Concerted proton-coupled electron transfer (EPT) reactions in which both electrons and protons transfer in tandem are at the heart of many chemical and biological conversions including photosystem II. We report here the direct observation of absorption bands arising from photoEPT transitions, in this case, in H-bonded complexes between N -methyl-4,4′-bipyridinium cation and biologically relevant donors including tyrosine. The importance of these observations follows from the earlier experimental observations by Taube and coworkers on intervalence transfer in mixed-valence complexes. The observation of these photoEPT transitions and the appearance of reactive radical products also points to a possible, if inefficient, role in DNA photodamage and, possibly, in the formation of reactive oxygen intermediates.
Gagliardi, Christopher J., et al. "Direct observation of light-driven, concerted electron–proton transfer." Proceedings of the National Academy of Sciences of the United States of America, vol. 113, no. 40, Sep. 2016. https://doi.org/10.1073/pnas.1611496113
Gagliardi, Christopher J., Wang, Li, Dongare, Prateek, Brennaman, M. Kyle, Papanikolas, John M., Meyer, Thomas J., & Thompson, David W. (2016). Direct observation of light-driven, concerted electron–proton transfer. Proceedings of the National Academy of Sciences of the United States of America, 113(40). https://doi.org/10.1073/pnas.1611496113
Gagliardi, Christopher J., Wang, Li, Dongare, Prateek, et al., "Direct observation of light-driven, concerted electron–proton transfer," Proceedings of the National Academy of Sciences of the United States of America 113, no. 40 (2016), https://doi.org/10.1073/pnas.1611496113
@article{osti_1326239,
author = {Gagliardi, Christopher J. and Wang, Li and Dongare, Prateek and Brennaman, M. Kyle and Papanikolas, John M. and Meyer, Thomas J. and Thompson, David W.},
title = {Direct observation of light-driven, concerted electron–proton transfer},
annote = {Significance Concerted proton-coupled electron transfer (EPT) reactions in which both electrons and protons transfer in tandem are at the heart of many chemical and biological conversions including photosystem II. We report here the direct observation of absorption bands arising from photoEPT transitions, in this case, in H-bonded complexes between N -methyl-4,4′-bipyridinium cation and biologically relevant donors including tyrosine. The importance of these observations follows from the earlier experimental observations by Taube and coworkers on intervalence transfer in mixed-valence complexes. The observation of these photoEPT transitions and the appearance of reactive radical products also points to a possible, if inefficient, role in DNA photodamage and, possibly, in the formation of reactive oxygen intermediates. },
doi = {10.1073/pnas.1611496113},
url = {https://www.osti.gov/biblio/1326239},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
issn = {ISSN 0027-8424},
number = {40},
volume = {113},
place = {United States},
publisher = {Proceedings of the National Academy of Sciences},
year = {2016},
month = {09}}
Univ. of North Carolina at Chapel Hill, Chapel Hill, NC (United States)
Sponsoring Organization:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
SC0001011
OSTI ID:
1326239
Alternate ID(s):
OSTI ID: 1464947
Journal Information:
Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Issue: 40 Vol. 113; ISSN 0027-8424