Femto- to Microsecond Photodynamics of an Unusual Bacteriophytochrome

Tilo Mathes, Janneke Ravensbergen, Miroslav Kloz, Tobias Gleichmann, Kevin D. Gallagher, Nicole C. Woitowich, Rachael St. Peter, Svetlana E. Kovaleva, Emina A. Stojković, John T.M. Kennis*

*Corresponding author for this work

Research output: Contribution to journalArticle

24 Scopus citations

Abstract

A bacteriophytochrome from Stigmatella aurantiaca is an unusual member of the bacteriophytochrome family that is devoid of hydrogen bonding to the carbonyl group of ring D of the biliverdin (BV) chromophore. The photodynamics of BV in SaBphP1 wild type and the single mutant T289H reintroducing hydrogen bonding to ring D show that the strength of this particular weak interaction determines excited-state lifetime, Lumi-R quantum yield, and spectral heterogeneity. In particular, excited-state decay is faster in the absence of hydrogen-bonding to ring D, with excited-state half-lives of 30 and 80 ps for wild type and the T289H mutant, respectively. Concomitantly, the Lumi-R quantum yield is two times higher in wild type as compared with the T289H mutant. Furthermore, the spectral heterogeneity in the wild type is significantly higher than that in the T289H mutant. By extending the observable time domain to 25 μs, we observe a new deactivation pathway from the Lumi-R intermediate in the 100 ns time domain that corresponds to a backflip of ring D to the original Pr 15Za isomeric state. (Chemical Equation Presented).

Original languageEnglish (US)
Pages (from-to)239-243
Number of pages5
JournalJournal of Physical Chemistry Letters
Volume6
Issue number2
DOIs
StatePublished - Jan 15 2015

ASJC Scopus subject areas

  • Materials Science(all)
  • Physical and Theoretical Chemistry

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    Mathes, T., Ravensbergen, J., Kloz, M., Gleichmann, T., Gallagher, K. D., Woitowich, N. C., St. Peter, R., Kovaleva, S. E., Stojković, E. A., & Kennis, J. T. M. (2015). Femto- to Microsecond Photodynamics of an Unusual Bacteriophytochrome. Journal of Physical Chemistry Letters, 6(2), 239-243. https://doi.org/10.1021/jz502408n