aggregates were formed in acid solution, and relatively ordered nanorods were formed when pH=1; Aggregates displayed very new absorption and fluorescence emission compared with the porphyrin monomer. And resonance light scattering showed that porphyrin self-aggregates particle size was positively related to the time. Electrochemical methods showed TCPP self-aggregates have good photoelectric response and reversibility. Self-aggregate of TCPP was inferred from hydrophobic association and π-π stacking interactions.Chapter III:The interaction between cationic porphyrin TTAP and anionic porphyrin TCPP, anionic porphyrin TSPP were investigated through UV-Vis absorption spectroscopy, fluorescence spectroscopy and resonance light scattering, found that the mixture aggregated in netural solution, the ratio were TTAP:TCPP=2:1 and TTAP:TSPP=1:1. In addition, microscopy showed the structure of TTAP and TSPP mix-aggregates were petal crystal shapes, and the size of mix-aggregates was investigated by atomic force microscopy (AFM), which was 160nm high and 0.48μm wide.Chapter IV:The interaction between cationic porphyrin TTAP and metals Fe, Co, Ni which similar of characteristics was investigated in aques media by UV-Vis and fluorescence spectroscopy. The results showed that TTAP form metal complexes with transition metal Fe, Co, Ni, their UV-Vis absorption and fluorescence spectra were different with TTAP monomer; the variation was related to characteristics of ligand metal. The maximum absorption of Fe-TTAP and Co-TTAP were redshifts, and the maximum absorption peak of Ni-TTAP did not change; the fluorescence intensity all decreases or quenching. The mechanisms of change about spectra were discussed.