硫代磷酸酯修饰的寡脱氧核糖核苷酸。III. 源自非对映体O-乙基硫代磷酸酯的Rp-Rp、Sp-Sp和Rp-Sp双链体[d(GGSAATTCC)]2的核磁共振和紫外光谱研究。
Phosphorothioate-modified oligodeoxyribonucleotides. III. NMR and UV spectroscopic studies of the Rp-Rp, Sp-Sp, and Rp-Sp duplexes, [d(GGSAATTCC)]2, derived from diastereomeric O-ethyl phosphorothioates.
作者信息
LaPlanche L A, James T L, Powell C, Wilson W D, Uznanski B, Stec W J, Summers M F, Zon G
出版信息
Nucleic Acids Res. 1986 Nov 25;14(22):9081-93. doi: 10.1093/nar/14.22.9081.
Abstract
2D-NOE and 1H NMR chemical shift data obtained for the title oligonucleotides were compared with similar data previously reported [Broido et al. (1985) Eur. J. Biochem. 150, 117-128] for the unmodified "parent" structure, [d(GGAATTCC)]2. The spectroscopically detectable structural perturbations caused by replacement of phosphate oxygen with sulfur were mostly localized within the GsA moiety, and were greater for the Rp configuration wherein sulfur is oriented into the major groove of the B-helix. UV-derived Tm measurements gave the following order of stability for the duplexes in 0.4 M NaCl: unmodified (33.9 +/- 0.1 degrees C) approximately Sp-Sp (34.1 degrees C) greater than Rp-Rp (31.7 degrees C). The title compounds were prepared by a new and convenient synthetic route which utilized HPLC to separate the diastereomeric O-ethyl phosphorothioate precursors, (Rp)- and (Sp)-d[GG(S,Et)AATTCC], for subsequent de-ethylation by ammonia in water.
摘要
将所获得的标题寡核苷酸的二维核Overhauser效应（2D-NOE）和氢核磁共振（1H NMR）化学位移数据，与先前报道的[布罗伊多等人（1985年）《欧洲生物化学杂志》150卷，第117 - 128页]未修饰的“亲本”结构[d（GGAATTCC）]2的类似数据进行了比较。由硫取代磷酸氧所引起的可通过光谱检测到的结构扰动，大多局限于鸟嘌呤-腺嘌呤（GsA）部分，并且对于硫朝向B型螺旋大沟的Rp构型而言扰动更大。紫外衍生的熔解温度（Tm）测量给出了在0.4M氯化钠中双链体稳定性的以下顺序：未修饰的（33.9±0.1℃）≈Sp-Sp（34.1℃）＞Rp-Rp（31.7℃）。标题化合物是通过一种新的便捷合成路线制备的，该路线利用高效液相色谱（HPLC）分离非对映体的O-乙基硫代磷酸酯前体，即（Rp）-和（Sp）-d[GG（S，Et）AATTCC]，随后在水中用氨进行脱乙基反应。
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