阳离子5-配位Zn(II)-5,10,15,20-四(4- n -甲基吡啶基)卟啉与DNA和模型多核苷酸的结合:离子强度依赖的[poly(dG-dC)]插层

Biospectroscopy Pub Date : 1999-09-22 DOI:10.1002/(SICI)1520-6343(1999)5:5<302::AID-BSPY5>3.0.CO;2-N

Vladimir S. Chirvony, Victor A. Galievsky, Sergei N. Terekhov, Boris M. Dzhagarov, Vladimir V. Ermolenkov, Pierre-Yves Turpin

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引用次数: 23

摘要

研究了水溶性阳离子卟啉ZnTMpyP(4)[5,10,15,20-四(4- n -甲基吡啶基)卟啉的Zn(II)衍生物]在与[poly(dG-dC)]2配合物中的定位与溶液离子强度μ (μ = 0.20-0.03)的关系。结果表明，ZnTMpyP(4)的Soret波段最大值在络合时从436 nm位移到446 nm，而当μ从0.20降低到0.03时，其强度显著降低(约40%)。这表明卟啉在μ = 0.03时主要嵌入在[poly(dG-dC)]2中。在μ = 0.03时，ZnTMpyP(4)络合到[poly(dG-dC)]2的共振拉曼标记线也支持卟啉嵌入。最后，对分子氧猝灭卟啉三重态的时间分辨瞬态吸收研究表明，在μ = 0.03时，观察到三重态猝灭的双指数动力学，时间常数为~ 12 μs(40%)和~ 35 μs(60%)，远长于自由ZnTMpyP(4)的时间常数(~ 3 μs)。这种强大的[poly(dG-dC)]2的“屏蔽效应”导致了~ 35 μs的分量，这是卟啉插层的特征。另一个在~ 12 μs的组分可能对应于多核苷酸中保护较少的“部分插入”物种。假设离子强度μ(就Na+浓度而言)的降低降低了多核苷酸磷酸基团负电荷的中和作用，因此，允许阳离子ZnTMpyP(4)分子更靠近核苷酸，这有利于在第二步中完全(或部分)插层。由于已知ZnTMpyP(4)被一个H2O分子轴向连接，插入无疑会导致其轴向配体的损失。据我们所知，这是第一次在金属卟啉中观察到这种轴向配体释放，这种释放是由嵌入DNA序列引起的。©1999 John Wiley &儿子,Inc。生物光谱学学报，2009,31 (2):393 - 398

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Binding of the cationic 5-coordinate Zn(II)-5,10,15,20-tetrakis(4-N-methylpyridyl)porphyrin to DNA and model polynucleotides: Ionic-strength dependent intercalation in [poly(dG-dC)]2

The localization of the water-soluble cationic porphyrin ZnTMpyP(4) [Zn(II) derivative of 5,10,15,20-tetrakis(4-N-methylpyridyl)porphyrin] in its complex with [poly(dG-dC)]₂ is studied as a function of the solution ionic strength μ (μ = 0.20–0.03). It is shown that the position of the Soret band maximum of ZnTMpyP(4) shifts from 436 to 446 nm on complexation, while its intensity markedly decreases (∼40%) when μ decreases from 0.20 to 0.03. This suggests that the porphyrin is mainly intercalated in [poly(dG-dC)]₂ at μ = 0.03. Shifts of resonance Raman marker lines under ZnTMpyP(4) complexation to [poly(dG-dC)]₂ at μ = 0.03 also support porphyrin intercalation. At last, a time-resolved transient absorption study of the porphyrin triplet state quenching by molecular oxygen shows that, at μ = 0.03, biexponential kinetics of triplet state quenching is observed with time constants ∼12 μs (40%) and ∼35 μs (60%), that is, much longer than that of the free ZnTMpyP(4) species (∼3 μs). Such a strong “shielding effect” of [poly(dG-dC)]₂, resulting in the ∼35-μs component, is characteristic for porphyrin intercalation. The other component at ∼12 μs likely corresponds to a less protected, “partially intercalated” species in the polynucleotide. It is assumed that a decrease of the ionic strength μ (in terms of Na⁺ concentration) decreases the neutralization of the negative charges of the polynucleotide phosphate groups and, therefore, allows cationic ZnTMpyP(4) molecules to come closer to the nucleotides, this favoring, in a second step, full (or partial) intercalation. Since ZnTMpyP(4) is known to be axially ligated by a H₂O molecule, intercalation undoubtedly must result in a loss of its axial ligand. As far as we know, this is the first observation of such an axial ligand release in metalloporphyrin, induced by intercalation in a DNA sequence. © 1999 John Wiley & Sons, Inc. Biospectroscopy 5: 302–312, 1999

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Biospectroscopy

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