Porphyrins in complex with DNA: Modes of interaction and oxidation reactions

• Porphyrins can bind double-stranded and G-quadruplex DNA.
• Oxidative DNA damage.
• Porphyrin-based DNAzymes.

Metalloporphyrins are efficient biomimetic models of heme enzymes such as cytochrome P450 and peroxidases. They are also endowed with high affinity for double-stranded and G-quadruplex DNA. The different DNA specific binding modes of porphyrins will be reviewed. After a summary of current knowledge on the mechanism of action of heme enzymes and their models some examples of the oxidation reactions carried out by porphyrins tightly bound to DNA are presented. The oxidation mediated by the porphyrin model may be directed toward DNA and the porphyrin/DNA complex leads to DNA damage (artificial nuclease) or may be directed toward small substrates present in the bulk (DNAzyme). The chosen examples of porphyrins interacting with either double-stranded DNA or G-quadruplex DNA hosts highlight how DNA participates in the reaction or contributes to a better understanding of the chemistry of porphyrin models.

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