DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Core-Level Spectroscopy of 2-Thiouracil at the Sulfur L1- and L2,3-Edges Utilizing a SASE Free-Electron Laser

Abstract

In this paper, we report X-ray absorption and core-level electron spectra of the nucleobase derivative 2-thiouracil at the sulfur L1- and L2,3-edges. We used soft X-rays from the free-electron laser FLASH2 for the excitation of isolated molecules and dispersed the outgoing electrons with a magnetic bottle spectrometer. We identified photoelectrons from the 2p core orbital, accompanied by an electron correlation satellite, as well as resonant and non-resonant Coster–Kronig and Auger–Meitner emission at the L1- and L2,3-edges, respectively. We used the electron yield to construct X-ray absorption spectra at the two edges. The experimental data obtained are put in the context of the literature currently available on sulfur core-level and 2-thiouracil spectroscopy.

Authors:
; ORCiD logo; ; ; ; ; ; ORCiD logo; ; ; ; ; ; ORCiD logo; ; ORCiD logo;
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Volkswagen Foundation; Federal Ministry of Education and Research (BMBF); German Research Foundation (DFG); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; European Research Council (ERC); Swedish Research Council (VR); Knut and Alice Wallenberg Foundation
OSTI Identifier:
1828079
Alternate Identifier(s):
OSTI ID: 1877676; OSTI ID: 1878586
Grant/Contract Number:  
NA; AC02-76SF00515; GU 1478/1-1; 637756
Resource Type:
Published Article
Journal Name:
Molecules
Additional Journal Information:
Journal Name: Molecules Journal Volume: 26 Journal Issue: 21; Journal ID: ISSN 1420-3049
Publisher:
MDPI AG
Country of Publication:
Switzerland
Language:
English
Subject:
47 OTHER INSTRUMENTATION; X-ray; photoelectron; sulfur; thiouracil; nucleobases; Coster–Kronig; Auger–Meitner; NEXAFS; FLASH

Citation Formats

Lever, Fabiano, Mayer, Dennis, Metje, Jan, Alisauskas, Skirmantas, Calegari, Francesca, Düsterer, Stefan, Feifel, Raimund, Niebuhr, Mario, Manschwetus, Bastian, Kuhlmann, Marion, Mazza, Tommaso, Robinson, Matthew Scott, Squibb, Richard J., Trabattoni, Andrea, Wallner, Måns, Wolf, Thomas J. A., and Gühr, Markus. Core-Level Spectroscopy of 2-Thiouracil at the Sulfur L1- and L2,3-Edges Utilizing a SASE Free-Electron Laser. Switzerland: N. p., 2021. Web. doi:10.3390/molecules26216469.
Lever, Fabiano, Mayer, Dennis, Metje, Jan, Alisauskas, Skirmantas, Calegari, Francesca, Düsterer, Stefan, Feifel, Raimund, Niebuhr, Mario, Manschwetus, Bastian, Kuhlmann, Marion, Mazza, Tommaso, Robinson, Matthew Scott, Squibb, Richard J., Trabattoni, Andrea, Wallner, Måns, Wolf, Thomas J. A., & Gühr, Markus. Core-Level Spectroscopy of 2-Thiouracil at the Sulfur L1- and L2,3-Edges Utilizing a SASE Free-Electron Laser. Switzerland. https://doi.org/10.3390/molecules26216469
Lever, Fabiano, Mayer, Dennis, Metje, Jan, Alisauskas, Skirmantas, Calegari, Francesca, Düsterer, Stefan, Feifel, Raimund, Niebuhr, Mario, Manschwetus, Bastian, Kuhlmann, Marion, Mazza, Tommaso, Robinson, Matthew Scott, Squibb, Richard J., Trabattoni, Andrea, Wallner, Måns, Wolf, Thomas J. A., and Gühr, Markus. Tue . "Core-Level Spectroscopy of 2-Thiouracil at the Sulfur L1- and L2,3-Edges Utilizing a SASE Free-Electron Laser". Switzerland. https://doi.org/10.3390/molecules26216469.
@article{osti_1828079,
title = {Core-Level Spectroscopy of 2-Thiouracil at the Sulfur L1- and L2,3-Edges Utilizing a SASE Free-Electron Laser},
author = {Lever, Fabiano and Mayer, Dennis and Metje, Jan and Alisauskas, Skirmantas and Calegari, Francesca and Düsterer, Stefan and Feifel, Raimund and Niebuhr, Mario and Manschwetus, Bastian and Kuhlmann, Marion and Mazza, Tommaso and Robinson, Matthew Scott and Squibb, Richard J. and Trabattoni, Andrea and Wallner, Måns and Wolf, Thomas J. A. and Gühr, Markus},
abstractNote = {In this paper, we report X-ray absorption and core-level electron spectra of the nucleobase derivative 2-thiouracil at the sulfur L1- and L2,3-edges. We used soft X-rays from the free-electron laser FLASH2 for the excitation of isolated molecules and dispersed the outgoing electrons with a magnetic bottle spectrometer. We identified photoelectrons from the 2p core orbital, accompanied by an electron correlation satellite, as well as resonant and non-resonant Coster–Kronig and Auger–Meitner emission at the L1- and L2,3-edges, respectively. We used the electron yield to construct X-ray absorption spectra at the two edges. The experimental data obtained are put in the context of the literature currently available on sulfur core-level and 2-thiouracil spectroscopy.},
doi = {10.3390/molecules26216469},
journal = {Molecules},
number = 21,
volume = 26,
place = {Switzerland},
year = {2021},
month = {10}
}

Works referenced in this record:

Non-invasive online wavelength measurements at FLASH2 and present benchmark
journal, January 2018

  • Braune, Markus; Buck, Jens; Kuhlmann, Marion
  • Journal of Synchrotron Radiation, Vol. 25, Issue 1
  • DOI: 10.1107/S1600577517013893

Flash II: Perspectives and challenges
journal, April 2011

  • Faatz, B.; Baboi, N.; Ayvazyan, V.
  • Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 635, Issue 1
  • DOI: 10.1016/j.nima.2010.10.065

Simulated and Experimental Time-Resolved Photoelectron Spectra of the Intersystem Crossing Dynamics in 2-Thiouracil
journal, November 2018


On the decay of the triplet state of thionucleobases
journal, January 2017

  • Bai, Shuming; Barbatti, Mario
  • Physical Chemistry Chemical Physics, Vol. 19, Issue 20
  • DOI: 10.1039/C7CP02050C

URSA-PQ: A Mobile and Flexible Pump-Probe Instrument for Gas Phase Samples at the FLASH Free Electron Laser
journal, November 2020

  • Metje, Jan; Lever, Fabiano; Mayer, Dennis
  • Applied Sciences, Vol. 10, Issue 21
  • DOI: 10.3390/app10217882

Photophysics and Photochemistry of Canonical Nucleobases’ Thioanalogs: From Quantum Mechanical Studies to Time Resolved Experiments
journal, June 2017


Photo-cross-linking and high-resolution mass spectrometry for assignment of RNA-binding sites in RNA-binding proteins
journal, August 2014

  • Kramer, Katharina; Sachsenberg, Timo; Beckmann, Benedikt M.
  • Nature Methods, Vol. 11, Issue 10
  • DOI: 10.1038/nmeth.3092

Femtosecond Time-Resolved Photoelectron Spectroscopy
journal, April 2004

  • Stolow, Albert; Bragg, Arthur E.; Neumark, Daniel M.
  • Chemical Reviews, Vol. 104, Issue 4
  • DOI: 10.1021/cr020683w

Ultrafast dynamics of 2-thiouracil investigated by time-resolved Auger spectroscopy
journal, January 2020

  • Lever, F.; Mayer, D.; Picconi, D.
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 54, Issue 1
  • DOI: 10.1088/1361-6455/abc9cb

Efficient DNA interstrand crosslinking by 6-thioguanine and UVA radiation
journal, August 2011


Magnetic field paralleliser for 2π electron-spectrometer and electron-image magnifier
journal, April 1983


The tautomeric equilibria of thio analogues of nucleic acid bases. Part 3. Ultraviolet photoelectron spectra of 2-thiouracil and its methyl derivatives
journal, January 1990

  • Katritzky, Alan R.; Szafran, Miroslaw; Pfister-Guillouzo, Genevi�ve
  • Journal of the Chemical Society, Perkin Transactions 2, Issue 6
  • DOI: 10.1039/p29900000871

Ultrafast X-ray Auger probing of photoexcited molecular dynamics
journal, June 2014

  • McFarland, B. K.; Farrell, J. P.; Miyabe, S.
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5235

Core-level spectroscopy and dynamics of free molecules
journal, January 2011

  • Feifel, R.; Piancastelli, M. N.
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 183, Issue 1-3
  • DOI: 10.1016/j.elspec.2010.04.011

Experimental strategies for optical pump – soft x-ray probe experiments at the LCLS
journal, April 2014


Increase in the photoreactivity of uracil derivatives by doubling thionation
journal, January 2015

  • Pollum, M.; Jockusch, S.; Crespo-Hernández, C. E.
  • Phys. Chem. Chem. Phys., Vol. 17, Issue 41
  • DOI: 10.1039/C5CP04822B

Carbon and oxygen kll and sulfur lmm auger spectra of ocs
journal, January 1990


Observing Femtosecond Fragmentation Using Ultrafast X-ray-Induced Auger Spectra
journal, July 2017

  • Wolf, Thomas; Holzmeier, Fabian; Wagner, Isabella
  • Applied Sciences, Vol. 7, Issue 7
  • DOI: 10.3390/app7070681

Tautomerism in 4-Hydroxypyrimidine, S -Methyl-2-thiouracil, and 2-Thiouracil
journal, December 2010

  • Giuliano, Barbara M.; Feyer, Vitaliy; Prince, Kevin C.
  • The Journal of Physical Chemistry A, Vol. 114, Issue 48
  • DOI: 10.1021/jp106883s

Direct observation of electron dynamics in the attosecond domain
journal, July 2005

  • Föhlisch, A.; Feulner, P.; Hennies, F.
  • Nature, Vol. 436, Issue 7049
  • DOI: 10.1038/nature03833

A Static Picture of the Relaxation and Intersystem Crossing Mechanisms of Photoexcited 2-Thiouracil
journal, August 2015

  • Mai, Sebastian; Marquetand, Philipp; González, Leticia
  • The Journal of Physical Chemistry A, Vol. 119, Issue 36
  • DOI: 10.1021/acs.jpca.5b06639

The resonant Auger effect
journal, January 2000

  • Armen, G. Bradley; Aksela, Helena; Åberg, Teijo
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 33, Issue 2
  • DOI: 10.1088/0953-4075/33/2/201

Spatial Factors for Triplet Fusion Reaction of Singlet Oxygen Photosensitization
journal, October 2017


Electron shake-up and correlation satellites and continuum shake-off distributions in X-Ray photoelectron spectra of the rare gas atoms
journal, January 1988

  • Svensson, Svante; Eriksson, Bengt; Mårtensson, Nils
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 47
  • DOI: 10.1016/0368-2048(88)85020-5

4-thiothymidine sensitization of DNA to UVA offers potential for a novel photochemotherapy
journal, January 2012

  • Reelfs, Olivier; Karran, Peter; Young, Antony R.
  • Photochem. Photobiol. Sci., Vol. 11, Issue 1
  • DOI: 10.1039/C1PP05188A

Probing ultrafast ππ*/nπ* internal conversion in organic chromophores via K-edge resonant absorption
journal, June 2017


Photochemical and Photodynamical Properties of Sulfur-Substituted Nucleic Acid Bases,
journal, September 2018

  • Ashwood, Brennan; Pollum, Marvin; Crespo-Hernández, Carlos E.
  • Photochemistry and Photobiology, Vol. 95, Issue 1
  • DOI: 10.1111/php.12975

Novel DNA lesions generated by the interaction between therapeutic thiopurines and UVA light
journal, March 2007


Simultaneous operation of two soft x-ray free-electron lasers driven by one linear accelerator
journal, June 2016


Role of Postreplicative DNA Mismatch Repair in the Cytotoxic Action of Thioguanine
journal, August 1996


Ionization and fragmentation of OCS and CS2 after photoexcitation around the sulfur 2p edge
journal, August 1997


Normal and resonant Auger spectroscopy of isocyanic acid, HNCO
journal, July 2018

  • Holzmeier, F.; Wolf, T. J. A.; Gienger, C.
  • The Journal of Chemical Physics, Vol. 149, Issue 3
  • DOI: 10.1063/1.5030621

Transient resonant Auger–Meitner spectra of photoexcited thymine
journal, January 2021

  • Wolf, Thomas J. A.; Paul, Alexander C.; Folkestad, Sarai D.
  • Faraday Discussions, Vol. 228
  • DOI: 10.1039/D0FD00112K

Photoactivation of DNA thiobases as a potential novel therapeutic option
journal, July 2001


Tracing the 267 nm-Induced Radical Formation in Dimethyl Disulfide Using Time-Resolved X-ray Absorption Spectroscopy
journal, February 2019

  • Schnorr, Kirsten; Bhattacherjee, Aditi; Oosterbaan, Katherine J.
  • The Journal of Physical Chemistry Letters, Vol. 10, Issue 6
  • DOI: 10.1021/acs.jpclett.9b00159

2-Thiouracil intersystem crossing photodynamics studied by wavelength-dependent photoelectron and transient absorption spectroscopies
journal, January 2017

  • Sánchez-Rodríguez, José A.; Mohamadzade, Abed; Mai, Sebastian
  • Physical Chemistry Chemical Physics, Vol. 19, Issue 30
  • DOI: 10.1039/C7CP02258A

Shake-up transitions in S 2p, S 2s and F 1s photoionization of the SF 6 molecule
journal, February 2009

  • Decleva, P.; Fronzoni, G.; Kivimäki, A.
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 42, Issue 5
  • DOI: 10.1088/0953-4075/42/5/055102