Synthesis and proton-NMR studies of oligonucleotides containing an apurinic (AP) site.
Synthesis and proton-NMR studies of oligonucleotides containing an apurinic (AP) site.
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含有无嘌呤 (AP) 位点的寡核苷酸的合成和质子 NMR 研究。
DOI：
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发表时间：
1987
影响因子：
4.4
通讯作者：
C. W. Hilbers
中科院分区：
文献类型：
--
作者：
J. Raap;C. Dreef;G. A. van der Marel;J. V. van Boom;C. W. Hilbers
为了阐明碱基缺失的寡脱氧核糖核苷酸的构象性质，采用磷酸三酯法合成了分子d-CpS(pCpG)n （n = 1,2; S =糖），并用1H-NMR对其进行了表征。通过1D和2d核磁共振技术获得了两种化合物的所有非交换质子共振的完整分配。结合计算机模拟，这些光谱得到了高精度的质子-质子和质子-磷耦合常数。这些数据为糖和主链构象提供了有价值的信息。似乎d-Cp1Sp2Cp3G4在任何研究条件下都不形成双相。相反，碱基缺失的六聚体d-Cp1Sp2Cp3Gp4Cp5G6在280 K时以右手“交错”双链形式出现：该双链的核心由残基C(3)-G(6)组成；两个“悬空”残基C(1)和S(2)位于双链的两个5'端。[d-CpS(pCpG)2]2对应的小质子共振的分配是基于它们的热行为：这些共振的谱线展宽作为温度的函数进行了研究。化学位移和亚质子共振的数目与上述交错双相结构中可以形成的沃森-克里克碱基对的数目和类型是一致的。通过分析芳香碱和H-1′质子的化学位移随温度的变化曲线，得到了双相反应的热力学参数。这表明C(1)的胞嘧啶环至少部分时间与位于互补链上的核苷酸残基G(6)上的鸟嘌呤环堆叠在一起。研究了Lys-Trp-Lys与[d-CpS(pCpG)2]2和[d-CpGpCpG]1的结合。由此可见，色氨酸残基的吲哚环可能堆积在这两个双链的3′末端鸟嘌呤碱基上，而不是堆积在无嘌呤（AP）位点附近的核酸碱基上。
In order to elucidate the conformational properties of base-deleted oligodeoxyribonucleotides, the molecules d-CpS(pCpG)n (n = 1,2; S = sugar) were synthesized by the phosphotriester method and characterized by 1H-NMR spectroscopy. Complete assignment of all non-exchangeable proton resonances of both compounds was obtained by 1D- and 2D-NMR techniques. In combination with computer simulation, these spectra yielded proton-proton and proton-phosphorus coupling constants of high accuracy. These data provide valuable information about the sugar and the backbone conformation. It appears that d-Cp1Sp2Cp3G4 does not form a duplex under any of the conditions studied. On the contrary, the base-deleted hexamer d-Cp1Sp2Cp3Gp4Cp5G6 occurs as a right-handed' staggered' DNA duplex at 280 K: the core of this duplex is formed by the residues C(3)-G(6); two 'dangling' residues C(1) and S(2) are located at the two 5'-ends of the duplex. The assignment of the corresponding imino proton resonances for [d-CpS(pCpG)2]2 was based on their thermal behavior: the line broadening of these resonances was studied as a function of temperature. The chemical shift and the number of imino proton resonances accord well with the number and type of Watson-Crick base pairs which can be formed in the staggered duplex described above. Thermodynamic parameters of duplex formation were obtained from an analysis of the chemical shift versus temperature profiles of aromatic base and H-1' protons. It is suggested that the cytosine ring of C(1) stacks, at least part of the time, with the guanine ring on the nucleotide residue, G(6), situated in the complementary strand. The binding of Lys-Trp-Lys to [d-CpS(pCpG)2]2 as well as to [d-CpGpCpG]1 was investigated. It is concluded that the indole ring of the tryptophan residue probably stacks on top of the 3'-terminal guanine base of both duplexes, but not on the nucleic acid bases next to the apurinic (AP) site.
DOI：
10.1073/pnas.83.11.3746
发表时间：
1986-06-01
影响因子：
11.1
作者：
BRESLAUER, KJ;FRANK, R;MARKY, LA
通讯作者：
MARKY, LA
赖氨酰-5-氟色氨酸的非对映体三肽与 DNA 的相互作用。
影响因子：
2.9
作者：
Shine,NR;James,TL
通讯作者：
James,TL