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

doi:10.1021/jacs.7b13455

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

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 then 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 CH ₂S 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.

Authors:

Ochmann, Miguel ^[1]; Hussain, Abid ^[2]; von Ahnen, Inga ^[1]; Cordones, Amy A. ^[3]; Hong, Kiryong ^[4]; Lee, Jae Hyuk ^[5]; Ma, Rory ^[6]; Adamczyk, Katrin ^[1];

^[6]; Schoenlein, Robert W. ^[7];

^[8];

^[1]

Univ. of Hamburg and Max Planck Inst. for the Structure and Dynamics of Matter (MPSD), Hamburg (Germany). Center for Free Electron Laser Science (CFEL) and Dept. of Physics
Univ. of Hamburg and Max Planck Inst. for the Structure and Dynamics of Matter (MPSD), Hamburg (Germany). Center for Free Electron Laser Science (CFEL) and Dept. of Physics; Pakistan Inst. of Engineering and Applied Sciences, Nilore (Pakistan). Dept. of Physics and Applied Mathematics
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Ultrafast X-ray Science Lab. and Chemical Sciences Division; SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE)
Pusan National Univ., Busan (Korea, Republic of). Dept. of Chemistry and Chemistry Inst. of Functional Materials; Korea Research Inst. of Standards and Science, Daejeon (Korea, Republic of). Center for Gas Analysis and Division of Metrology for Quality of Life
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Ultrafast X-ray Science Lab. and Chemical Sciences Division; Pohang Accelerator Lab. (PAL) (Korea, Republic of)
Pusan National Univ., Busan (Korea, Republic of). Dept. of Chemistry and Chemistry Inst. of Functional Materials
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Ultrafast X-ray Science Lab. and Chemical Sciences Division; SLAC National Accelerator Lab., Menlo Park, CA (United States). Linac Coherent Light Source (LCLS)
Deutsches Elektronen-Synchrotron (DESY) and Hamburg Centre for Ultrafast Imaging (CUI), Hamburg (Germany). Center for Free-Electron Laser Science (CFEL); Aarhus Univ. (Denmark). Dept. of Physics and Astronomy

Publication Date:: 2018-05-17

Research Org.:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division; National Research Foundation of Korea (NRF); Max Planck Society, Munich (Germany); German Research Foundation (DFG)

OSTI Identifier:: 1461352

Grant/Contract Number:: [AC02-05CH11231; 2016R1E1A1A01941978; 2014R1A4A1001690; 2016K1A4A4A01922028]

Resource Type:: Accepted Manuscript

Journal Name:: Journal of the American Chemical Society

Additional Journal Information:: [ Journal Volume: 140; Journal Issue: 21; Related Information: 10.1021/jacs.7b13455]; Journal ID: ISSN 0002-7863

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; disulfide; sulfur; X-ray spectroscopy

Citation Formats


                    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, and Huse, Nils. UV-Photochemistry of the Disulfide Bond: Evolution of Early Photoproducts from Picosecond X-ray Absorption Spectroscopy at the Sulfur K-Edge.  United States: N. p., 2018. 
        Web.  doi:10.1021/jacs.7b13455.

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                    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.  United States.  doi:10.1021/jacs.7b13455.

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                    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, and Huse, Nils. Thu .  
        "UV-Photochemistry of the Disulfide Bond: Evolution of Early Photoproducts from Picosecond X-ray Absorption Spectroscopy at the Sulfur K-Edge".  United States.  doi:10.1021/jacs.7b13455.  https://www.osti.gov/servlets/purl/1461352.

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@article{osti_1461352,

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

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

  abstractNote = {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 then 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.},

  doi          = {10.1021/jacs.7b13455},

  journal      = {Journal of the American Chemical Society},

  number       = [21],

  volume       = [140],

  place        = {United States},

  year         = {2018},

  month        = {5}

}

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DOI: 10.1021/jacs.7b13455

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Cited by: 5 works

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Figures / Tables:

Figure 1: A. Sulfur K‐edge spectrum of DMDS along with the computed lowest sulfur‐1s transitions. B. Differential absorption spectra at time delays of 0.1, 5, 50, and 150 ns after excitation with 267 nm pulses. C. Time evolution of the absorbance changes at three distinct photon energies, indicated by color‐ coded arrows in panel B (spheres and doted lines) along with exponential decays (solid lines) fit to the experimental data.

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Works referencing / citing this record:

Unraveling the Mechanisms of the Excited‐State Intermolecular Proton Transfer (ESPT) for a D‐π‐A Molecular Architecture
journal, June 2019

Hong, Dan‐Li; Luo, Yang‐Hui; He, Xiao‐Tong
Chemistry – A European Journal
DOI: 10.1002/chem.201900856

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

Abstract

Citation Formats

Figures / Tables:

Unraveling the Mechanisms of the Excited‐State Intermolecular Proton Transfer (ESPT) for a D‐π‐A Molecular Architecture journal, June 2019

Unraveling the Mechanisms of the Excited‐State Intermolecular Proton Transfer (ESPT) for a D‐π‐A Molecular Architecture
journal, June 2019