Comparison between non-peripherally and peripherally tetra-substituted zinc (II) phthalocyanines as photosensitizers: Synthesis, spectroscopic, photochemical and photobiological properties

A series of zinc phthalocyanines tetra-alpha-substituted with 4-(butoxycarbonyl) phenoxy groups (1a) or 4-carboxylphenoxy groups (2a) or 4-(2-carboxyl-ethyl)phenoxy groups (3a), and the corresponding tetra-beta-substituted (1-3b) analogues, have been synthesized and characterized. The effects of the position of substituents at the phthalocyanine skeleton on their spectroscopic, photochemical and photobiological properties have been revealed. When compared with the tetra-beta-substituted phthalocyanines, the corresponding tetra-alpha-substituted analogues exhibit a less aggregating trend in the cellular growth medium, a slightly higher singlet oxygen quantum yield and higher photo-stability in DMF, and a comparable cellular uptake. As a result, the tetra-alpha-substituted zinc phthalocyanines exhibit a higher photocytotoxicity toward MGC803 human gastric carcinoma cells than the tetra-beta-substituted counterparts. Among all these compounds, phthalocyanine 2a shows the highest photodynamic activity, which may mainly be due to its non-aggregated nature in cellular culture medium and high cellular uptake. (C) 2008 Elsevier B.V. All rights reserved.