Active and silent chromophore isoforms for phytochrome Pr photoisomerization: An alternative evolutionary strategy to optimize photoreaction quantum yields

Structural Dynamics
Yang YangKarsten Heyne

Abstract

Photoisomerization of a protein bound chromophore is the basis of light sensing of many photoreceptors. We tracked Z-to-E photoisomerization of Cph1 phytochrome chromophore PCB in the Pr form in real-time. Two different phycocyanobilin (PCB) ground state geometries with different ring D orientations have been identified. The pre-twisted and hydrogen bonded PCB(a) geometry exhibits a time constant of 30 ps and a quantum yield of photoproduct formation of 29%, about six times slower and ten times higher than that for the non-hydrogen bonded PCB(b) geometry. This new mechanism of pre-twisting the chromophore by protein-cofactor interaction optimizes yields of slow photoreactions and provides a scaffold for photoreceptor engineering.

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Citations

May 7, 2019·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Christian Wiebeler, Igor Schapiro
Jun 28, 2020·Proceedings of the National Academy of Sciences of the United States of America·Chavdar SlavovJosef Wachtveitl
Apr 15, 2016·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Patrick SingerRolf Diller
Feb 28, 2014·Photochemistry and Photobiology·Vitaly SineshchekovJon Hughes
May 14, 2017·Photochemistry and Photobiology·Till StensitzkiKarsten Heyne
Jan 19, 2016·Frontiers in Molecular Biosciences·Janne A IhalainenHeli Lehtivuori
May 14, 2017·Photochemistry and Photobiology·Aba LosiKai-Hong Zhao
Apr 21, 2021·Physical Chemistry Chemical Physics : PCCP·Aditya G RaoIgor Schapiro
Dec 15, 2016·The Journal of Physical Chemistry. B·Francisco Velazquez EscobarMaria Andrea Mroginski
Aug 12, 2015·The Journal of Physical Chemistry Letters·Tilo MathesJohn T M Kennis
Jun 7, 2018·The Journal of Physical Chemistry Letters·Julia S KirpichDelmar S Larsen
Jul 3, 2020·The Journal of Physical Chemistry Letters·Dihao WangDongping Zhong

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Methods Mentioned

BETA
nuclear magnetic resonance
NMR

Software Mentioned

ExSeAn

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