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Understanding the Aldo-Enediolate Tautomerism of Glycolaldehyde in Basic Aqueous Solutions

dc.contributor.authorAzofra, Luis Miguel
dc.contributor.authorQuesada-Moreno, María del Mar
dc.contributor.authorAlkorta, Ibon
dc.contributor.authorAvilés-Moreno, Juan Ramón
dc.contributor.authorElguero, José
dc.contributor.authorLópez-González, Juan Jesús
dc.date.accessioned2025-01-30T07:25:05Z
dc.date.available2025-01-30T07:25:05Z
dc.date.issued2015
dc.description.abstractThe biochemically important interconversion process between aldoses and ketoses is assumed to take place via 1,2-enediol or 1,2-enediolate intermediates, but such intermediates have never been isolated. The current work was undertaken in an attempt to detect the presence of the 1,2-enediol structure of glycolaldehyde in alkaline medium, actually a 1,2-enediolate, and to try to clarify the scarce data existing about both the formation of the deprotonated enediol and the aldo-enediolate equilibrium. The Raman spectra of neutral and basic solutions were recorded as a function of time for eleven days. Several bands associated with the presence of the enediolate were observed in alkaline medium. Glycolaldehyde exists as three different structures in aqueous solution at neutral pH, i.e. hydrated aldehydes, aldehydes and dimers, with a respective ratio of approximately 4:0.25:1. Additionally, the formation of Z-enediolate forms takes place at basic pH, together with the increase of aldehyde species, as 2-oxoethan-1-olate, and the decrease of hydrated aldehyde and dimeric forms. The theoretical ratio ~1.5:1 aldehyde:Z-enediolate reproduces the experimental Raman spectrum in basic medium, with the additional contribution of the previously mentioned ratio between hydrated aldehyde and dimeric forms. Finally, Raman spectroscopy allowed us to monitor the enolization of this carbohydrate model and to conclude that the aldo-enediol tautomerism, formally aldo-enediolate, happens when a suitable amount of basic species is added.es_ES
dc.description.sponsorshipLMA thanks the MICINN for a PhD grant (No. BES-2010-031225). MMQM thanks the Universidad de Jaén for a predoctoral fellowship. This work has been supported by the CTQ2012-35513-C02-02 (MINECO), P08-FQM-04096 (CICE, Junta de Andalucía) and S2013/MIT-2841 (Fotocarbon, Comunidad Autónoma de Madrid) Projects. Computer, storage and other resources from CTI (CSIC) are gratefully acknowledged. Gratitude is also due to University of Jaén for continuing financial support and to its CICT for instrumental facilities. The Authors also thank D. Francisco Hermoso Torres for his help in the laboratory.es_ES
dc.identifier.citationChemPhysChem 2015, 16,2226–2236es_ES
dc.identifier.issn1439-7641es_ES
dc.identifier.other10.1002/cphc.201500139es_ES
dc.identifier.urihttps://hdl.handle.net/10953/4567
dc.language.isoenges_ES
dc.publisherWileyes_ES
dc.relation.ispartofChemPhysChemes_ES
dc.rightsAtribución-NoComercial-SinDerivadas 3.0 España*
dc.rights.accessRightsinfo:eu-repo/semantics/openAccesses_ES
dc.rights.urihttp://creativecommons.org/licenses/by-nc-nd/3.0/es/*
dc.subjectHydrogen bondses_ES
dc.subjectQuantum chemical calculationses_ES
dc.subjectRaman spectroscopyes_ES
dc.subjectSolventses_ES
dc.subjectTautomerismes_ES
dc.titleUnderstanding the Aldo-Enediolate Tautomerism of Glycolaldehyde in Basic Aqueous Solutionses_ES
dc.typeinfo:eu-repo/semantics/articlees_ES
dc.type.versioninfo:eu-repo/semantics/acceptedVersiones_ES

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