Synthesis of Phthalocyanines and Porphyrazines for Photodynamic Therapy and Bioalytical Purposes




Doctor of Philosophy (PhD)



Document Type



A series of novel symmetric and asymmetric phthalocyanines (Pcs) and porphyrazines (Pzs) bearing solubilizing groups and peripheral functionalities such as nitro, amine, acid, aminooxy, and azide, some of which can be used for conjugation or labeling reactions were synthesized in good yields. Statistical condensation method, and ring opening metathesis polymerization capture and release strategy were employed but a solid solid-phase method synthesis of these macrocycles by one pot cyclotetramerization with simultaneous insertion of metal led to maximum yields of 10-15 % of the asymmetric product. The conjugation abilities of these Pcs have been demonstrated by the successful conjugation of one of the azide Pcs with a peptide elaborated with an alkyne function. Use of microwave for the synthesis of these compounds, resulted in shorter reaction times (1-2) hours, higher yields, and higher degree of purity. In the solid-phase method, the compounds are formed by cross condensation of maleonitrile or phthalonitrile elaborated with ester or ethylene glycol functions with phthalonitrile covalently bonded to the solid support with an amino linking group. The polymer bound Pc or Pz is separated by filtration, and washing the symmetrical Pc or Pz by product. The desired product is cleaved from the resin using a cocktail of DCM/ TFA to produce the 3:1 asymmetrically substituted Pc or Pz. The hydrophilic nature of the polyethylene glycol (PEG)-based resin allows the symmetrical compounds to be removed completely by washing. The indole linker is acid sensitive which makes it easier to cleave the product under mild conditions to give products with high degree of purity. These chemically robust, near-IR absorbing new compounds with potential biomedical applications and labeling abilities are characterized by NMR, electronic absorbance, fluorescence as well as mass spectroscopy.



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Committee Chair

Hammer, Robert P.



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