Properties of Gaseous Deprotonated L-Cysteine S-Sulfate Anion [cysS-SO3]−: Intramolecular H-Bond Network, Electron Affinity, Chemically Active Site, and Vibrational Fingerprints
L-cysteine S-sulfate, Cys-SSO3H, and their derivatives play essential roles in biological chemistry and pharmaceutical synthesis, yet their intrinsic molecular properties have not been studied to date. In this contribution, the deprotonated anion [cysS-SO3]– was introduced in the gas phase by electrospray and characterized by size-selected, cryogenic, negative ion photoelectron spectroscopy. The electron affinity of the [cysS-SO3]• radical was determined to be 4.95 ± 0.10 eV. In combination with theoretical calculations, it was found that the most stable structure of [cysS-SO3]– (S1) is stabilized via three intramolecular hydrogen bonds (HBs); i.e., one O–H$$\cdots\cdots$$N between the –COOH and –NH2 groups, and two N–H$$\cdots\cdots$$O HBs between –NH2 and –SO3, in which the amino group serves as both HB acceptor and donor. In addition, a nearly iso-energetic conformer (S2) with the formation of an O–H$$\cdots\cdots$$N–H$$\cdots\cdots$$O–S chain-type binding motif competes with S1 in the source. The most reactive site of the molecule susceptible for electrophilic attacks is the linkage S atom. Theoretically predicted infrared spectra indicate that O–H and N–H stretching modes are the fingerprint region (2800 to 3600 cm–1) to distinguish different isomers. The obtained information lays out a foundation to better understand the transformation and structure–reactivity correlation of Cys-SSO3H in biologic settings.
- Research Organization:
- Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation of China (NSFC); University Cooperation and Innovation Program of Anhui Province
- Grant/Contract Number:
- Division of Chemical Sciences, Geosciences and Biosciences; AC05-76RL01830; 21873003; 12074004; 11674003; GXXT 2020-004
- OSTI ID:
- 1909285
- Alternate ID(s):
- OSTI ID: 1924523
- Report Number(s):
- PNNL-SA-180250; IJMCFK; PII: ijms24021682
- Journal Information:
- International Journal of Molecular Sciences (Online), Journal Name: International Journal of Molecular Sciences (Online) Vol. 24 Journal Issue: 2; ISSN 1422-0067
- Publisher:
- MDPI AGCopyright Statement
- Country of Publication:
- Switzerland
- Language:
- English
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