Photochemically Generated Thiyl Free Radicals Observed by X-ray Absorption Spectroscopy

Sneeden, Eileen Y.; Hackett, Mark J.; Cotelesage, Julien J. H.; Prince, Roger C.; Barney, Monica; Goto, Kei; Block, Eric; Pickering, Ingrid J.; George, Graham N.

doi:10.1021/jacs.7b05116

Title: Photochemically Generated Thiyl Free Radicals Observed by X-ray Absorption Spectroscopy

Abstract

Sulfur-based thiyl radicals are known to be involved in a wide range of chemical and biological processes, but they are often highly reactive, which makes them difficult to observe directly. We report herein X-ray absorption spectra and analysis that support the direct observation of two different thiyl species generated photochemically by X-ray irradiation. The thiyl radical sulfur K-edge X-ray absorption spectra of both species are characterized by a uniquely low energy transition at about 2465 eV, which occurs at a lower energy than any previously observed feature at the sulfur K-edge and corresponds to a 1s → 3p transition to the singly occupied molecular orbital of the free radical. In conclusion, our results constitute the first observation of substantial levels of thiyl radicals generated by X-ray irradiation and detected by sulfur K-edge X-ray absorption spectroscopy.

Authors:

Sneeden, Eileen Y. ^[1];

^[2]; Cotelesage, Julien J. H. ^[3];

^[4]; Barney, Monica ^[5]; Goto, Kei ^[6];

^[7];

^[3];

^[3]

Stanford Univ., Menlo Park, CA (United States)
Univ. of Saskatchewan, Saskatoon, SK (Canada); Curtin Univ., Bentley, WA (Australia)
Univ. of Saskatchewan, Saskatoon, SK (Canada)
Stonybrook Apiary, Pittstown, NJ (United States)
Chevron Energy Technology Co., Richmond, CA (United States)
Tokyo Institute of Technology, Tokyo (Japan)
Univ. at Albany, State Univ. of New York, Albany, NY (United States)

Publication Date:: Thu Jul 27 00:00:00 EDT 2017

Research Org.:: SLAC National Accelerator Lab., Menlo Park, CA (United States)

Sponsoring Org.:: USDOE

OSTI Identifier:: 1394076

Grant/Contract Number:: AC02-76SF00515; CHE-1265679; 04632-2014; 05810-2016; GM57375

Resource Type:: Accepted Manuscript

Journal Name:: Journal of the American Chemical Society

Additional Journal Information:: Journal Volume: 139; Journal Issue: 33; 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

Citation Formats


                    Sneeden, Eileen Y., Hackett, Mark J., Cotelesage, Julien J. H., Prince, Roger C., Barney, Monica, Goto, Kei, Block, Eric, Pickering, Ingrid J., and George, Graham N. Photochemically Generated Thiyl Free Radicals Observed by X-ray Absorption Spectroscopy.  United States: N. p., 2017. 
Web.  doi:10.1021/jacs.7b05116.

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                    Sneeden, Eileen Y., Hackett, Mark J., Cotelesage, Julien J. H., Prince, Roger C., Barney, Monica, Goto, Kei, Block, Eric, Pickering, Ingrid J., & George, Graham N. Photochemically Generated Thiyl Free Radicals Observed by X-ray Absorption Spectroscopy.  United States.  https://doi.org/10.1021/jacs.7b05116

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                    Sneeden, Eileen Y., Hackett, Mark J., Cotelesage, Julien J. H., Prince, Roger C., Barney, Monica, Goto, Kei, Block, Eric, Pickering, Ingrid J., and George, Graham N. Thu .  
"Photochemically Generated Thiyl Free Radicals Observed by X-ray Absorption Spectroscopy".  United States.  https://doi.org/10.1021/jacs.7b05116.  https://www.osti.gov/servlets/purl/1394076.

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@article{osti_1394076,

  title        = {Photochemically Generated Thiyl Free Radicals Observed by X-ray Absorption Spectroscopy},

  author       = {Sneeden, Eileen Y. and Hackett, Mark J. and Cotelesage, Julien J. H. and Prince, Roger C. and Barney, Monica and Goto, Kei and Block, Eric and Pickering, Ingrid J. and George, Graham N.},

  abstractNote = {Sulfur-based thiyl radicals are known to be involved in a wide range of chemical and biological processes, but they are often highly reactive, which makes them difficult to observe directly. We report herein X-ray absorption spectra and analysis that support the direct observation of two different thiyl species generated photochemically by X-ray irradiation. The thiyl radical sulfur K-edge X-ray absorption spectra of both species are characterized by a uniquely low energy transition at about 2465 eV, which occurs at a lower energy than any previously observed feature at the sulfur K-edge and corresponds to a 1s → 3p transition to the singly occupied molecular orbital of the free radical. In conclusion, our results constitute the first observation of substantial levels of thiyl radicals generated by X-ray irradiation and detected by sulfur K-edge X-ray absorption spectroscopy.},

  doi          = {10.1021/jacs.7b05116},

  journal      = {Journal of the American Chemical Society},

  number       = 33,

  volume       = 139,

  place        = {United States},

  year         = {Thu Jul 27 00:00:00 EDT 2017},

  month        = {Thu Jul 27 00:00:00 EDT 2017}

}

Copy to clipboard

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Works referenced in this record:

Theoretical Study of the Thermal Decomposition of Dimethyl Disulfide
journal, October 2010

Vandeputte, Aäron G.; Reyniers, Marie-Françoise; Marin, Guy B.
The Journal of Physical Chemistry A, Vol. 114, Issue 39
DOI: 10.1021/jp103357z

Thiyl Radicals in Organic Synthesis
journal, January 2014

Dénès, Fabrice; Pichowicz, Mark; Povie, Guillaume
Chemical Reviews, Vol. 114, Issue 5
DOI: 10.1021/cr400441m

Effect of Substituents on the Stability of Sulfur-Centered Radicals
journal, September 2016

Degirmenci, Isa; Coote, Michelle L.
The Journal of Physical Chemistry A, Vol. 120, Issue 37
DOI: 10.1021/acs.jpca.6b08223

Role of Hydrogen Bonding on the Reactivity of Thiyl Radicals: A Mass Spectrometric and Computational Study Using the Distonic Radical Ion Approach
journal, October 2016

Osburn, Sandra; Chan, Bun; Ryzhov, Victor
The Journal of Physical Chemistry A, Vol. 120, Issue 41
DOI: 10.1021/acs.jpca.6b08544

Comparison of Thiyl, Alkoxyl, and Alkyl Radical Addition to Double Bonds: The Unusual Contrasting Behavior of Sulfur and Oxygen Radical Chemistry
journal, March 2016

Degirmenci, Isa; Coote, Michelle L.
The Journal of Physical Chemistry A, Vol. 120, Issue 10
DOI: 10.1021/acs.jpca.6b00538

One- and two-electron oxidation of thiols: mechanisms, kinetics and biological fates
journal, November 2015

Trujillo, Madia; Alvarez, Beatriz; Radi, Rafael
Free Radical Research, Vol. 50, Issue 2
DOI: 10.3109/10715762.2015.1089988

Thiyl radicals and induction of protein degradation
journal, August 2015

Schöneich, Christian
Free Radical Research, Vol. 50, Issue 2
DOI: 10.3109/10715762.2015.1077385

Reversible, Long-Range Radical Transfer in E. coli Class Ia Ribonucleotide Reductase
journal, June 2013

Minnihan, Ellen C.; Nocera, Daniel G.; Stubbe, JoAnne
Accounts of Chemical Research, Vol. 46, Issue 11
DOI: 10.1021/ar4000407

Assessments of Thiyl Radicals in Biosystems: Difficulties and New Applications
journal, September 2011

Stoyanovsky, Detcho A.; Maeda, Akihiro; Atkins, James L.
Analytical Chemistry, Vol. 83, Issue 17
DOI: 10.1021/ac200418s

Paramagnetic Resonance in L‐Cysteine Hydrochloride Irradiated at 77°K
journal, August 1965

Akasaka, Kazuyuki
The Journal of Chemical Physics, Vol. 43, Issue 4
DOI: 10.1063/1.1696900

On the electron spin resonance detection of RS radicals in irradiated solids: radicals of type RSSR ^– , RS–SR ₂ , and R ₂ SSR ₂ ⁺
journal, January 1974

Symons, Martyn C. R.
J. Chem. Soc., Perkin Trans. 2, Issue 13
DOI: 10.1039/P29740001618

Sulphur radicals formed by cutting α-keratin
journal, August 1987

Chandra, Harish; Symons, Martyn C. R.
Nature, Vol. 328, Issue 6133
DOI: 10.1038/328833a0

Resonance Raman spectra and structure of phenylthiyl radical
journal, June 1992

Tripathi, G. N. R.; Sun, Qun; Armstrong, David A.
The Journal of Physical Chemistry, Vol. 96, Issue 13
DOI: 10.1021/j100192a031

Sulfur K-Edge XAS as a Probe of Sulfur-Centered Radical Intermediates
journal, March 2007

Martin-Diaconescu, Vlad; Kennepohl, Pierre
Journal of the American Chemical Society, Vol. 129, Issue 11
DOI: 10.1021/ja0676760

Light-Induced Radical Formation and Isomerization of an Aromatic Thiol in Solution Followed by Time-Resolved X-ray Absorption Spectroscopy at the Sulfur K-Edge
journal, March 2017

Ochmann, Miguel; von Ahnen, Inga; Cordones, Amy A.
Journal of the American Chemical Society, Vol. 139, Issue 13
DOI: 10.1021/jacs.6b12992

Synthesis, Structure, and Reactions of a Sulfenic Acid Bearing a Novel Bowl-Type Substituent: The First Synthesis of a Stable Sulfenic Acid by Direct Oxidation of a Thiol
journal, February 1997

Goto, Kei; Holler, Michel; Okazaki, Renji
Journal of the American Chemical Society, Vol. 119, Issue 6
DOI: 10.1021/ja962994s

Analysis of Sulfur Biochemistry of Sulfur Bacteria Using X-ray Absorption Spectroscopy ^†
journal, July 2001

Pickering, Ingrid J.; George, Graham N.; Yu, Eileen Y.
Biochemistry, Vol. 40, Issue 27
DOI: 10.1021/bi0105532

X-Ray Absorption Spectroscopy as a Probe of Microbial Sulfur Biochemistry: the Nature of Bacterial Sulfur Globules Revisited
journal, August 2008

George, G. N.; Gnida, M.; Bazylinski, D. A.
Journal of Bacteriology, Vol. 190, Issue 19
DOI: 10.1128/JB.00539-08

Measurement of soft X-ray absorption spectra with a fluorescent ion chamber detector
journal, October 1984

Lytle, F. W.; Greegor, R. B.; Sandstrom, D. R.
Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 226, Issue 2-3
DOI: 10.1016/0168-9002(84)90077-9

Sulfur K-Edge Absorption Spectra of Na ₂ SO ₄ , Na ₂ SO ₃ , Na ₂ S ₂ O ₃ , and Na ₂ S ₂ O _x ( x =5–8)
journal, February 1986

Sekiyama, Hideo; Kosugi, Nobuhiro; Kuroda, Haruo
Bulletin of the Chemical Society of Japan, Vol. 59, Issue 2
DOI: 10.1246/bcsj.59.575

An all‐electron numerical method for solving the local density functional for polyatomic molecules
journal, January 1990

Delley, B.
The Journal of Chemical Physics, Vol. 92, Issue 1
DOI: 10.1063/1.458452

From molecules to solids with the DMol3 approach
journal, November 2000

Delley, B.
The Journal of Chemical Physics, Vol. 113, Issue 18
DOI: 10.1063/1.1316015

Generalized Gradient Approximation Made Simple
journal, October 1996

Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
DOI: 10.1103/PhysRevLett.77.3865

COSMO: a new approach to dielectric screening in solvents with explicit expressions for the screening energy and its gradient
journal, January 1993

Klamt, A.; Schüürmann, G.
J. Chem. Soc., Perkin Trans. 2, Issue 5
DOI: 10.1039/P29930000799

Density-functional approximation for the correlation energy of the inhomogeneous electron gas
journal, June 1986

Perdew, John P.
Physical Review B, Vol. 33, Issue 12
DOI: 10.1103/PhysRevB.33.8822

Electronic Structure Description of the cis -MoOS Unit in Models for Molybdenum Hydroxylases
journal, January 2008

Doonan, Christian J.; Rubie, Nick D.; Peariso, Katrina
Journal of the American Chemical Society, Vol. 130, Issue 1
DOI: 10.1021/ja068512m

Determination of the number of factors and the experimental error in a data matrix
journal, April 1977

Malinowski, Edmund R.
Analytical Chemistry, Vol. 49, Issue 4
DOI: 10.1021/ac50012a027

Sulfur K-edge X-ray absorption spectroscopy for determining the chemical speciation of sulfur in biological systems
journal, December 1998

Pickering, Ingrid J.; Prince, Roger C.; Divers, Thomas
FEBS Letters, Vol. 441, Issue 1
DOI: 10.1016/S0014-5793(98)01402-1

Rate constants and transition-state geometry of reactions of alkyl, alkoxyl, and peroxyl radicals with thiols
journal, April 2009

Denisov, Evgeny; Chatgilialoglu, Crissostomos; Shestakov, Aleksander
International Journal of Chemical Kinetics, Vol. 41, Issue 4
DOI: 10.1002/kin.20404

X-ray-induced photo-chemistry and X-ray absorption spectroscopy of biological samples
journal, October 2012

George, Graham N.; Pickering, Ingrid J.; Pushie, M. Jake
Journal of Synchrotron Radiation, Vol. 19, Issue 6
DOI: 10.1107/S090904951203943X

Generation and characterization of the phenylthiyl radical and its oxidation to the phenylthiylperoxy and phenylsulfonyl radicals
journal, January 2016

Mardyukov, Artur; Schreiner, Peter R.
Physical Chemistry Chemical Physics, Vol. 18, Issue 37
DOI: 10.1039/C6CP04278C

Substituent Effects in the Reaction of OH Radicals with Aromatics: Toluene
journal, October 2003

Albarran, Guadalupe; Bentley, J.; Schuler, Robert. H.
The Journal of Physical Chemistry A, Vol. 107, Issue 39
DOI: 10.1021/jp030550u

Insights into the Nature of the Chemical Bonding in Thiophene-2-thiol from X-ray Absorption Spectroscopy
journal, August 2016

Cotelesage, Julien J. H.; Pushie, M. Jake; Vogt, Linda
The Journal of Physical Chemistry A, Vol. 120, Issue 35
DOI: 10.1021/acs.jpca.6b05874

Effects of Hyperconjugation on the Electronic Structure and Photoreactivity of Organic Sulfonyl Chlorides
journal, December 2008

Martin-Diaconescu, Vlad; Kennepohl, Pierre
Inorganic Chemistry, Vol. 48, Issue 3
DOI: 10.1021/ic801665f

The chemical biology of the persulfide (RSSH)/perthiyl (RSS·) redox couple and possible role in biological redox signaling
journal, December 2016

Bianco, Christopher L.; Chavez, Tyler A.; Sosa, Victor
Free Radical Biology and Medicine, Vol. 101
DOI: 10.1016/j.freeradbiomed.2016.09.020

A Redetermination of the Crystal and Molecular Structure of Glutathione (gamma-L-Glutamyl-L-cysteinylglycine) at 120 K.
journal, January 1987

Görbitz, C. H.; Eklund, Ann-Marie; Enzell, Curt R.
Acta Chemica Scandinavica, Vol. 41b
DOI: 10.3891/acta.chem.scand.41b-0362

Works referencing / citing this record:

Synchrotron X-radiolysis of l -cysteine at the sulfur K-edge: Sulfurous products, experimental surprises, and dioxygen as an oxidoreductant
journal, March 2019

Frank, Patrick; Sarangi, Ritimukta; Hedman, Britt
The Journal of Chemical Physics, Vol. 150, Issue 10
DOI: 10.1063/1.5079419

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Similar Records

Title: Photochemically Generated Thiyl Free Radicals Observed by X-ray Absorption Spectroscopy

Abstract

Citation Formats

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Resonance Raman spectra and structure of phenylthiyl radical journal, June 1992

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Analysis of Sulfur Biochemistry of Sulfur Bacteria Using X-ray Absorption Spectroscopy † journal, July 2001

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Sulfur K-Edge Absorption Spectra of Na 2 SO 4 , Na 2 SO 3 , Na 2 S 2 O 3 , and Na 2 S 2 O x ( x =5–8) journal, February 1986

An all‐electron numerical method for solving the local density functional for polyatomic molecules journal, January 1990

From molecules to solids with the DMol3 approach journal, November 2000

Generalized Gradient Approximation Made Simple journal, October 1996

COSMO: a new approach to dielectric screening in solvents with explicit expressions for the screening energy and its gradient journal, January 1993

Density-functional approximation for the correlation energy of the inhomogeneous electron gas journal, June 1986

Electronic Structure Description of the cis -MoOS Unit in Models for Molybdenum Hydroxylases journal, January 2008

Determination of the number of factors and the experimental error in a data matrix journal, April 1977

Sulfur K-edge X-ray absorption spectroscopy for determining the chemical speciation of sulfur in biological systems journal, December 1998

Rate constants and transition-state geometry of reactions of alkyl, alkoxyl, and peroxyl radicals with thiols journal, April 2009

X-ray-induced photo-chemistry and X-ray absorption spectroscopy of biological samples journal, October 2012

Generation and characterization of the phenylthiyl radical and its oxidation to the phenylthiylperoxy and phenylsulfonyl radicals journal, January 2016

Substituent Effects in the Reaction of OH Radicals with Aromatics: Toluene journal, October 2003

Insights into the Nature of the Chemical Bonding in Thiophene-2-thiol from X-ray Absorption Spectroscopy journal, August 2016

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One- and two-electron oxidation of thiols: mechanisms, kinetics and biological fates
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On the electron spin resonance detection of RS radicals in irradiated solids: radicals of type RSSR ^– , RS–SR ₂ , and R ₂ SSR ₂ ⁺
journal, January 1974

Sulphur radicals formed by cutting α-keratin
journal, August 1987

Resonance Raman spectra and structure of phenylthiyl radical
journal, June 1992

Sulfur K-Edge XAS as a Probe of Sulfur-Centered Radical Intermediates
journal, March 2007

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Synthesis, Structure, and Reactions of a Sulfenic Acid Bearing a Novel Bowl-Type Substituent: The First Synthesis of a Stable Sulfenic Acid by Direct Oxidation of a Thiol
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Analysis of Sulfur Biochemistry of Sulfur Bacteria Using X-ray Absorption Spectroscopy ^†
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X-Ray Absorption Spectroscopy as a Probe of Microbial Sulfur Biochemistry: the Nature of Bacterial Sulfur Globules Revisited
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Measurement of soft X-ray absorption spectra with a fluorescent ion chamber detector
journal, October 1984

Sulfur K-Edge Absorption Spectra of Na ₂ SO ₄ , Na ₂ SO ₃ , Na ₂ S ₂ O ₃ , and Na ₂ S ₂ O _x ( x =5–8)
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An all‐electron numerical method for solving the local density functional for polyatomic molecules
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From molecules to solids with the DMol3 approach
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Generalized Gradient Approximation Made Simple
journal, October 1996

COSMO: a new approach to dielectric screening in solvents with explicit expressions for the screening energy and its gradient
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Density-functional approximation for the correlation energy of the inhomogeneous electron gas
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Electronic Structure Description of the cis -MoOS Unit in Models for Molybdenum Hydroxylases
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Determination of the number of factors and the experimental error in a data matrix
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Sulfur K-edge X-ray absorption spectroscopy for determining the chemical speciation of sulfur in biological systems
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Substituent Effects in the Reaction of OH Radicals with Aromatics: Toluene
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The chemical biology of the persulfide (RSSH)/perthiyl (RSS·) redox couple and possible role in biological redox signaling
journal, December 2016

A Redetermination of the Crystal and Molecular Structure of Glutathione (gamma-L-Glutamyl-L-cysteinylglycine) at 120 K.
journal, January 1987

Synchrotron X-radiolysis of l -cysteine at the sulfur K-edge: Sulfurous products, experimental surprises, and dioxygen as an oxidoreductant
journal, March 2019