Study On Axially Substituted Phthacyanines: Synthesis, Characterization, And Properties

Photodynamic Therapy (PDT) is a new and developing technique for therapy ofcancer, which has been received a greater attention in medical community. The mode ofoperation in PDT is based on visible light excitation of a tumor-localized photosensitizer. Itis considerable interest in phthalocyanines(Pc) containing both non-transition metals andaxial groups for use as photosensitizers. The appropriate axial groups couldadvantageously influence the photophysical and photochemical properties ofphthalocyanine ring. Furthermore, by contrast with peripherally substitutedpcthalocyanines, axially substituted ones are easily prepared as the single isomers, which isvery favorable for the purpose of development of new drugs. The effect of axial ligandsubstitution of Pc complexes on their properties including molecule spectra, photodynamicactivities and so on, has not received much attention and remains little studied. In order to evaluate the effect various axially groups on the relative properties ofsilicon Pc or aluminum Pc, some relative research was carried out in this dissertation. Themain results are summarized as following.(1) Twenty axially substituted phthalocyanines have been synthesized, and characterized by elemental analysis, IR, UV/Vis,MS , HNMR and HPLC. Eighteen of these complexes have not been reported so far, according to the best of our knowledge. Among them, the central ions are Si4+ and Al3+, and axial substituents are diversiform, including hydrophilic aminosulfonyl, lipophilic naphthyloxy, and the substituted pyrimidinoxy, phenoxy,ethoxy,benzyloxy and so on.(2) Some physical and chemical properties involved PDT has been studied, including partition coefficients, stabilities, molecule spectra and existing state. It is found that the partition coefficients of complexes can be tuned by changing axial substituents. The result shows that part compounds exist steadily in DMF and CEL solution. ii轴向取代酞菁配合物的合成,表征与性质研究Moreover, part compounds exist in the form of monomer in a saline solution containing 2%(v/v)Cremophor EL, and show an intense and sharp Q band at 660nm-700nm, which are very helpful forPDT.The relationships between structure and property of axially substituted Phthalocyaninesare simply discussed.(3) The in vitro photodynamic activities have also been investigated. The result showsbis(4-methoxycarboxyl phenoxy)phthalocyaninatosilicon(IV) has photodynamic killing activitiesagainst B16 melanoma cells with a LD50 (half lethal dose) of 1.2×10-4 mol·L-1.