Universität zu Köln

Herrmann, Nils ORCID: 0000-0002-6468-9180, Heinz, Norah, Dolg, Michael ORCID: 0000-0002-0538-0837 and Cao, Xiaoyan ORCID: 0000-0002-3438-575X (2016). Quantum chemical study of the autoxidation of ascorbate. J. Comput. Chem., 37 (20). S. 1914 - 1924. HOBOKEN: WILEY. ISSN 1096-987X

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Abstract

Reactions involved in the autoxidation of ascorbate have been investigated with quantum chemical first-principles and ab initio methods. Reaction energies and Gibbs energies of the reactions were calculated at the density functional theory level applying the gradient-corrected BP86 and the hybrid B3LYP functionals together with def2-TZVP basis sets. Results of single-point CC2, CCSD, and CCSD(T) calculations were used for calibration of the density functional theory data and show excellent agreement with the B3LYP values. Based on the Gibbs energy ascorbic acid AscH(2) is found to be the energetically lowest species in aqueous solution, whereas the monoanion ascorbate AscH - is the most abundant one near pH=7. Asc 2- was found to be the preferred reducing agent for autoxidation and oxidation processes. The results also support a metal-catalyzed synthesis of the reactive oxygen species H2O2 according to a redox cycling mechanism proposed in literature. (c) 2016 Wiley Periodicals, Inc.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Herrmann, Nils UNSPECIFIED orcid.org/0000-0002-6468-9180 UNSPECIFIED Heinz, Norah UNSPECIFIED UNSPECIFIED UNSPECIFIED Dolg, Michael UNSPECIFIED orcid.org/0000-0002-0538-0837 UNSPECIFIED Cao, Xiaoyan UNSPECIFIED orcid.org/0000-0002-3438-575X UNSPECIFIED
URN:	urn:nbn:de:hbz:38-269341
DOI:	10.1002/jcc.24408
Journal or Publication Title:	J. Comput. Chem.
Volume:	37
Number:	20
Page Range:	S. 1914 - 1924
Date:	2016
Publisher:	WILEY
Place of Publication:	HOBOKEN
ISSN:	1096-987X
Language:	English
Faculty:	Faculty of Mathematics and Natural Sciences
Divisions:	Faculty of Mathematics and Natural Sciences > Department of Chemistry > Institute of Theoretical Chemistry
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language ACID VITAMIN-C; ELECTRONIC-STRUCTURE CALCULATIONS; AUXILIARY BASIS-SETS; GAUSSIAN-BASIS SETS; CRYSTAL-STRUCTURE; AB-INITIO; VIBRATIONAL CHARACTERISTICS; MOLECULAR-DYNAMICS; CORRELATION-ENERGY; CATALYTIC METALS Multiple languages Chemistry, Multidisciplinary Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/26934