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 “driver mechanism” able to overcome the clutter of abiotic chemistry, thus permitting formation of pre-RNA molecules probably with a “self-organized process.”
G. Baccolini, C. Boga, G. Micheletti (2010). The Phosphoenolpyruvate Phosphorylation: A Self-Organized Mechanism with Implications to Understand the RNA Transformations Volume 185, Issue 11, 2010, Pages 2303 – 2315. PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS, 185, 2303-2315 [10.1080/10426501003598655].
The Phosphoenolpyruvate Phosphorylation: A Self-Organized Mechanism with Implications to Understand the RNA Transformations Volume 185, Issue 11, 2010, Pages 2303 – 2315
BACCOLINI, GRAZIANO;BOGA, CARLA;MICHELETTI, GABRIELE
2010
Abstract
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 “driver mechanism” able to overcome the clutter of abiotic chemistry, thus permitting formation of pre-RNA molecules probably with a “self-organized process.”I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
