Study On Some Functional Substituted Phthalocyanines: Syththesis, Characterization And Properties

Due to phthalocyanines substituted by functional groups possess unique properties in photodynamic therapy(PDT), Langmuir-Blodgett (LB) film, liquid crystals, nonlinear optics etc., more and more attention focus on it. This paper focuses on amphiphilic phthalocyanines, which have showed potential advantages used in photodynamic therapy. And then, a series of functional substituted phthalocyanines were synthesized and their properties were studied. The main results are summarized as following: 1. Seven phthalocyanine precursors and nine functional zinc phthalocyanines have been synthesized, and characterized by elemental analysis, IR, UV/VIS, MS, HNMR and HPLC. Five of nine zinc phthalocyanines have also been transformed to the corresponding salts. All of these compounds except 4-[(5-sulfonic)quinoline-8-yloxy] phthalonitrile and 2,9,16,23-tert-[(5-sulfonic)quinoline-8-yloxy]phthalocyaninatozinc(II) have not been reported so far, according to the best of our knowledge. The nine zinc phthalocyanines are 1-[4-(propanoic acid)phenoxy]phthalocyaninstozinc(II),1-[4-(butyl formate)phenoxy]phthalocyaninatozinc(II),disnitro-phthalocyaninatozinc(II),1-[(5-sulfonic)quinoline-8-yloxy]phthalocyaninatozinc(II),1,8,15,22-tert-[(5-sulfonic)quinoline-8-yloxy]phthalocyaninatozinc(II),2,9,16,23-tert-[(5-sulfonic)quinoline-8-yloxy]phthalocyaninatozinc(II),1,8,15,22-tert-[4-(4-acetylpiperazine)phenoxy]phthalocyaninatozinc(II),2,9,16,23-tert-[4-(4-acetylpiperazine)phenoxy]phthalocyaninatozinc(II),and2,3,9,10,16,17,23,24-octa-[4-(4-acetylpiperazine)phenoxy] phthalocyaninatozinc(II). 2. Some physical and chemical properties have been studied, including partition coefficients, stabilities, molecular spectra and existing state. The relationships between structure and property of these phthalocyanines are simply discussed. The results show that: (1) six of all Pc complexes exhibit amphiphilic nature. (2) Pcs exist steadily in DMF solution. (3) All Pcs exist in the form of monomer in organic solutions such as DMF, THF, isopropanol and 1-octanol, and in an aqueous solution containing 2%(v/v) Cremophor EL. They show an intense and sharp Q band at 670nm-700nm with a mole extinction coefficient of ca. 105mol-1?L?cm-1, which are very helpful for photodynamic therapy. (4)Tetrasubstituted groups in αpositions, in comparison with βpositions, can help Pcs exist in monomeric form and let their Q bands red shift. 3. The in vitro photodynamic activities have also been investigated. The result shows 1,8,15,22-tert-[(5-sulfonic)quinoline-8-yloxy]phthalocyaninatozinc(II) potassium (ZnPc-4-3') has a high photodynamic killing activities against HepG2 human hepatocarinoma cells with a IC50 (half lethal dose) of 3μmol·L-1.