Protonation of the Biliverdin IXα Chromophore in the Red and Far-Red Photoactive States of Bacteriophytochrome
Modi, V., Donnini, S., Groenhof, G., & Morozov, D. (2019). Protonation of the Biliverdin IXα Chromophore in the Red and Far-Red Photoactive States of Bacteriophytochrome. Journal of Physical Chemistry B, 123(10), 2325-2334. https://doi.org/10.1021/acs.jpcb.9b01117
Published in
Journal of Physical Chemistry BDate
2019Copyright
© 2019 American Chemical Society.
The tetrapyrrole chromophore biliverdin IXα (BV) in the bacteriophytochrome from Deinococcus radiodurans (DrBphP) is usually assumed to be fully protonated, but this assumption has not been systematically validated by experiments or extensive computations. Here, we use force field molecular dynamics simulations and quantum mechanics/molecular mechanics calculations with density functional theory and XMCQDPT2 methods to investigate the effect of the five most probable protonation forms of BV on structural stability, binding pocket interactions, and absorption spectra in the two photochromic states of DrBphP. While agreement with X-ray structural data and measured UV/vis spectra suggest that in both states the protonated form of the chromophore dominates, we also find that a minor population with a deprotonated D-ring could contribute to the red-shifted tail in the absorption spectra.
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American Chemical SocietyISSN Search the Publication Forum
1520-6106Publication in research information system
https://converis.jyu.fi/converis/portal/detail/Publication/28922295
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Research Council of FinlandFunding program(s)
Postdoctoral Researcher, AoF; Others, AoFAdditional information about funding
This work was funded by the Academy of Finland (grant 304455 to G.G. and V.M., grant 285481 to D.M., and grant 266274 to S.D.).License
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