Photogeneration of Singlet Oxygen by Tetra(p-Hydroxyphenyl)porphyrins Modified with Oligo- and Polyalkylene Oxides

Mono- and diethylene oxide derivatives of tetra(p-hydroxyphenyl)porphyrin (THPP) with different conformation states are synthesized. These compounds exhibit high photosensitization activity in the generation of singlet oxygen in organic and aqueous (in the solubilized state) phases. It is shown that introducing ethylene oxide moieties into the hydroxyphenyl substituents of THPP increases its solubility in chloroform. In addition, the activity of singlet oxygen 1Δg generation in the reaction of anthracene photooxidation by THPP tetra derivatives in chloroform, where the ethylene oxide fragments are introduced into two phenyl rings and hexadecyl fragments are introduced into another two, is higher than the activity of mono- and di-modified THPP molecules with enthylene oxide molecules at one hydroxyphenyl cycle. The activity of tetra-substituted porphyrin in chloroform, however, is comparable to that of nonsubstituted tetraphenylporphyrin, considered to be one of the most active photosensitizers. The produced ethylene oxide derivatives of THPP are solubilized with pluronic F-127 (triblock copolymer of ethylene- and propylene-oxides)—one of the least toxic and effective polymeric detergents—forming water-soluble forms of the respective porphyrins. It is established that the pluronic solubilization capability (the lowest molar concentration of pluronic required for the complete transfer of porphyrin of a particular molar concentration dissolved in organic phase to the water-soluble form) is higher for asymmetrical mono- and di-derivatives of the THPP than for symmetric tetra-substituted THPP. It is shown that the activity of the solubilized water-soluble form of mono- and tetra-derivatives in tryptophan photoxidation is higher than that of unsubstituted THPP and is comparable to the activity of tetraphenylporphyrin.