UV photochemistry of the L-cystine disulfide bridge in aqueous solution investigated by femtosecond X-ray absorption spectroscopy.


Journal

Nature communications
ISSN: 2041-1723
Titre abrégé: Nat Commun
Pays: England
ID NLM: 101528555

Informations de publication

Date de publication:
13 Oct 2024
Historique:
received: 31 03 2024
accepted: 19 09 2024
medline: 14 10 2024
pubmed: 14 10 2024
entrez: 13 10 2024
Statut: epublish

Résumé

The photolysis of disulfide bonds is implicated in denaturation of proteins exposed to ultraviolet light. Despite this biological relevance in stabilizing the structure of many proteins, the mechanisms of disulfide photolysis are still contested after decades of research. Herein, we report new insight into the photochemistry of L-cystine in aqueous solution by femtosecond X-ray absorption spectroscopy at the sulfur K-edge. We observe homolytic bond cleavage upon ultraviolet irradiation and the formation of thiyl radicals as the single primary photoproduct. Ultrafast thiyl decay due to geminate recombination proceeds at a quantum yield of >80 % within 20 ps. These dynamics coincide with the emergence of a secondary product, attributed to the generation of perthiyl radicals. From these findings, we suggest a mechanism of perthiyl radical generation from a vibrationally excited parent molecule that asymmetrically fragments along a carbon-sulfur bond. Our results point toward a dynamic photostability of the disulfide bridge in condensed-phase.

Identifiants

pubmed: 39397016
doi: 10.1038/s41467-024-52748-x
pii: 10.1038/s41467-024-52748-x
doi:

Types de publication

Journal Article

Langues

eng

Sous-ensembles de citation

IM

Pagination

8838

Informations de copyright

© 2024. The Author(s).

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Auteurs

Miguel Ochmann (M)

Department of Physics, University of Hamburg and Center for Free-Electron Laser Science, Hamburg, Germany.

Jessica Harich (J)

Department of Physics, University of Hamburg and Center for Free-Electron Laser Science, Hamburg, Germany.

Rory Ma (R)

Pohang Accelerator Laboratory, POSTECH, Pohang, Republic of Korea.

Antonia Freibert (A)

Department of Physics, University of Hamburg and Center for Free-Electron Laser Science, Hamburg, Germany. antonia.freibert@physik.uni-hamburg.de.

Yujin Kim (Y)

Pohang Accelerator Laboratory, POSTECH, Pohang, Republic of Korea.

Madhusudana Gopannagari (M)

Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon, Republic of Korea.

Da Hye Hong (DH)

Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon, Republic of Korea.

Daewoong Nam (D)

Pohang Accelerator Laboratory, POSTECH, Pohang, Republic of Korea.
Photon Science Center, Pohang University of Science and Technology, Pohang, Republic of Korea.

Sangsoo Kim (S)

Pohang Accelerator Laboratory, POSTECH, Pohang, Republic of Korea.

Minseok Kim (M)

Pohang Accelerator Laboratory, POSTECH, Pohang, Republic of Korea.

Intae Eom (I)

Pohang Accelerator Laboratory, POSTECH, Pohang, Republic of Korea.
Photon Science Center, Pohang University of Science and Technology, Pohang, Republic of Korea.

Jae Hyuk Lee (JH)

Pohang Accelerator Laboratory, POSTECH, Pohang, Republic of Korea.
Photon Science Center, Pohang University of Science and Technology, Pohang, Republic of Korea.

Briony A Yorke (BA)

School of Chemistry, University of Leeds, Leeds, United Kingdom.

Tae Kyu Kim (TK)

Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon, Republic of Korea. taekyu.kim@kaist.ac.kr.

Nils Huse (N)

Department of Physics, University of Hamburg and Center for Free-Electron Laser Science, Hamburg, Germany. nils.huse@uni-hamburg.de.

Classifications MeSH