Synthesis And Characterization Of Some Axially Substituted Silicon(Ⅳ), Titanium(Ⅳ) And Tin(Ⅳ) Phthalocyanines

Metallophthalocyanines(MPc) are a class of efficient photosensitizers with light oxidation-reduction reaction, and had aroused extensive interest in photodynamic therapy (PDT) of cancer or macular degeneration. MPc itself is a class of macrocyclic compounds possessing a system of conjugatedÏ€-electrons, and cannot avoid molecular aggregation, so this will drastically shorten its triplet state lifetime, and reduce its photosensitizing efficiency. It was found that, axial substitution phthalocyanines could prevent their molecular aggregation, and enhance their photosensitizing efficiency. Therefore, three types of axially substituted metal phthalocyanines were synthesized and characterized. One is the axially substituted silicon phthalocyanine: dipridiyloxy axially substituted silicon(â…£) phthalocyanine(SiPc(OR₁)₂) and di(2-isopropyl-6-methyl-4-pyrimidyloxy) axially substituted silicon(â…£) phthalocyanine(SiPc(OR₂)₂); the other is hydrophobic substituted titanium phthalocyanine: catecholato axially substituted tetra-α-(pentoxy) titanium() phthalocyanine(TiPc(OC₅H₁₁)₄-Catechol) and hematoxylin axially substitutedtetra-α-(pentoxy)titanium(â…£) phthalocyanine(TiPc(OC₅H₁₁)₄-Hematoxylin); the last one was di(2-isopropyl-6-methyl-4-pyrimidyloxy)-tetra-(α-pentyloxy) axially substitutedtetra-α-(pentoxy)tin(â…£) phthalocyanine(Sn(OR₂)₂Pc(OC₅H₁₁)₄). Their structure were characterized by elemental analysis, IR,¹H NMR , MS ,UV-Vis and fluorescence spectra.Lys (z)-NCA was synthesized from N^ε-carbobenzoyloxy-L-Lysine and triphosgene in THF. Amphiphilic triblock copolymers poly(N'-carbobenzyloxy-L-Lysine)(poly (N'-CBZ-Lysine)-PEG-poly (N'-CBZ-Lysine)) were synthesized in DMF in the condition that both amino-end PEG was used as initiator via a ring-opening polymerization. The structures of polymers were characterized by IR and ¹H NMR. Then polymeric micells were prepared by dialyse method. The diameter of polymeric micelle was about 35nm by AFM. The formation machnism of polyion complex micelles was discussed.