Effect of N-alkyl substituents on the DNA binding properties of meso-tetrakis (4-N-alkylpyridinium-4-yl)porphyrins and their nickel derivatives.
Effect of N-alkyl substituents on the DNA binding properties of meso-tetrakis (4-N-alkylpyridinium-4-yl)porphyrins and their nickel derivatives.
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DOI：
10.1016/0162-0134(91)80013-8
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发表时间：
1991-02
影响因子：
3.9
通讯作者：
T. Gray;K. Yue;L. Marzilli
中科院分区：
文献类型：
--
作者：
T. Gray;K. Yue;L. Marzilli
共振拉曼，NMR，和可见光谱，以及粘度和平衡透析研究被用来评估的中位-四（4-N-烷基吡啶-4-基）卟啉阳离子的N-烷基取代基对DNA结合的影响。研究的DNA包括天然DNA、小牛胸腺DNA（CT DNA）、合成的多核苷酸[poly（dGdC）] 2和[poly（dAdT）]2以及寡核苷酸d（TATACGTATA）2。用N-烷基=丙基（TPrpyP（4）和NiTPrpyP（4））和2-羟基乙基（TEtOHpyP（4）和NiTEtOHpyP（4））对卟啉和含Ni（II）的金属卟啉进行了研究。将结果与具有N-甲基取代基的母体卟啉（TMPyP（4）和NiTMPyP（4））的结果进行比较。对于几乎所有的比较，新的卟啉阳离子给出的结果非常相似的TMPyP（4）物种。共振拉曼研究表明，对于三种DNA聚合物，所有的Ni物种在结合到所有三种聚合物时都处于四配位形式。TPrpyP（4）和TEtOHpyP（4）都以与TMPyP（4）相同的嵌入方式与DNA的GC区域结合，其中N-烷基取代基延伸到溶剂中。对于DNA的AT区域，TPrpyP（4）和TEtOHpyP（4）的结合是非嵌入的，如先前对TMPyP（4）所发现的。NiTPrpy（4）和NiTEtOHpyP（4）阳离子以与脱卟啉类似的方式与这些聚合物结合。加入[poly（dAdT）] 2后三种镍卟啉的类似拉曼光谱变化表明部分嵌入没有发生，因为模型表明难以容纳更大的N-烷基取代基。
Resonance Raman, NMR, and visible spectroscopies, as well as viscosity and equilibrium dialysis studies were used to assess the effect of the N-alkyl substituent of meso-tetrakis(4-N-alkylpyridinium-4-yl)porphyrin cations on DNA binding. The DNAs studied include the native DNA, calf thymus DNA (CT DNA), the synthetic polynucleotides [poly(dGdC)]2and [poly(dAdT)]2, and the oligonucleotide d(TATACGTATA)2. Both the porphyrins and the metalloporphyrins containing Ni(II) were examined with the N-alkyl = propyl (TPrpyP(4) and NiTPrpyP(4)) and 2-hydroxyethyl (TEtOHpyP(4) and NiTEtOHpyP(4)). The results were compared to those from the parent porphyrins with the N-methyl substituent (TMpyP(4) and NiTMpyP(4)). For almost all the comparisons made, the new porphyrin cations gave results very similar to those for the TMpyP(4) species. The resonance Raman study indicated that for the three DNA polymers all the Ni species were in the four-coordinate form when bound to all three polymers. It is suggested that both TPrpyP(4) and TEtOHpyP(4) bind to GC regions of DNA in the same intercalative manner as TMpyP(4) with the N-alkyl substituent extended into the solvent. For AT regions of DNA, the binding of TPrpyP(4) and TEtOHpyP(4) is nonintercalative, as found previously for TMpyP(4). The NiTPrpy(4) and NiTEtOHpyP(4) cations bind to these polymers in a similar manner to the apo-porphyrins. The similar Raman spectral changes for the three Ni porphyrins upon addition of [poly(dAdT)]2suggest that partial intercalation is not occurring because models indicate that it would be difficult to accommodate the bulkier N-alkyl substituents.