Binding modes of V(=O)meso-tetrakis(N-methylpyridinium-4-yl)porphyrin to various synthetic DNAs studied by polarized spectroscopy.

Binding modes of V(=O)meso-tetrakis(N-methylpyridinium-4-yl)porphyrin to various synthetic DNAs studied by polarized spectroscopy.
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通过偏振光谱研究 V(=O) 内消旋四(N-甲基吡啶鎓-4-基)卟啉与各种合成 DNA 的结合模式。

DOI:
10.1016/j.bbagen.2005.11.003
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发表时间:
2006
期刊:
Biochimica et biophysica acta
影响因子:
--
通讯作者:
Seog K. Kim
Seog K. Kim
中科院分区:
--
文献类型:
--
作者:
Taegi Park;J. Ko;Ah Young Ryoo;Jong;D. W. Cho;Seog K. Kim

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采用吸收光谱、圆二色性光谱(CD)和线性二色性光谱(LD)研究了水溶性阳离子氧钒基卟啉(VOTMPyP)与多种合成的聚[d(A-T)2]、聚[d(G-C)2]和聚[d(I-C)2]的相互作用。当VOTMPyP与poly[d(a - t)2]和poly[d(I-C)2]形成络合物时,产生低[VOTMPyP]/[DNA]比值(R比)的正CD信号和R≥0.15以上的强激子CD信号。votmpp -poly[d(G-C)2]配合物的CD光谱表现非常不同:在低R比下观察到少量的负CD,而在高R比下观察到非常小的激子CD。考虑到前两种多核苷酸的小凹槽相似,聚[d(I-C)2]的主凹槽与聚[d(G-C)2]的主凹槽相似,可以得出结论,VOTMPyP以较低的R比结合在所有DNA的小凹槽上,而以较高的R比堆积在DNA的外部。与R比无关,LD研究的VOTMPyP与所有多核苷酸的结合几何形状似乎是均匀的。研究发现,VOTMPyP具有五、六价配位态。对比VOTMPyP与poly[d(A-T)2]和poly[d(G-C)2]配合物的吸收光谱,在较低的R比处(420 ~ 430 nm)和442 nm处),五配位和六配位物质的吸收特征明显。低R比下,六配位的VOTMPyP偏向聚[d(A-T)2],而五配位的VOTMPyP偏向聚[d(G-C)2]。随着R比的增大,叠置种数的增加,六配位种成为主要的结合种。这些观察结果使我们得出结论,鸟嘌呤碱基氨基不仅在决定VOTMPyP的结合模式中起着至关重要的作用,而且在六配位种向五配位种的转化中也起着至关重要的作用。
The interactions between water-soluble cationic oxovanadyl[meso-tetrakis(4-N-methylpyridiumyl)]porphyrin (VOTMPyP) and various synthetic polynucleotide including poly[d(A–T)2], poly[d(G–C)2], and poly[d(I–C)2] were studied using absorption, circular dichroism (CD), and linear dichroism (LD) spectroscopy. When VOTMPyP formed a complex with poly[d(A–T)2] and poly[d(I–C)2], a positive CD signal at low [VOTMPyP]/[DNA] ratios (R ratios) and strong excitonic CD signals at above R≥0.15 were induced. The appearance of the CD spectra of the VOTMPyP-poly[d(G–C)2] complex were very different: a small negative CD at low R ratios and very small excitonic CD at high R ratios were observed. Considering the facts that the minor grooves of the former two polynucleotides resemble and the major groove of poly[d(I–C)2] is similar with that of poly[d(G–C)2], it is conclusive that VOTMPyP binds to the minor groove of all DNA at lower R ratios while they stack at the outside of DNA at higher R ratios. The binding geometry of VOTMPyP to all polynucleotides studied by LD seemed to be homogenous, irrespective of the R ratio. It has been found that VOTMPyP can have five- and six-fluxional coordination states. Comparing the absorption spectra of VOTMPyP complexed with poly[d(A–T)2] and poly[d(G–C)2], the distinctive absorptions of the five- and six-coordinated species were observed at lower R ratios which centered at 420–430 nm and 442 nm, respectively. While the six-coordinated VOTMPyP favored the poly[d(A–T)2], the five-coordinated species favored the poly[d(G–C)2] at the low R ratios. As the stacked species increased with an increasing R ratio, the six-coordinated species became the major bound species. These observations lead us to conclude that the guanine base′ amino group plays a crucial role not only in determining the binding mode of VOTMPyP but also in the conversion of the six-coordinated species to the five-coordinated species.
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
发表时间: 1990
影响因子: 3.9
作者:
Bütje,K;Nakamoto,K
通讯作者: Nakamoto,K