The Phosphoenolpyruvate Phosphorylation: A Self-Organized Mechanism with Implications to Understand the RNA Transformations

The Phosphoenolpyruvate Phosphorylation: A Self-Organized Mechanism with Implications to Understand the RNA Transformations
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DOI:
10.1080/10426501003598655
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发表时间:
2010-01-01
影响因子:
1.3
通讯作者:
Micheletti, Gabriele
Micheletti, Gabriele
中科院分区:
化学4区
文献类型:
--
作者:
Baccolini, Graziano;Boga, Carla;Micheletti, Gabriele

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本文利用31 P核磁共振技术研究了磷酸烯醇式丙酮酸(PEP)的非酶水解反应。我们已经证明,PEP在水中主要存在作为一个非常稳定的环状五配位磷化合物与其他环状形式的平衡。这解释了PEP在水中的稳定性。相反,在将醇添加到PEP水溶液中之后,形成了其他非常不稳定的环状五配位中间体,其立即崩溃,给出了醇的可行磷酸化。已知环状五配位磷中间体比相应的非环状中间体更受青睐,其优势系数为106-108,并且在本研究中也发现,这种偏好可能是能够克服非生物化学混乱的驱动机制,从而允许前体RNA分子的形成可能具有自组织过程。
In this article, we present a study about the non-enzymatic hydrolysis of phosphoenolpyruvate (PEP) by following the reaction course through 31P NMR spectroscopy. We have demonstrated that PEP in water exists mainly as a very stable cyclic pentacoordinate phosphorus compound in equilibrium with other cyclic forms. This explains the PEP stability in water. In contrast, after addition of an alcohol to a PEP aqueous solution, other very unstable cyclic pentacoordinated intermediates are formed, which immediately collapse, giving a feasible phosphorylation of the alcohol. It is known that cyclic pentacoordinated phosphorus intermediates are favored over the corresponding acyclic intermediates by a factor of 106-108, and this preference, found also in this study, might be the odriver mechanismo able to overcome the clutter of abiotic chemistry, thus permitting formation of pre-RNA molecules probably with a oself-organized process.o.