English
 
User Manual Privacy Policy Disclaimer Contact us
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT
  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.

Item is

Basic

show hide
Item Permalink: http://hdl.handle.net/21.11116/0000-0001-AC2E-B Version Permalink: http://hdl.handle.net/21.11116/0000-0001-AC2F-A
Genre: Journal Article

Files

show Files
hide Files
:
jacs.7b13455.pdf (Publisher version), 2MB
 
File Permalink:
-
Name:
jacs.7b13455.pdf
Description:
-
Visibility:
Private
MIME-Type / Checksum:
application/pdf
Technical Metadata:
Copyright Date:
-
Copyright Info:
-
License:
-

Locators

show
hide
Locator:
https://dx.doi.org/10.1021/jacs.7b13455 (Publisher version)
Description:
-

Creators

show
hide
 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              

Content

show
hide
Free keywords: -
 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.

Details

show
hide
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. Method: Peer
 Identifiers: DOI: 10.1021/jacs.7b13455
 Degree: -

Event

show

Legal Case

show

Project information

show hide
Project name : This work was supported by the Director, O ffi ce of Science, O ffi ce of Basic Energy Sciences, the Chemical Sciences, Geo- sciences, and Biosciences Division under the Department of Energy, Contract No. DE-AC02-05CH11231 (A.C., K.H., J.L., and R.W.S.). This research has been supported by grants of the National Research Foundation of Korea (NRF) funded through the Ministry of Science and ICT (No. 2016R1E1A1A01941978, 2014R1A4A1001690, and 2016K1A4A4A01922028) to K.H., R.M., and T.K.K. M.O., I.v.A., K.A., and N.H. acknowledge funding from the Max Planck Society and the City of Hamburg. M.O. and N.H. gratefully acknowledge fi nancial support by the German Science Foundation (DFG) through the SFB 925 “ Light induced dynamics and control of correlated quantum systems ” . This research used resources of the Advanced Light Source (LBNL), which is a DOE O ffi ce of Science User Facility. We thank Bruce Rude for his continuous support of the experimental hardware.
Grant ID : -
Funding program : -
Funding organization : -

Source 1

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