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[通过氢离子交换动力学方法研究溶液中聚(rG)和聚(rG)-聚(rC)的反应能力与结构]

[Reaction capabilities and structure of poly(rG) and poly(rG)-poly(rC) in solution by the method of the kinetics of hydrogen ion exchange].

作者信息

Lesnik E A, Maslova R N, Varshavskiĭ I M

出版信息

Mol Biol (Mosk). 1976 Jan-Feb;10(1):114-21.

PMID:183102
Abstract

Data on the kinetics of 1H greater than 3H exchange between water and C(8)H groups of guanylic residues in the poly(rG) and poly poly(rG)-poly(rC) are presented. Furthermore, optical properties (CD spectra and hyperchromism) of neutral solutions of these polymers from 20 to 100 degrees C are described. It is shown that the exchange in poly(rG) within the temperature range from 20 to 80 degrees C proceeds faster than in rGMP. Within the temperature range from 20 to 40 degrees C such an acceleration of the exchange is observed also in poly(rG)-poly(rC). According to the ylide mechanism of the exchange reaction the observed accleration of the exchanged in in C(8)H groups of guanylic residues is considered as a consequence of an increase of the positive charge at N(7) atoms. This effect is due to formation of additional hydrogen bonds in which N(7) atoms take part. The exchange in poly(rG)-poly(rG) at temperatures hihger than 75 degrees C, when these additional hydrogen bonds are absent, proceeds more slowly than in rGMP. Such picture is usual in other previously studied polynucleotides whose structure in solution is stabilized only by Watson - Crick hydrogen bonds and stacking interactions. The data obtained support a Guschelbauer's model of the four-stranded stranded poly(rG). They also indicate the posibility of associates formation in poly(rG)-poly(rC) solutions at temperature lower than 40 degrees C being stabilized by hydrogen bonds in which N(7) atoms of guanylic residues take part.

摘要

本文给出了聚(rG)以及聚(rG)-聚(rC)中鸟苷酸残基的水与C(8)H基团之间1H大于3H交换动力学的数据。此外,还描述了这些聚合物在20至100摄氏度中性溶液中的光学性质(圆二色光谱和增色效应)。结果表明,在20至80摄氏度温度范围内,聚(rG)中的交换比在rGMP中进行得更快。在20至40摄氏度温度范围内,聚(rG)-聚(rC)中也观察到这种交换加速现象。根据交换反应的叶立德机理,鸟苷酸残基C(8)H基团中观察到的交换加速被认为是N(7)原子上正电荷增加的结果。这种效应是由于形成了N(7)原子参与的额外氢键。在高于75摄氏度的温度下,当不存在这些额外氢键时,聚(rG)-聚(rG)中的交换比在rGMP中进行得更慢。在其他先前研究的多核苷酸中也常见这种情况,其在溶液中的结构仅通过沃森-克里克氢键和堆积相互作用得以稳定。所获得的数据支持了古舍尔鲍尔提出的四链聚(rG)模型。它们还表明,在低于40摄氏度的温度下,聚(rG)-聚(rC)溶液中可能形成由鸟苷酸残基的N(7)原子参与的氢键稳定的缔合体。

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