Universität zu Köln

Peckelsen, Katrin, Martens, Jonathan ORCID: 0000-0001-9537-4117, Czympiel, Lisa, Oomens, Jos ORCID: 0000-0002-2717-1278, Berden, Giel, Gruendemann, Dirk, Meijer, Anthony J. H. M. and Schaefer, Mathias ORCID: 0000-0002-5943-4335 (2017). Ergothioneine and related histidine derivatives in the gas phase: tautomer structures determined by IRMPD spectroscopy and theory. Phys. Chem. Chem. Phys., 19 (34). S. 23362 - 23373. CAMBRIDGE: ROYAL SOC CHEMISTRY. ISSN 1463-9084

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Abstract

L-Ergothioneine (ET) is a sulfur-containing derivative of the amino acid histidine that offers unique antioxidant properties. The enzyme independent redox-chemistry of ET relies on the availability of the thiol tautomer to allow oxidative formation of disulfide bridges, i.e., the tautomeric equilibrium. To study the intrinsic properties of ET the tautomeric equilibrium is studied in the gas-phase by infrared multiphoton dissociation (IRMPD) spectroscopy. The IR ion spectra of isolated molecular ions of ET and of the biosynthetic precursors of ET, i.e., hercynine and N-epsilon-methyl-hercynine are acquired. The analyte structures are independently investigated by density functional theory (DFT) and computed linear IR-spectra of tautomer ion structures are compared with the gas-phase spectra for identification. For the molecular ion of ET the simulated IR spectra of thione and thiol structures match the recorded IRMPD spectrum and that prevents an individual structure assignment. On the other hand, theory suggests that ET adopts a thione tautomer in MeOH solution which could be carried over from the condensed phase to gas phase and could be kinetically trapped after effective electrospray phase transfer and desolvation. Such a non-thermal behavior is also found for the molecular ions of protonated hercynine and N-epsilon-methylhercynine. Contrary to that, the sodium complex ions of ET, hercynine and N-epsilon-methyl-hercynine adopt the respective ground structures predicted by theory, which are reliably identified spectroscopically. For ET the thione tautomer is by far the most stable isomer in the sodium complex molecular ion.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Peckelsen, Katrin UNSPECIFIED UNSPECIFIED UNSPECIFIED Martens, Jonathan UNSPECIFIED orcid.org/0000-0001-9537-4117 UNSPECIFIED Czympiel, Lisa UNSPECIFIED UNSPECIFIED UNSPECIFIED Oomens, Jos UNSPECIFIED orcid.org/0000-0002-2717-1278 UNSPECIFIED Berden, Giel UNSPECIFIED UNSPECIFIED UNSPECIFIED Gruendemann, Dirk UNSPECIFIED UNSPECIFIED UNSPECIFIED Meijer, Anthony J. H. M. UNSPECIFIED UNSPECIFIED UNSPECIFIED Schaefer, Mathias UNSPECIFIED orcid.org/0000-0002-5943-4335 UNSPECIFIED
URN:	urn:nbn:de:hbz:38-217803
DOI:	10.1039/c7cp03843g
Journal or Publication Title:	Phys. Chem. Chem. Phys.
Volume:	19
Number:	34
Page Range:	S. 23362 - 23373
Date:	2017
Publisher:	ROYAL SOC CHEMISTRY
Place of Publication:	CAMBRIDGE
ISSN:	1463-9084
Language:	English
Faculty:	Faculty of Mathematics and Natural Sciences
Divisions:	Faculty of Mathematics and Natural Sciences > Department of Chemistry > Institute of Organic Chemistry
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language PHOTON DISSOCIATION SPECTROSCOPY; INFRARED ION SPECTROSCOPY; MASS-SPECTROMETRY; PROTONATED HISTIDINE; BASIS-SETS; COMPLEXES; BIOSYNTHESIS; TRANSPORTER; IONIZATION; HERCYNINE Multiple languages Chemistry, Physical; Physics, Atomic, Molecular & Chemical Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/21780