MOE Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou, PR China.
Spectrochim Acta A Mol Biomol Spectrosc. 2010 Mar;75(3):1108-14. doi: 10.1016/j.saa.2009.12.065. Epub 2010 Jan 4.
The interactions of 5,10,15-tris(1-methylpyridinium-4-yl)-20-(4-hydroxyphenyl)porphyrinatozinc(II) ZnTMPyHP (2) along with CuTMPyHP (3), CoTMPyHP (4), MnTMPyHP (5) and the free base porphyrin H(2)TMPyHP (1) with duplex DNA have been studied by using a combination of absorption, fluorescence titration, surface-enhanced Raman spectroscopy (SERS), induced circular dichroism (ICD) spectroscopy, thermal DNA denaturation, viscosity measurements as well as gel electrophoresis experiment. Their binding modes and intrinsic binding constants (K(b)) to calf DNA (CT DNA) were comparatively studied and were found significantly influenced by different metals coordinated with the porphyrin plane. Except 3, which has four-coordination structure at the metal, all the metal derivatives showed non-intercalative DNA-binding mode and lower K(b) than the free base porphyrin 1, most probably due to the steric hindrance results from the axial ligands of the inserted metals which are five or six-coordination structures. Meanwhile, the insertion of metals into cationic porphyrin greatly removed the self-aggregation of the metal-free porphyrins, and thus fully enhanced the singlet oxygen ((1)O(2)) productivities in the DNA photocleavage experiments. Therefore, these metalloporphyrins have comparable DNA cleavage ability with the free base porphyrin.
5,10,15-三(1-甲基吡啶-4-基)-20-(4-羟基苯基)卟啉锌(II) ZnTMPyHP（2）与 CuTMPyHP（3）、CoTMPyHP（4）、MnTMPyHP（5）和游离卟啉 H(2)TMPyHP（1）与双链 DNA 的相互作用已通过吸收、荧光滴定、表面增强拉曼光谱（SERS）、诱导圆二色性（ICD）光谱、热 DNA 变性、粘度测量以及凝胶电泳实验进行了研究。比较研究了它们与小牛 DNA（CT DNA）的结合模式和固有结合常数（K(b)），发现它们受与卟啉平面配位的不同金属的显著影响。除了 3 具有金属的四配位结构外，所有金属衍生物均显示非嵌入 DNA 结合模式，且与游离卟啉 1 的 K(b)值较低，这可能是由于插入金属的轴向配体为五或六配位结构，导致空间位阻较大。同时，金属插入阳离子卟啉中大大减少了无金属卟啉的自聚集，从而在 DNA 光解实验中充分提高了单线态氧（(1)O(2)）的产率。因此，这些金属卟啉与游离卟啉具有相当的 DNA 切割能力。
