UV-Photochemistry of the Disulfide Bond: Evolution of Early Photoproducts from Picosecond X-ray Absorption Spectroscopy at the Sulfur K-Edge
- 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
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.
- Research Organization:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; National Research Foundation of Korea (NRF); Max Planck Society, Munich (Germany); German Research Foundation (DFG)
- Grant/Contract Number:
- AC02-05CH11231; 2016R1E1A1A01941978; 2014R1A4A1001690; 2016K1A4A4A01922028
- OSTI ID:
- 1461352
- Journal Information:
- Journal of the American Chemical Society, Vol. 140, Issue 21; Related Information: 10.1021/jacs.7b13455; ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)Copyright Statement
- Country of Publication:
- United States
- Language:
- English
Web of Science
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