The New York Center for Astrobiology and Department of Chemistry & Chemical Biology, Rensselaer Polytechnic Institute, Troy, NY, 12180, USA.
J Mol Evol. 2013 Jun;76(6):371-9. doi: 10.1007/s00239-013-9568-x. Epub 2013 Jun 18.
The montmorillonite-catalyzed reactions of the 5'-phosphorimidazolide of adenosine used as a model generated RNA type oligomers. These reactions were found to be dependent on the presence of mineral salts. Whereas montmorillonite (pH 7) produced only dimers and traces of trimer in water, addition of sodium chloride (0.1-2.0 M) enhanced the chain length of oligomers to 10-mers as detected by HPLC. Maximum catalytic activity was observed with sodium chloride at a concentration between 0.8 and 1.2 M. This concentration of sodium chloride resembled its abundance in the ancient oceans (0.9-1.2 M). Magnesium chloride produced a similar effect but its joint action with sodium chloride did not produce any difference in the oligomer chain length. Therefore, Mg(2+) was not deemed necessary for generating longer oligomers. The effect of monovalent cations upon RNA chain length was: Li(+) > Na(+) > K(+). A similar effect was observed with the anions with enhanced oligomer length in the following order: Cl(-) > Br(-) > I(-). Thus, the smaller ions facilitated the formation of the longest oligomers. Inorganic salts that tend to salt out organic compounds from water and salts which show salt-in effects had no influence on the oligomerization process indicating that the montmorillonite-catalyzed RNA synthesis is not affected by either of these hydrophobic or hydrophilic interactions. A 2.3-fold decrease in the yield of cyclic dimer was observed upon increasing the sodium chloride concentration from 0.2 to 2.0 M. Inhibition of cyclic dimer formation is vital for increasing the yield of linear dimers and longer oligomers. In summary, sodium chloride is likely to have played an essential role in any clay mineral-catalyzed prebiotic RNA synthesis.
作为模型生成的 RNA 型寡聚物,使用腺苷的 5'-磷酸亚氨基咪唑化合物进行的蒙脱土催化反应。这些反应被发现依赖于矿物盐的存在。虽然蒙脱土(pH7)在水中仅产生二聚体和痕量三聚体,但添加氯化钠(0.1-2.0M)可将寡聚物的链长增强至 10 聚体,如 HPLC 检测到的那样。在 0.8 至 1.2M 的氯化钠浓度下观察到最大催化活性。这种氯化钠浓度类似于其在古代海洋中的丰度(0.9-1.2M)。氯化镁产生类似的效果,但它与氯化钠的共同作用并未使寡聚物链长产生任何差异。因此,Mg(2+) 被认为不是产生更长寡聚物的必要条件。单价阳离子对 RNA 链长的影响为:Li(+)>Na(+)>K(+)。用阴离子观察到类似的效果,增强的寡聚物长度按以下顺序排列:Cl(-)>Br(-)>I(-)。因此,较小的离子有利于形成最长的寡聚物。倾向于将有机化合物从水中沉淀出来的无机盐以及表现出盐效应的盐对寡聚化过程没有影响,这表明蒙脱土催化的 RNA 合成不受这些疏水性或亲水性相互作用的影响。当氯化钠浓度从 0.2 增加到 2.0M 时,环状二聚体的产率观察到 2.3 倍的降低。抑制环状二聚体的形成对于提高线性二聚体和更长寡聚物的产率至关重要。总之,氯化钠可能在任何粘土矿物催化的原始 RNA 合成中都发挥了重要作用。