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.”
Titolo: | The Phosphoenolpyruvate Phosphorylation: A Self-Organized Mechanism with Implications to Understand the RNA Transformations Volume 185, Issue 11, 2010, Pages 2303 – 2315 |
Autore/i: | BACCOLINI, GRAZIANO; BOGA, CARLA; MICHELETTI, GABRIELE |
Autore/i Unibo: | |
Anno: | 2010 |
Rivista: | |
Digital Object Identifier (DOI): | http://dx.doi.org/10.1080/10426501003598655 |
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.” |
Data prodotto definitivo in UGOV: | 2010-11-08 10:29:22 |
Appare nelle tipologie: | 1.01 Articolo in rivista |