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  UV-Photochemistry of the Disulfide Bond: Evolution of Early Photoproducts from Picosecond X-ray Absorption Spectroscopy at the Sulfur K-Edge

Ochmann, M., Hussain, A., von Ahnen, I., Cordones, A. A., Hong, K., Lee, J. H., et al. (2018). UV-Photochemistry of the Disulfide Bond: Evolution of Early Photoproducts from Picosecond X-ray Absorption Spectroscopy at the Sulfur K-Edge. Journal of the American Chemical Society, 140(21), 6554-6561. doi:10.1021/jacs.7b13455.

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Suuporting information: Temporal modeling, possible cation formation, relative yield analysis, diffusion-limited product formation, energy calibration, and RASSCF calculations
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https://dx.doi.org/10.1021/jacs.7b13455 (Publisher version)
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 Creators:
Ochmann, M.1, 2, 3, Author              
Hussain, A.1, 2, Author              
von Ahnen, I.1, 3, Author              
Cordones, A. A.4, Author
Hong, K.5, Author
Lee, J. H.4, Author
Ma, R.5, Author
Adamczyk, K.1, 2, 3, Author              
Kim, T. K.5, Author
Schoenlein, R. W.4, Author
Vendrell, O.3, 6, Author
Huse, N.1, 2, 3, Author              
Affiliations:
1Ultrafast Molecular Dynamics, Atomically Resolved Dynamics Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society, ou_1938289              
2Department of Physics, University of Hamburg, ou_persistent22              
3Center for Free Electron Laser Science, ou_persistent22              
4Ultrafast X-ray Science Lab, Chemical Sciences Division, Lawrence Berkeley National Laboratory, ou_persistent22              
5Department of Chemistry and Chemistry Institute of Functional Materials, Pusan National University, ou_persistent22              
6The Hamburg Centre for Ultrafast Imaging, ou_persistent22              

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 Abstract: We have investigated dimethyl disulfide as the basic moiety for understanding the photochemistry of disulfide bonds, which are central to a broad range of biochemical processes. Picosecond time-resolved X-ray absorption spectroscopy at the sulfur K-edge provides unique element-specific insight into the photochemistry of the disulfide bond initiated by 267 nm femtosecond pulses. We observe a broad but distinct transient induced absorption spectrum which recovers on at least two time scales in the nanosecond range. We employed RASSCF electronic structure calculations to simulate the sulfur-1s transitions of multiple possible chemical species, and identified the methylthiyl and methylperthiyl radicals as the primary reaction products. In addition, we identify disulfur and the CH2S thione as the secondary reaction products of the perthiyl radical that are most likely to explain the observed spectral and kinetic signatures of our experiment. Our study underscores the importance of elemental specificity and the potential of time-resolved X-ray spectroscopy to identify short-lived reaction products in complex reaction schemes that underlie the rich photochemistry of disulfide systems.

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Language(s): eng - English
 Dates: 2017-12-192018-05-172018-05-30
 Publication Status: Published in print
 Pages: 8
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/jacs.7b13455
 Degree: -

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Title: Journal of the American Chemical Society
  Other : J. Am. Chem. Soc.
  Abbreviation : JACS
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 140 (21) Sequence Number: - Start / End Page: 6554 - 6561 Identifier: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870