ATTENTION: The software behind KU ScholarWorks is being upgraded to a new version. Starting July 15th, users will not be able to log in to the system, add items, nor make any changes until the new version is in place at the end of July. Searching for articles and opening files will continue to work while the system is being updated.
If you have any questions, please contact Marianne Reed at mreed@ku.edu .
Low-Temperature NMR Characterization of Reaction of Sodium Pyruvate with Hydrogen Peroxide
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 |