亲核水攻击不是光系统II中氧-氧键形成的可能机制。
Nucleophilic water attack is not a possible mechanism for O-O bond formation in photosystem II.
作者信息
Siegbahn Per E M
机构信息
Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, SE-106 91, Stockholm, Sweden
出版信息
Proc Natl Acad Sci U S A. 2017 May 9;114(19):4966-4968. doi: 10.1073/pnas.1617843114. Epub 2017 Apr 24.
Abstract
Two different types of mechanisms are at present suggested for the O-O bond-formation step in photosystem II. The first one is a coupling between an oxyl radical and a bridging oxo. The second one is a nucleophilic water attack on a terminal oxo (or oxyl) group. In the present short paper, the six most reasonable versions of the latter mechanism have been studied and compared with the oxo-oxyl mechanism. The barriers are found to be much too high for the water attack, and that mechanism can therefore safely be ruled out. The reason is that the protonated peroxide product is always very high in energy.
摘要
目前，关于光系统II中O-O键形成步骤提出了两种不同类型的机制。第一种是氧自由基与桥连氧之间的耦合。第二种是亲核水对末端氧（或氧基）基团的进攻。在本简短论文中，研究了后一种机制的六个最合理版本，并与氧-氧基机制进行了比较。发现水进攻的势垒过高，因此可以安全地排除该机制。原因是质子化过氧化物产物的能量总是非常高。
相似文献
1
Nucleophilic water attack is not a possible mechanism for O-O bond formation in photosystem II.
Proc Natl Acad Sci U S A. 2017 May 9;114(19):4966-4968. doi: 10.1073/pnas.1617843114. Epub 2017 Apr 24.
2
Water oxidation mechanism in photosystem II, including oxidations, proton release pathways, O-O bond formation and O2 release.
Biochim Biophys Acta. 2013 Aug-Sep;1827(8-9):1003-19. doi: 10.1016/j.bbabio.2012.10.006. Epub 2012 Oct 24.
3
Alternative mechanisms for O2 release and O-O bond formation in the oxygen evolving complex of photosystem II.
Phys Chem Chem Phys. 2015 May 14;17(18):12168-74. doi: 10.1039/c5cp00138b.
4
Redox-coupled substrate water reorganization in the active site of Photosystem II-The role of calcium in substrate water delivery.
Biochim Biophys Acta. 2016 Jun;1857(6):740-8. doi: 10.1016/j.bbabio.2016.01.015. Epub 2016 Jan 27.
5
Photosynthetic water oxidation: insights from manganese model chemistry.
Acc Chem Res. 2015 Mar 17;48(3):567-74. doi: 10.1021/ar5004175. Epub 2015 Mar 2.
6
Structures and energetics for O2 formation in photosystem II.
Acc Chem Res. 2009 Dec 21;42(12):1871-80. doi: 10.1021/ar900117k.
7
Nucleophilic attack of hydroxide on a Mn(V) oxo complex: a model of the O-O bond formation in the oxygen evolving complex of photosystem II.
J Am Chem Soc. 2009 Jul 1;131(25):8726-7. doi: 10.1021/ja901139r.
8
Photosynthesis. Electronic structure of the oxygen-evolving complex in photosystem II prior to O-O bond formation.
Science. 2014 Aug 15;345(6198):804-8. doi: 10.1126/science.1254910. Epub 2014 Aug 14.
9
Photosystem II like water oxidation mechanism in a bioinspired tetranuclear manganese complex.
Inorg Chem. 2015 Jan 5;54(1):342-51. doi: 10.1021/ic5024983. Epub 2014 Dec 8.
10
Quantum mechanics/molecular mechanics study of the catalytic cycle of water splitting in photosystem II.
J Am Chem Soc. 2008 Mar 19;130(11):3428-42. doi: 10.1021/ja076130q. Epub 2008 Feb 22.
引用本文的文献
1
The Low Oxidation State Paradigm is More Consistent with XFEL Observations of the S₃ → [S₄] → S₀ Transition in Photosystem II.
Chemistry. 2025 Jul 8;31(38):e202501010. doi: 10.1002/chem.202501010. Epub 2025 Jun 18.
2
High-Spin Manganese(V) in an Active Center Analogue of the Oxygen-Evolving Complex.
J Am Chem Soc. 2025 Mar 5;147(9):7336-7344. doi: 10.1021/jacs.4c14543. Epub 2025 Feb 19.
3
Kinetics of reformation of the S state capable of progressing to the S state after the O release by photosystem II.
Photosynth Res. 2025 Jan 15;163(1):5. doi: 10.1007/s11120-024-01131-4.
4
Mechanism of proton release during water oxidation in Photosystem II.
Proc Natl Acad Sci U S A. 2024 Dec 24;121(52):e2413396121. doi: 10.1073/pnas.2413396121. Epub 2024 Dec 19.
5
The Effect of Removal of External Proteins PsbO, PsbP and PsbQ on Flash-Induced Molecular Oxygen Evolution and Its Biphasicity in Tobacco PSII.
Curr Issues Mol Biol. 2024 Jul 8;46(7):7187-7218. doi: 10.3390/cimb46070428.
6
Evolution in the Design of Water Oxidation Catalysts with Transition-Metals: A Perspective on Biological, Molecular, Supramolecular, and Hybrid Approaches.
ACS Omega. 2024 Feb 23;9(9):9886-9920. doi: 10.1021/acsomega.3c07847. eCollection 2024 Mar 5.
7
Insights into PSII's SY State: An Electronic and Magnetic Analysis.
J Phys Chem Lett. 2024 Jan 18;15(2):499-506. doi: 10.1021/acs.jpclett.3c03026. Epub 2024 Jan 8.
8
Theoretical elucidation of the structure, bonding, and reactivity of the CaMnO clusters in the whole Kok cycle for water oxidation embedded in the oxygen evolving center of photosystem II. New molecular and quantum insights into the mechanism of the O-O bond formation.
Photosynth Res. 2024 Dec;162(2-3):291-330. doi: 10.1007/s11120-023-01053-7. Epub 2023 Nov 9.
9
The electron-proton bottleneck of photosynthetic oxygen evolution.
Nature. 2023 May;617(7961):623-628. doi: 10.1038/s41586-023-06008-5. Epub 2023 May 3.
10
Solar energy conversion by photosystem II: principles and structures.
Photosynth Res. 2023 Jun;156(3):279-307. doi: 10.1007/s11120-022-00991-y. Epub 2023 Feb 24.
本文引用的文献
1
Recent developments in biological water oxidation.
Curr Opin Chem Biol. 2016 Apr;31:113-9. doi: 10.1016/j.cbpa.2016.02.007. Epub 2016 Mar 17.
2
Chemical Equilibrium Models for the S3 State of the Oxygen-Evolving Complex of Photosystem II.
Inorg Chem. 2016 Jan 19;55(2):502-11. doi: 10.1021/acs.inorgchem.5b02471. Epub 2015 Dec 30.
3
Alternative mechanisms for O2 release and O-O bond formation in the oxygen evolving complex of photosystem II.
Phys Chem Chem Phys. 2015 May 14;17(18):12168-74. doi: 10.1039/c5cp00138b.
4
Optimizing the oxygen evolution reaction for electrochemical water oxidation by tuning solvent properties.
Nanoscale. 2015 Mar 14;7(10):4514-21. doi: 10.1039/c4nr07277d.
5
Native structure of photosystem II at 1.95 Å resolution viewed by femtosecond X-ray pulses.
Nature. 2015 Jan 1;517(7532):99-103. doi: 10.1038/nature13991. Epub 2014 Nov 26.
6
Photosynthesis. Electronic structure of the oxygen-evolving complex in photosystem II prior to O-O bond formation.
Science. 2014 Aug 15;345(6198):804-8. doi: 10.1126/science.1254910. Epub 2014 Aug 14.
7
Quantum chemical studies of mechanisms for metalloenzymes.
Chem Rev. 2014 Apr 9;114(7):3601-58. doi: 10.1021/cr400388t. Epub 2014 Jan 13.
8
Reflections on substrate water and dioxygen formation.
Biochim Biophys Acta. 2013 Aug-Sep;1827(8-9):1020-30. doi: 10.1016/j.bbabio.2013.01.013. Epub 2013 Feb 1.
9
Water oxidation mechanism in photosystem II, including oxidations, proton release pathways, O-O bond formation and O2 release.
Biochim Biophys Acta. 2013 Aug-Sep;1827(8-9):1003-19. doi: 10.1016/j.bbabio.2012.10.006. Epub 2012 Oct 24.
10
Detection of the water-binding sites of the oxygen-evolving complex of Photosystem II using W-band 17O electron-electron double resonance-detected NMR spectroscopy.
J Am Chem Soc. 2012 Oct 10;134(40):16619-34. doi: 10.1021/ja3053267. Epub 2012 Sep 27.
Zotero 插件