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

Miguel Ochmann, Abid Hussain, Inga Von Ahnen, Amy A. Cordones, Kiryong Hong, Jae Hyuk Lee, Rory Ma, Katrin Adamczyk, Tae Kyu Kim, Robert W. Schoenlein, Oriol Vendrell, Nils Huse

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10 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)6554-6561
Number of pages8
JournalJournal of the American Chemical Society
Volume140
Issue number21
DOIs
Publication statusPublished - 2018 May 30

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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    Ochmann, M., Hussain, A., Von Ahnen, I., Cordones, A. A., Hong, K., Lee, J. H., Ma, R., Adamczyk, K., Kim, T. K., Schoenlein, R. W., Vendrell, O., & Huse, N. (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. https://doi.org/10.1021/jacs.7b13455