Structural and dynamic insights into Mn4Ca cluster-depleted Photosystem II

Author(s):  
Daniele Narzi ◽  
Leonardo Guidoni

In the first steps of natural oxygenic photosynthesis, Sun light is used to oxidize water molecules into protons, electrons and molecular oxygen. This reaction takes place on the Mn$_4$Ca cluster...

2020 ◽  
Vol 22 (28) ◽  
pp. 15831-15841
Author(s):  
Naoki Sakashita ◽  
Hiroshi Ishikita ◽  
Keisuke Saito

In the channel of photosystem II, rigidly hydrogen-bonded water molecules facilitate the Grotthuss-like proton transfer, whereas flexible water molecules prevent proton transfer in the channel of aquaporin.


2020 ◽  
Vol 117 (23) ◽  
pp. 12624-12635 ◽  
Author(s):  
Mohamed Ibrahim ◽  
Thomas Fransson ◽  
Ruchira Chatterjee ◽  
Mun Hon Cheah ◽  
Rana Hussein ◽  
...  

In oxygenic photosynthesis, light-driven oxidation of water to molecular oxygen is carried out by the oxygen-evolving complex (OEC) in photosystem II (PS II). Recently, we reported the room-temperature structures of PS II in the four (semi)stable S-states, S1, S2, S3, and S0, showing that a water molecule is inserted during the S2→ S3transition, as a new bridging O(H)-ligand between Mn1 and Ca. To understand the sequence of events leading to the formation of this last stable intermediate state before O2formation, we recorded diffraction and Mn X-ray emission spectroscopy (XES) data at several time points during the S2→ S3transition. At the electron acceptor site, changes due to the two-electron redox chemistry at the quinones, QAand QB, are observed. At the donor site, tyrosine YZand His190 H-bonded to it move by 50 µs after the second flash, and Glu189 moves away from Ca. This is followed by Mn1 and Mn4 moving apart, and the insertion of OX(H) at the open coordination site of Mn1. This water, possibly a ligand of Ca, could be supplied via a “water wheel”-like arrangement of five waters next to the OEC that is connected by a large channel to the bulk solvent. XES spectra show that Mn oxidation (τ of ∼350 µs) during the S2→ S3transition mirrors the appearance of OXelectron density. This indicates that the oxidation state change and the insertion of water as a bridging atom between Mn1 and Ca are highly correlated.


Biochemistry ◽  
2020 ◽  
Vol 59 (35) ◽  
pp. 3216-3224 ◽  
Author(s):  
Keisuke Saito ◽  
Manoj Mandal ◽  
Hiroshi Ishikita

2008 ◽  
Vol 105 (46) ◽  
pp. 17632-17635 ◽  
Author(s):  
Javier J. Concepcion ◽  
Jonah W. Jurss ◽  
Joseph L. Templeton ◽  
Thomas J. Meyer

Light-driven water oxidation occurs in oxygenic photosynthesis in photosystem II and provides redox equivalents directed to photosystem I, in which carbon dioxide is reduced. Water oxidation is also essential in artificial photosynthesis and solar fuel-forming reactions, such as water splitting into hydrogen and oxygen (2 H2O + 4 hν → O2 + 2 H2) or water reduction of CO2 to methanol (2 H2O + CO2 + 6 hν → CH3OH + 3/2 O2), or hydrocarbons, which could provide clean, renewable energy. The “blue ruthenium dimer,” cis,cis-[(bpy)2(H2O)RuIIIORuIII(OH2)(bpy)2]4+, was the first well characterized molecule to catalyze water oxidation. On the basis of recent insight into the mechanism, we have devised a strategy for enhancing catalytic rates by using kinetically facile electron-transfer mediators. Rate enhancements by factors of up to ≈30 have been obtained, and preliminary electrochemical experiments have demonstrated that mediator-assisted electrocatalytic water oxidation is also attainable.


Biochemistry ◽  
2018 ◽  
Vol 57 (29) ◽  
pp. 4299-4311 ◽  
Author(s):  
Christopher J. Kim ◽  
Han Bao ◽  
Robert L. Burnap ◽  
Richard J. Debus

Biochemistry ◽  
2007 ◽  
Vol 46 (49) ◽  
pp. 14245-14249 ◽  
Author(s):  
Ryouta Takahashi ◽  
Miwa Sugiura ◽  
Takumi Noguchi

2017 ◽  
Vol 60 (3) ◽  
pp. 485-493
Author(s):  
R. R. Valiev ◽  
B. F. Minaev

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