Synthesis And Photosensitivity Of Metallophthalocyanines Substituted With Aromaticoxy With Nitrogen

Photodynamic Therapy (PDT)has been an availability technique for the treatment of cancer.Compared with traditional cancer therapies such as surgery,chemotherapy and radiation therapy, PDT has many excellences such as without destroying healthy tissue and apparatus,no suffering ,little by-effect etc.. Photosensitizer,light and tissue's oxygen are three factors for PDT. Photosensitizer is a key factor. The effect of PDT mostly depends on the photodynamic activity of photosensitizer, and the photodynamic activity of photosensitizer depends on its photophysical and photochemical properties and bio-appetency to target tissue. Synthesis of novel photosensitizers and studing on their structure-activity relationships may push forward the PDT.Since the 1980s,phthalocyanine had been investigated for the new photosensitizer. Metallophthalocyanines substituted with aromaticoxy with nitrogen bases on their bio-appetency were investigated in this dissertation.A series of Metallophthalocyanines substituted with aromaticoxy with nitrogen were synthesized,their photophysical and photochemical properties and their photodynamic activity were investigated .The main works and results are summarized as follows: 1. Ten precursors were synthesized in this dissertation which could be used to prepare metallophthalocyanines: 3-(p-aminophenyloxy) phthalonitrile, 3-(m-aminophenyloxy) phthalonitrile, 3-(4-pyridyloxy)phthalonitrile, 3-(8-quinolinoxy) phthalonitrile, 3-(2-methyl-8-quinolinoxy) phthalonitrile, 4-(p-aminophenyloxy) phthalonitrile, 4-(m-aminophenyloxy) phthalonitrile, 4-(4-pyridyloxy)phthalonitrile, 4-(8-quinolinoxy) phthalonitrile, 4-(2-methyl-8-quinolinoxy) phthalonitrile.And they were characterized by Elemental Analysis,IR,1HNMR as well as Mass spectrum. 43 kinds substituted metallophthalocyanines (M=Zn,Cu,Ni,Co,Al) were synthesized,and they were characterized by Elemental Analysis, IR, UV-Vis as well as Mass spectrum.So far 49 kinds of compounds had not been reported except 4-(4-pyridyloxy)phthalonitril,β-(PyO)4PcZn,4-(8-quinolinoxy) phthalonitrile and β-(QO)4PcZn. 2. The UV-Vis spectra of title compounds were investigated in this dissertation. The effects of center metal ,substituted group (kind and position) and solvent onλmax in their Q-band were discussed. The results indicate that the metallophthalocyanines'λmax in Q-band shifting to red region more distinctly with the increase of d-electrons of central mental. The effects of substituted groups' position on the metallophthalocyanines' λmax in Q-band were much more distinct. For α substituted metallophthalocyanines,the λmax in Q-band shifted to red region more distinctly than that of β substituted metallophthalocyanines. The effects of solvents DMF, DMSO, THF and Py on the title compounds were not distinct, which means the cordination between the compound and solvent isn't visible. 3. The fluorescence spectra and T-T time resolved absorption spectra were,were investigated in this dissertation.The effect of center metal , kinds of substituted group and position on the properties of the excited singlet stste and excited triplet state of title compounds were discussed. 4. The abilities of title compounds for photo-generating singlet oxygen(1O2)and photo-oxidation for aminophenol were studied. The effects of compose and structure on their photophysical and photochemical properties were discussed. The results show that the metallophthalocyanines with full shell central metal ,substituted group with big conjugate system and α-position ,have stronger photosensitivity. 5. The in vitro photodynamic activities of some of the title compounds were studied. It is found that azo-aromaticoxy substituted phthalocyanie-zinc have strong photodynamic effect to kill cancer cells. They may be photosensitizers for PDT.