dc.contributor.author | Asmus, Christopher Erik Helmut | |
dc.contributor.author | Mozziconacci, Olivier | |
dc.contributor.author | Schöneich, Christian | |
dc.date.accessioned | 2017-04-27T17:46:41Z | |
dc.date.available | 2017-04-27T17:46:41Z | |
dc.date.issued | 2015-02-12 | |
dc.identifier.citation | Asmus, C., Mozziconacci, O., & Schöneich, C. (2015). Low-Temperature NMR Characterization of Reaction of Sodium Pyruvate with Hydrogen Peroxide. The Journal of Physical Chemistry. A, 119(6), 966–977. http://doi.org/10.1021/jp511831b | en_US |
dc.identifier.uri | http://hdl.handle.net/1808/23836 | |
dc.description.abstract | It was proposed that the reaction of sodium pyruvate and H2O2 generates the intermediate 2-hydroperoxy-2-hydroxypropanoate, which converts into acetate, CO2, and H2O (Aleksankin et al. Kernenergie 1962, 5, 362–365). These conclusions were based on the products generated in 18O-enriched water and H2O2 reacting with pyruvic acid at room temperature; however, the lifetime of 2-hydroperoxy-2-hydroxypropanoate at room temperature is too short for direct spectroscopic observation. Therefore, we applied the combination of low-temperature and 13C NMR techniques to verify, for the first time, the formation of 2-deuteroperoxy-2-deuteroxypropanoate in mixtures of D2O and methanol-d4 and to monitor directly each species involved in the reaction between D2O2 and 13C-enriched pyruvate. Our NMR results confirm the formation of 2-deuteroperoxy-2-deuteroxypropanoate, where the respective chemical shifts are supported by density functional theory (DFT) calculations. At near-neutral apparent pD (pD*) and −35 °C, the formation of 2-deuteroperoxy-2-deuteroxypropanoate occurred with k = 2.43 × 10−3 dm3·mol−1·s−1. The subsequent decomposition of 2-deuteroperoxy-2-deuteroxypropanoate into acetate, CO2, and D2O occurred with k = 2.58 × 10−4 s−1 at −35 °C. In order to provide a full kinetic analysis, we also monitored the equilibrium of pyruvate and methanol with the hemiacetal (2-deuteroxy-2-methoxypropanoate). The kinetics for the reaction of sodium pyruvate and D2O2 were fitted by taking into account all these equilibria and species. | en_US |
dc.publisher | American Chemical Society | en_US |
dc.rights | This document is the Accepted Manuscript version of a Published Work that appeared in final form in the Journal of Physical Chemistry A, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://dx.doi.org/10.1021/jp511831b. | en_US |
dc.title | Low-Temperature NMR Characterization of Reaction of Sodium Pyruvate with Hydrogen Peroxide | en_US |
dc.type | Article | en_US |
kusw.kuauthor | Asmus, Christopher | |
kusw.kuauthor | Mozziconacci, Olivier | |
kusw.kuauthor | Schöneich, Christian | |
kusw.kudepartment | Pharmaceutical Chemistry | en_US |
dc.identifier.doi | 10.1021/jp511831b | en_US |
kusw.oaversion | Scholarly/refereed, author accepted manuscript | en_US |
kusw.oapolicy | This item meets KU Open Access policy criteria. | en_US |
dc.identifier.pmid | PMC4782753 | en_US |
dc.rights.accessrights | openAccess | |