Deciphering the Conformations of Glutathione Oxidized Peptide: A Comparative NMR Study in Solution and Solid-State Environments

Senapati, D and Yarava, J and Ramanathan, KV and Raghothama, S (2024) Deciphering the Conformations of Glutathione Oxidized Peptide: A Comparative NMR Study in Solution and Solid-State Environments. In: Magnetic Resonance in Chemistry .

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Abstract

Glutathione (GSH) and its oxidized dimer (GSSG) play an important role in living systems as an antioxidant, balancing the presence of reactive oxygen species (ROS). The central thiol (-S-S-) bond in GSSG can undergo free rotation, providing multiple conformations with respect to the S-S bridge. The six titratable sites of GSSG, which are influenced by pH variations, affect these conformations in solution, whereas in solids, additionally crystal packing effects come into play. In view of differing reports about the structure of GSSG in literature, we have here conducted an extensive reexamination of its conformations using NMR, and contrasting results have been obtained for solution and solid state. In solution, the existence of more than one antiparallel orientation of the monomer unit with different hydrogen bonding schemes has been indicated by NOE and amide temperature coefficient results. On the other hand, in the solid-state, a 1H-1H double-quantum (DQ) to 13C single-quantum (SQ) correlation study has confirmed a parallel orientation, consistent with the reported X-ray crystal structure. Experimentally assigned solid-state NMR resonances have been validated using GIPAW calculations incorporated in the Quantum ESPRESSO package. © 2024 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Item Type:	Journal Article
Publication:	Magnetic Resonance in Chemistry
Publisher:	John Wiley and Sons Ltd
Additional Information:	The copyright for this article belongs to publishers.
Keywords:	Conformations; Crystal orientation; Electron spin resonance spectroscopy; Nuclear magnetic resonance; Nuclear magnetic resonance spectroscopy; Single crystals, Free rotation; Gluthathione; GSSG; Living systems; NMR studies; NOE; Peptide conformation; Reactive oxygen species; Solid state NMR; Solution NMR, Hydrogen bonds
Department/Centre:	Division of Physical & Mathematical Sciences > Physics
Date Deposited:	14 Nov 2024 22:14
Last Modified:	14 Nov 2024 22:14
URI:	http://eprints.iisc.ac.in/id/eprint/86790

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