氰类和酯类取代基水溶金属卟啉与DNA相互作用的共振拉曼研究

用共振拉曼和紫外－可见吸收光谱研究了水溶金属卟啉４－Ｎ－乙酸乙酯基－吡啶基铜卟啉和镍卟啉［简称Ｃｕ（ＮＥＡＥ）和Ｎｉ（ＮＥＡＥ）］及４－Ｎ－乙腈基－吡啶基铜卟啉［简称Ｃｕ（ＮＡＣＮ）］与小牛胸腺ＤＮＡ的相互作用。分析表明Ｃｕ（ＮＥＡＥ）、Ｎｉ（ＮＥＡＥ）和Ｃｕ（ＮＡＣＮ）分别以外部键联、部分插入和沟槽方式与ＤＮＡ作用；卟啉插入ＤＮＡ时吡啶基团向卟啉环平面转动但不可能转成与之共面；而以非插入方式作用时吡啶基团会向垂直于或者平行于卟啉环平面转动。吡啶取代基的大小和空间位阻是影响相互作用方式的关键因素之一。

The Interaction of Water-soluble Quaternary Ammonium Pyridine Porphyrins with DNA Studied by Resonance Raman Spectroscopy

The interaction of metal water-soluble porphyrins Cu(NEAE), Ni(NEAE) Cu or Ni-tetrakis (4-N-ethylacetatepyridyl) Porphine] and Cu (NACN) Cu-tetrakis (4-N-acetonitrilepyridyl) Porphine] with calf thymus DNA has been investigated by resonance Raman and UV-visible spectroscopy. The results demonstrated that Cu (NEAE), Ni (NEAE) and Cu (NACN) interact with DNA by outside-binding , partial intercalation and groove-binding respectively; The intercalated structure requires the rotation of the pyridyl rings toward the porphyrin core plane, but it is impossible to rotate co-plane with porphyrin core plane. The pyridyl rings may rotate toward perpendicular direction or co-plane direction with porphyrin core plane for non-intercalated structure. The size and steric hindrance of substituent of porphyrin is one of the crucial factors to affect the interaction between porphyrins and DNA.