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

Research output: Contribution to journalArticle

6 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

Fingerprint

X-Ray Absorption Spectroscopy
Photochemistry
X ray absorption spectroscopy
Photochemical reactions
Reaction products
Sulfur
Disulfides
Biochemical Phenomena
Thiones
Electron transitions
X ray spectroscopy
Ultrashort pulses
Chemical elements
Electronic structure
Absorption spectra
Spectrum Analysis
X-Rays
Kinetics
Experiments

All Science Journal Classification (ASJC) codes

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

Cite this

Ochmann, Miguel ; Hussain, Abid ; Von Ahnen, Inga ; Cordones, Amy A. ; Hong, Kiryong ; Lee, Jae Hyuk ; Ma, Rory ; Adamczyk, Katrin ; Kim, Tae Kyu ; Schoenlein, Robert W. ; Vendrell, Oriol ; Huse, Nils. / UV-Photochemistry of the Disulfide Bond : Evolution of Early Photoproducts from Picosecond X-ray Absorption Spectroscopy at the Sulfur K-Edge. In: Journal of the American Chemical Society. 2018 ; Vol. 140, No. 21. pp. 6554-6561.
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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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Ochmann, M, Hussain, A, Von Ahnen, I, Cordones, AA, Hong, K, Lee, JH, Ma, R, Adamczyk, K, Kim, TK, Schoenlein, RW, 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, vol. 140, no. 21, pp. 6554-6561. https://doi.org/10.1021/jacs.7b13455

UV-Photochemistry of the Disulfide Bond : Evolution of Early Photoproducts from Picosecond X-ray Absorption Spectroscopy at the Sulfur K-Edge. / Ochmann, Miguel; Hussain, Abid; Von Ahnen, Inga; Cordones, Amy A.; Hong, Kiryong; Lee, Jae Hyuk; Ma, Rory; Adamczyk, Katrin; Kim, Tae Kyu; Schoenlein, Robert W.; Vendrell, Oriol; Huse, Nils.

In: Journal of the American Chemical Society, Vol. 140, No. 21, 30.05.2018, p. 6554-6561.

Research output: Contribution to journalArticle

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T2 - Evolution of Early Photoproducts from Picosecond X-ray Absorption Spectroscopy at the Sulfur K-Edge

AU - Ochmann, Miguel

AU - Hussain, Abid

AU - Von Ahnen, Inga

AU - Cordones, Amy A.

AU - Hong, Kiryong

AU - Lee, Jae Hyuk

AU - Ma, Rory

AU - Adamczyk, Katrin

AU - Kim, Tae Kyu

AU - Schoenlein, Robert W.

AU - Vendrell, Oriol

AU - Huse, Nils

PY - 2018/5/30

Y1 - 2018/5/30

N2 - 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.

AB - 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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