Chiral bis-corrole 1 and 2 were prepared by reaction of （s）-2,2′-bis（bromomethyl）-1, 1′-binaphthyl and 10-（4-hydroxylphenyl）- 5,15-bis（pentafluorophenyl）corrole or 10-（3-hydroxylphenyl）-5,15-bis（pentafluorophenyl）corrole in DMF at 60 ℃ in the presence of anhydrous K2CO3 with an isolated yield -8%. Both 1 and 2 exhibit unsymmetrical induced circular dichroism （ICD） in the soret band with positive exciton chirality.
DNA photocleavage properties of halogenated mono-hydroxyl corrole 1-5 were investigated.It was found that these corroles were able to photocleavage supercoiled pBR 322 DNA（SC） into nicked-circular DNA（NC）.The activity of these corroles follows an order of 4>3>2≈1>5.The photosensitized singlet oxygen（Φ;） quantum yield by these corroles also follows that same order,showing the photocleavage activity is related to the heavy atom effect of halogen atoms on corroles.
The reductive demetalation of manganese corroles was investigated in CH2Cl2/HCl （aqueous） solvent by using SnCl2 as reducing agent. It was found that the demetalation yields depend on the substituents of corrole macrocycle significantly. Electron- rich manganese corrole undergoes reductive demetalation more easily than electron-deficient ones. The isolated reductive demetalation yield of manganese 5,10,15-tris（phenyl）corrole in present system is moderate （46%）. As for electron-deficient Mn（Ⅲ） 5,10,15-tris（pentafluorophenyl）corrole, the acid-induced demetalation in HOAc-HESO4 （V/V = 3：1） is preferable with an isolated yield of 67%.
Hai Yang LiuLing ChenFei YamHai Ying ZhanXiao YingXiang Li WangHuan Feng JiangChi Kwong Chang
The DNA nuclease-like activity of a water soluble manganese corrole 5, 10, 15-tris（N-methyl-4-pyridyl）- corrolatomanga- nese（III） （MnⅢTMPyC） has been investigated. MnⅢMPyC may bind strongly to DNA via outside groove binding mode as indicated by absorption spectra, viscosity measurements and CD spectra. MnInTMPyC exhibited excellent catalytic activity in the DNA oxidative cleavage in the presence of hydroperoxide.
Jun LuHai Yang LiuLei ShiXiang Li WangXiao YingLei ZhangLiang Nian JiLin Quan ZangChi K. Chang
