Eiko Ohno-Okumura

Syntheses and Functional Properties of Phthalocyanines

Metal phthalocyanine tetrasulfonic acids, metal phthalocyanine octacarboxylic acids, metal octakis(hexyloxymethyl)phthalocyanines, and metal anthraquinocyanines have been synthesized. Then, zinc bis(1,4-didecylbenzo)-bis(3,4-pyrido)porphyrazines, the cyclotetramerization products of a 1:1 mixture of 3,6-didecylphthalonitrile and 3,4-dicyanopyridine, were synthesized. Futher, subphthalocyanine and its derivatives, with substituents such as thiobutyl and thiophenyl moieties were synthesized. Electrochemical measurements were performed on the abovementioned phthalocyanine derivatives and analogues in order to examine their electron transfer abilities and electrochemical reaction mechanisms in an organic solvent. Moreover, 1,4,8,11,15,18,22,25-octakis(thio-phenylmethyl)phthalocyanes were synthesized. The Q-bands of the latter compounds appeared in the near-infrared region. Furthermore, non-colored transparent films in the visible region can be produced.

Photosensitizer efficacy of non-peripheral substituted alkylbenzopyridoporphyrazines for photodynamic therapy of cancer

The triplet state of zinc non-peripheral substituted alkylbenzopyridoporphyrazines and position isomers were measured, using laser-flash photolysis in poly(methyl methacrylate) film. The triplet lifetime increased with an increasing pyridine number in the molecule. The lowest symmetric isomer having two pyridine rings in the molecule showed the longest triplet state lifetime. The compound was suitable for the use the photosensitizer as a photodynamic therapy of cancer.

Synthesis of near-infrared absorbed metal phthalocyanine with S-aryl groups at non-peripheral positions

Phthalocyanines are used as various applications, including as organic charge carriers in photocopiers, laser light absorbers in data storage systems, photoconductors in photovoltaic cells and electrochromic displays, and non-colored transparent film in visible region. The absorption maxima of phthalocyanines are best if moved near the infrared region for these applications. The Q band of phthalocyanines can be moved to bathochromic effects through extension of a π conjugation system such as naphthalocyanines and anthracyanines. Yields of naphthalocyanines and anthracyanines are, however, low. To solve the problem, novel metal phthalocyanines having non-peripheral S-aryl substituent were synthesized. The novel phthalocyanines show a high strain structure and no liquid crystal property. The target compounds were synthesized: 15 phthalocyanines from 2,3-dicyanohydroquinone in 3 steps via 1,2-dicyanobenzene-3,6-bis(trifluorate) and 1,2-dicyanobenzene-3,6-thiophenols. The Q bands of obtained compounds appeare...

Synthesis of subphthalocyanine derivatives and their characterization

Subphthalocyanine and its derivatives which possessed substituents such as thiobutyl and thiophenyl were synthesized. These compounds were measured using spectroscopic measurements and cyclic voltammetry. Sensitization properties of synthetic subphthalocyanine (SubPC) in 2,4,6-Tris(trichloromethyl)-1,3,5-triazine as radical generation reaction in a poly(methyl methacrylate) film have been investigated by laser flash photolysis.

Synthesis of octasubstituted cobalt phthalocyanines and their redox properties

Octakis(alkoxymethyl) cobalt phthalocyanines with relatively short side chains were synthesized which exhibited no thermotropic liquid crystalline behaviour. The final products as well as the intermediates have been characterized by proton magnetic resonance, infrared and electron spectra and elemental analysis. Cyclic voltammograms were measured for octakis(alkoxymethyl) cobalt phthalocyanines in order to examine their electron transfer properties. The electron transfer properties of octakis (alkoxymethyl) cobalt phthalocyanines depend on the kind and number of substituents and are due to the interaction between the phthalocyanine ring, the central metal which is influenced by the conjugated π electron current of the porphyrazine ring.

Laser-flash photolysis of dialkylbenzodipyridoporphyrazines

In the course of a fundamental study of photosensitizers for photodynamic therapy of cancer, a non-peripheral substituted phthalocyanine analogue, zinc bis(1,4-didecylbenzo)bis(3,4-pyrido)porphyrazine and its position isomers were examined to measure their photoexcited triplet state lifetimes in poly(methyl methacrylate) film using laser-flash photolysis. The isomer mixture of zinc bis(1,4-didecylbenzo)bis(3,4-pyrido)porphyrazine showed the most intense absorption in the 660-710 nm region, and the longer triplet state lifetime. The lowest symmetry isomer of zinc bis(1,4-didecylbenzo)bis(3,4-pyrido)porphyrazine was found to have the longest triplet state lifetime when all isomers were separated. The compound is proposed to be suitable for use as a photosensitizer for photodynamic therapy of cancer.

Investigation of Zinc bis(1,4-didecylbenzo)-bis(2,3-pyrido) Porphyrazine for Application as Photosensitizer in Photodynamic Therapy of Cancer.

The phthalocyanine analogue containing nonperipheral long alkyl-substituted benzenoid rings and pyridine rings, zinc bis(1,4-didecylbenzo)-bis(2,3-pyrido) porphyrazine, was synthesized. Zinc bis(1,4-didecylbenzo)-bis(2,3-pyrido) porphyrazine reacted with dimethyl sulfate and monochloroacetic acid to produce their quaternized products and diethyl sulfate to produce the sulfo-substituted products. All quaternized and sulfo-substituted showed amphiphilic character. Identical peaks in cyclic voltammograms appeared for these products before and after quaternization. During the evaluation of zinc bis(1,4-didecylbenzo)-bis(2,3-pyrido) porphyrazine for its photodynamic therapy of cancer (PDT) efficacy by cancer cell culture, the light exposed dimethyl sulfate quaternized zinc bis(1,4-didecylbenzo)-bis(2,3-pyrido) porphyrazines in IU-002 cells produce cell disruption that can be detected as a decrease in fluorescence.