Rippe K, Fritsch V, Westhof E, Jovin T M
Abteilung Molekulare Biologie, Max-Planck-Institut für biophysikalische Chemie, Göttingen, Germany.
EMBO J. 1992 Oct;11(10):3777-86. doi: 10.1002/j.1460-2075.1992.tb05463.x.
The oligonucleotides d[(G-A)7G] and d[(G-A)12G] self-associate under physiological conditions (10 mM MgCl2, neutral pH) into a stable double-helical structure (psRR-DNA) in which the two polypurine strands are in a parallel orientation in contrast to the antiparallel disposition of conventional B-DNA. We have characterized psRR-DNA by gel electrophoresis, UV absorption, vacuum UV circular dichroism, monomer-excimer fluorescence of oligonucleotides end-labelled with pyrene, and chemical probing with diethyl pyrocarbonate and dimethyl sulfate. The duplex is stable at pH 4-9, suggesting that the structure is compatible with, but does not require, protonation of the A residues. The data support a model derived from force-field analysis in which the parallel-stranded d(G-A)n helix is right-handed and constituted of alternating, symmetrical Gsyn.Gsyn and Aanti.Aanti base pairs with N1H...O6 and N6H...N7 hydrogen bonds, respectively. This dinucleotide structure may be the source of a negative peak observed at 190 nm in the vacuum UV CD spectrum, a feature previously reported only for left-handed Z-DNA. The related sequence d[(GAAGGA)4G] also forms a parallel-stranded duplex but one that is less stable and probably involves a slightly different secondary structure. We discuss the potential intervention of psRR-DNA in recombination, gene expression and the stabilization of genomic structure.
寡核苷酸d[(G-A)7G]和d[(G-A)12G]在生理条件下(10 mM MgCl2,中性pH)会自我缔合形成一种稳定的双螺旋结构(psRR-DNA),其中两条多聚嘌呤链呈平行排列,这与传统B-DNA的反平行排列不同。我们通过凝胶电泳、紫外吸收、真空紫外圆二色性、用芘末端标记的寡核苷酸的单体-激基缔合物荧光以及焦碳酸二乙酯和硫酸二甲酯的化学探针法对psRR-DNA进行了表征。该双链体在pH 4-9时稳定,这表明该结构与A残基的质子化兼容,但并非必需。这些数据支持了一个源自力场分析的模型,其中平行链的d(G-A)n螺旋是右手螺旋,由交替的、对称的Gsyn.Gsyn和Aanti.Aanti碱基对组成,分别具有N1H...O6和N6H...N7氢键。这种二核苷酸结构可能是真空紫外圆二色光谱中在190 nm处观察到的负峰的来源,这一特征此前仅在左手Z-DNA中报道过。相关序列d[(GAAGGA)4G]也形成平行链双链体,但稳定性较差,可能涉及略有不同的二级结构。我们讨论了psRR-DNA在重组、基因表达和基因组结构稳定中的潜在作用。