Interaction of water-soluble Cu(II), Ni(II), and Co(III) porphyrins with polynucleotides.
Interaction of water-soluble Cu(II), Ni(II), and Co(III) porphyrins with polynucleotides.
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水溶性 Cu(II)、Ni(II) 和 Co(III) 卟啉与多核苷酸的相互作用。
DOI：
10.1016/0162-0134(90)80016-q
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发表时间：
1990
影响因子：
3.9
通讯作者：
Nakamoto,K
中科院分区：
文献类型：
--
作者：
Bütje,K;Nakamoto,K
用紫外-可见光谱和共振拉曼光谱研究了六种水溶性阳离子卟啉的Cu（II）、Ni（II）和Co（III）配合物与小牛胸腺DNA、poly（dG-dC）2和poly（dA-dT）2的相互作用：四（2-N-）和（3-N-甲基吡啶基）卟啉（1，2）;单苯基三（4-N-甲基吡啶基）卟啉（4）;顺-和反-二苯基-双（4-N-甲基吡啶基）卟啉（5，6）。与四（4-N-甲基吡啶基）卟啉（3）的结合进行了比较。如果N+-CH 3基团从帕拉（3）移动到Meta位（2），则自由卟啉与金属配合物的键合只会逐渐改变，因此，正方平面的Cu-和Ni-2在G-C位插入，而Co-2在A-T位以沟槽键合。另外，Ni-2也可能插层在A-T位上。当N+-CH 3基团位于邻位（1）时，2-N-甲基吡啶基的高旋转势垒阻止了Cu-和Ni-1的嵌入，导致弱的外结合。在离子强度μ = 0.2时，没有证据表明Co-1与任何多核苷酸发生了显著的相互作用。当3中的带电N-甲基吡啶基随后被苯基取代时（4，5/6），Cu（II）和Ni（II）络合物结合到螺旋外部或仅部分插入的趋势增加，以完全插入为代价。库仑吸引力仍然很强，在3、4、5和6之间没有检测到显著差异。Ni-4与poly（dA-dT）2的结合方式与Ni-3相同。Co-4、Co-5和Co-6的外结合与Co-2和Co-3的外结合略有不同。
The interaction of the Cu(II), Ni(II) and Co(III) complexes of the following six water-soluble cationic porphyrins with calf thymus DNA, poly(dG-dC)2and poly(dA-dT)2was studied by UV-visible and resonance Raman spectroscopy: tetrakis(2-N-) and (3-N-methylpyridyl) porphyrin (1,2); monophenyltris(4-N-methylpyridyl)porphyrin (4); cis- and trans-diphenyl-bis (4-N-methylpyridyl)porphyrin (5,6). The binding to nucleic acids was compared with that of tetrakis(4-N-methylpyridyl)porphyrin (3). If the N+-CH3group is moved from the para (3) to the meta position (2), binding of the free porphyrin as well as that of the metal complexes is only gradually modified; thus, the square-planar Cu- and Ni-2are intercalated at the G-C site whereas Co-2is groove-bound at A-T. Additionally, Ni-2is probably also intercalated at the A-T site. When the N+-CH3group is located at ortho position (1), the high rotation barrier of the 2-N-methylpyridyl group prevents intercalation of Cu- and Ni-1, resulting in weak outside binding. At ionic strength μ = 0.2, there is no evidence of significant interaction of Co-1with any of the polynucleotides. When the charged N-methylpyridyl groups in3are subsequently replaced by phenyl groups (4,5/6), the tendency of the Cu(II) and Ni(II) complexes to bind to the outside of the helix or to intercalate only partially increases at the expense of full intercalation. The coulombic attraction remains strong, no significant differences can be detected between3,4,5, and6. Ni-4binds to poly(dA-dT)2in the same complicated manner as Ni-3. The outside-binding in Co-4, -5and -6differs slightly from that in Co-2and Co-3.