Universität zu Köln

Cao, Xiaoyan ORCID: 0000-0002-3438-575X, Wu, Liangliang, Zhang, Jun and Dolg, Michael ORCID: 0000-0002-0538-0837 (2020). Density Functional Studies of Coenzyme NADPH and Its Oxidized Form NADP(+): Structures, UV-Vis Spectra, and the Oxidation Mechanism of NADPH. J. Comput. Chem., 41 (4). S. 305 - 317. HOBOKEN: WILEY. ISSN 1096-987X

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Abstract

Density functional theory has been used to study the biologically important coenzyme NADPH and its oxidized form NADP(+). It was found that free NADPH prefers a compact structure in gas phase and exists in more extended geometries in aqueous solution. Ultraviolet-visible absorption spectra in aqueous solution were calculated for NADPH with an explicit treatment of 100 surrounding water molecules in combination with the COSMO solvation model for bulk hydration effects. The obtained spectra using the B3LYP hybrid density functional agree quite well with experimental data. The changes of Gibbs free energies Delta G in reactions of NADPH with O-2 observed experimentally in cardiovascular and in chemical systems, that is, NADPH + 2 O-3(2) -> NADP(+) + 2 O-2(-) + H+ and NADPH + O-1(2) + H+ -> NADP(+) + H2O2, respectively, were calculated. The NADPH oxidation reaction in the cardiovascular system cannot proceed without activation since the obtained Delta G is positive. The reaction of NADPH in the chemical system with singlet oxygen was found to proceed in two ways, each consisting of two steps, that is, NADPH firstly reacts with O-1(2) barrierlessly to form NADP(+) and HO2-, from which H2O2 is formed in a spontaneous reaction with H+, or O-1(2) and H+ initially form (HO2+)-H-1, which further reacts with NADPH to yield NADP(+) and H2O2. (c) 2019 The Authors. Journal of Computational Chemistry published by Wiley Periodicals, Inc.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Cao, Xiaoyan UNSPECIFIED orcid.org/0000-0002-3438-575X UNSPECIFIED Wu, Liangliang UNSPECIFIED UNSPECIFIED UNSPECIFIED Zhang, Jun UNSPECIFIED UNSPECIFIED UNSPECIFIED Dolg, Michael UNSPECIFIED orcid.org/0000-0002-0538-0837 UNSPECIFIED
URN:	urn:nbn:de:hbz:38-127856
DOI:	10.1002/jcc.26103
Journal or Publication Title:	J. Comput. Chem.
Volume:	41
Number:	4
Page Range:	S. 305 - 317
Date:	2020
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 Physical Chemistry
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language PROTONATED ADENINE; CORRELATION-ENERGY; BASIS-SETS; ABSORPTION; APPROXIMATION; CONFORMATION; FLUORESCENCE; PERFORMANCE; EXCITATION; MOLECULES Multiple languages Chemistry, Multidisciplinary Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/12785