Synthetic control of interchromophoric interaction in cationic bis-porphyrins toward efficient DNA photocleavage and singlet oxygen production in aqueous solution.
We have synthesized cationic bis-porphyrins and their zinc(II) complexes with two TMPyP-like chromophores bridged by p- or m-xylylenediamine to develop effective DNA photocleaving agents. The xylylene linkers and zinc ion were introduced to control interchromophoric interaction that should be involved in photosensitization of the cationic bis-porphyrins. The molar absorptivities of all the bis-porphyrins in aqueous solution remained unchanged over a wide range of concentrations, indicating the absence of self-aggregation property. In particular, the molar absorptivity of the zinc(II) complex of the p-xylylenediamine-linked bis-porphyrin in aqueous solution was 2.0 times as large as that of unichromophoric ZnTMPyP, suggesting the absence of both intermolecular and intramolecular interchromophoric interaction. The metal-free p-xylylenediamine-linked bis-porphyrin showed the more efficient conversion ability of supercoiled to nicked circular pUC18 plasmid DNA by photosensitization than the metal-free m-xylylenediamine-linked one. Furthermore, the zinc complexes of the bis-porphyrins exhibited the more potent DNA photocleavage than did the metal-free bis-porphyrins. Singlet oxygen productivity of the four cationic bis-porphyrins was determined by measuring the decomposition rate of 1,3-diphenylisobenzofuran. The amount of singlet oxygen generated by photosensitization of the zinc(II) complex of the p-xylylenediamine-linked bis-porphyrin in aqueous solution was 2.1 times as large as ZnTMPyP, indicating the full singlet oxygen productivity. A significant relationship between the DNA photocleaving abilities and the singlet oxygen productivities of the cationic porphyrins in aqueous solution was found. Hence, the degree of the intramolecular interchromophoric interaction, the DNA photocleaving ability, and the singlet oxygen productivity of the cationic bis-porphyrins in aqueous solution were successfully controlled by means of the introduction of the appropriate linker and metal ion.
Ishikawa
Yoshinobu
Y
Graduate School of Pharmaceutical Sciences, Kumamoto University, 5-1 Oe-Honmachi, Kumamoto, Japan. ishikawa@gpo.kumamoto-u.ac.jp
Yamakawa
Naoki
N
Uno
Tadayuki
T
D004247:DNA / Q000737:chemistry* / Q000235:genetics; D004249:DNA Damage; D015394:Molecular Structure; D010777:Photochemistry; D010782:Photolysis; D010957:Plasmids / Q000235:genetics; D011166:Porphyrins / Q000737:chemistry*; D026082:Singlet Oxygen / Q000737:chemistry*
D011166:Porphyrins; D026082:Singlet Oxygen; D004247:DNA