Structural Factors That Alter the Redox Potential of Quinones in Cyanobacterial and Plant Photosystem I

Biochemistry
Keisuke Kawashima, Hiroshi Ishikita

Abstract

Using the cyanobacterial and plant photosystem I (PSI) crystal structures and by considering the protonation states of all titratable residues, redox potentials (Em) of the two phylloquinones-A1A and A1B-were calculated. The calculated Em values were Em(A1A) = -773 mV and Em(A1B) = -818 mV for the plant PSI structure and Em(A1A) = -612 mV and Em(A1B) = -719 mV for the cyanobacterial PSI structure. Our analysis of the PSI crystal structures suggested that the side-chain orientations of Lys-B542 and Gln-B678 in the cyanobacterial crystal structure differ from these side-chain orientations in the plant crystal structure. Quantum mechanical/molecular mechanical calculations indicated that the geometry of the cyanobacterial PSI crystal structure was best described as the conformation where Asp-B575 is protonated and A1A is reduced to A1A(•-), which might represent the high-potential A1A form ( Rutherford, A. W., Osyczka, A., Rappaport, F. ( 2012 ) FEBS Lett. 586 , 603 - 616 ). Reorienting the Lys-B542 and Gln-B678 side-chains and rearranging the H-bond pattern of the water cluster near Asp-B575 lowered the Em to Em(A1A) = -718 mV and Em(A1B) = -795 mV. It seems possible that PSI has two conformations: the high-potential A1A form and...Continue Reading

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Citations

Mar 9, 2019·Physiologia Plantarum·Stefano SantabarbaraGary Hastings
May 22, 2018·Chemical Science·Keisuke Kawashima, Hiroshi Ishikita
Jul 18, 2019·Frontiers in Plant Science·Stefano Santabarbara, Anna Paola Casazza
May 25, 2020·Photosynthesis Research·Neva AgarwalaGary Hastings
Jan 2, 2021·Biochimica Et Biophysica Acta. Bioenergetics·Leyla Rohani, Gary Hastings
Jul 16, 2019·Biochimica Et Biophysica Acta. Bioenergetics·Leyla RohaniGary Hastings
Oct 19, 2020·Biochimica Et Biophysica Acta. Bioenergetics·Hiroshi KurodaHiroshi Ishikita
Aug 3, 2021·The Journal of Physical Chemistry Letters·Tomoki KandaHiroshi Ishikita

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