Carbazole appended trans-dicationic pyridinium porphyrin finds supremacy in DNA binding/photocleavage over a non-carbazolyl analogue

Abstract

A carbazolyl appended trans-pyridyl porphyrin (1) was synthesized and its dicationic form 2 was obtained by methylation of the pyridyl group. Copper and zinc complexes of porphyrin 2 (Cu(II), 3; Zn(II), 4) were isolated and characterized by various modern spectroscopic techniques. The DNA binding properties of 2, 3, and 4 have been explored against calf thymus-DNA (CT-DNA). DNA binding was quantized using the intrinsic binding constant (K_b) that was calculated by UV-visible absorption spectroscopy, and the value K_b = 1.6 × 10⁶ M⁻¹ for compound 2 reveals a better interaction of 2 towards CT-DNA than those of 3 (3.1 × 10⁵ M⁻¹) and 4 (3.4 × 10⁵ M⁻¹), which follows the order 2 > 4 > 3. The fluorescence quenching efficiency and ethidium bromide quenching assay also indicated a good binding affinity of all the compounds towards CT-DNA. Furthermore, the spectroscopic data suggest that the possible mode of interaction is intercalation. The docking studies were in accordance with the experimental results. Notably, DNA cleavage studies reveal that 2 shows better damage than 3 and 4 which is in accordance with the binding affinity order 2 > 4 > 3. The observed quantum yield (2: 0.65, 3: 0.33, and 4: 0.97) and no change in DNA cleavage in the presence of NaN₃ reveal the involvement of singlet oxygen. The singlet excited state lifetimes were in the range of 6.3–1.2 ns. Furthermore, these porphyrins can be investigated as interesting photosensitizers in photodynamic therapy and photochemotherapy.