Photoinduced Electron Transfer between DNA and Water-Soluble Porphyrins

Photophysical properties of five kinds of porphyrins (H₂TMPyP, ZnTMPyP, PdTMPyP, H₂TPPS, and ZnTPPS) complexed with model DNAs (ctDNA and dGMP) have been investigated using steady-state absorption, circular dichroism (CD), and femtosecond transient absorption spectroscopy. Upon addition of ctDNA (or dGMP), larger hypochromism and red shifts are observed for H₂TMPyP and PdTMPyP compared to the other samples. The steady-state measurements have suggested that the binding modes of H₂TMPyP-ctDNA and PdTMPyP-ctDNA are partial intercalation and full intercalation, respectively, while ZnTMPyP-ctDNA shows outside groove binding. No significant interaction was observed between both H₂TPPS and ZnTPPS with two kinds of DNA. Upon excitation of the porphyrins into the higher excited state S₂ (Soret band), the appearance of the transient absorption from ∼500 to ∼620 nm at about 0.05 ps in H₂TMPyP-ctDNA, H₂TMPyP-dGMP, and PdTMPyP-dGMP indicates the occurrence of the electron transfer (ET) from guanine to H₂TMPyP and PdTMPyP. The forward ET are extremely fast (k_f ≥ 1.0 × 10¹³ s^-1), and the backward ET rates are ∼5.6 × 10¹² and ∼4.0 × 10¹² s^-1, respectively. The complexation with DNA may lead to the shorter lifetime of the fluorescence of H₂TMPyP and PdTMPyP.