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Title: Putting the Disulfide Bridge at Risk: How UV-C Radiation Leads to Ultrafast Rupture of the S-S Bond

Abstract

We investigate here the ultrafast photoinduced dynamics of the cyclic disulfide 1,2-dithiane upon 200 nm excitation by time-resolved photoelectron spectroscopy and show that the S-S bond breaks on an ultrafast time scale. This stands in stark contrast to excitation at longer wavelengths where the initially excited S1 state evolves as the wavepacket is guided towards a conical intersection with S0 by a torsional motion involving a partially broken bond between the sulfur atoms. This process at lower excitation energy allows for efficient (re-)population of S0, rendering dithiane intact. At 200 nm, in contrast, the excitation leads to a manifold of higher excited states, Sn, that are primarily of Rydberg character. We are able to follow the gradual transition from the initially excited state to the dissociative receiver state in real time. The Rydberg states are intersected by a repulsive valence state that mediates a transition to the repulsive S2 surface. Hence, we propose that the resulting diradical will eventually break apart on a longer timescale. The results imply that upon going from UV-B to UV-C light the structural integrity of the disulfide moiety is compromised and proteins irradiated in this range will not be able to reform the initial tertiarymore » structure, leading to loss of function.« less

Authors:
 [1];  [1];  [1];  [2];  [2];  [2];  [1]
+ Show Author Affiliations
  1. Univ. of Copenhagen (Denmark)
  2. Brown Univ., Providence, RI (United States)
Publication Date:
Research Org.:
Brown Univ., Providence, RI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1596738
Alternate Identifier(s):
OSTI ID: 1465905
Grant/Contract Number:  
SC0017995
Resource Type:
Accepted Manuscript
Journal Name:
ChemPhysChem
Additional Journal Information:
Journal Volume: 19; Journal Issue: 21; Journal ID: ISSN 1439-4235
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; disulfide bridge; rydberg state; time-resolved photoelectron spectroscopy; ultrafast bond breakage; ultraviolet-C radiation

Citation Formats

Larsen, Martin A. B., Skov, Anders B., Clausen, Christian M., Ruddock, Jennifer, Stankus, Brian, Weber, Peter M., and Sølling, Theis I. Putting the Disulfide Bridge at Risk: How UV-C Radiation Leads to Ultrafast Rupture of the S-S Bond. United States: N. p., 2018. Web. doi:10.1002/cphc.201800610.
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Larsen, Martin A. B., Skov, Anders B., Clausen, Christian M., Ruddock, Jennifer, Stankus, Brian, Weber, Peter M., & Sølling, Theis I. Putting the Disulfide Bridge at Risk: How UV-C Radiation Leads to Ultrafast Rupture of the S-S Bond. United States. https://doi.org/10.1002/cphc.201800610
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Larsen, Martin A. B., Skov, Anders B., Clausen, Christian M., Ruddock, Jennifer, Stankus, Brian, Weber, Peter M., and Sølling, Theis I. Tue . "Putting the Disulfide Bridge at Risk: How UV-C Radiation Leads to Ultrafast Rupture of the S-S Bond". United States. https://doi.org/10.1002/cphc.201800610. https://www.osti.gov/servlets/purl/1596738.
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@article{osti_1596738,
title = {Putting the Disulfide Bridge at Risk: How UV-C Radiation Leads to Ultrafast Rupture of the S-S Bond},
author = {Larsen, Martin A. B. and Skov, Anders B. and Clausen, Christian M. and Ruddock, Jennifer and Stankus, Brian and Weber, Peter M. and Sølling, Theis I.},
abstractNote = {We investigate here the ultrafast photoinduced dynamics of the cyclic disulfide 1,2-dithiane upon 200 nm excitation by time-resolved photoelectron spectroscopy and show that the S-S bond breaks on an ultrafast time scale. This stands in stark contrast to excitation at longer wavelengths where the initially excited S1 state evolves as the wavepacket is guided towards a conical intersection with S0 by a torsional motion involving a partially broken bond between the sulfur atoms. This process at lower excitation energy allows for efficient (re-)population of S0, rendering dithiane intact. At 200 nm, in contrast, the excitation leads to a manifold of higher excited states, Sn, that are primarily of Rydberg character. We are able to follow the gradual transition from the initially excited state to the dissociative receiver state in real time. The Rydberg states are intersected by a repulsive valence state that mediates a transition to the repulsive S2 surface. Hence, we propose that the resulting diradical will eventually break apart on a longer timescale. The results imply that upon going from UV-B to UV-C light the structural integrity of the disulfide moiety is compromised and proteins irradiated in this range will not be able to reform the initial tertiary structure, leading to loss of function.},
doi = {10.1002/cphc.201800610},
journal = {ChemPhysChem},
number = 21,
volume = 19,
place = {United States},
year = {Tue Aug 07 00:00:00 EDT 2018},
month = {Tue Aug 07 00:00:00 EDT 2018}
}
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https://doi.org/10.1002/cphc.201800610
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